A waterproofing membrane

Abstract

The present application provides a kind of waterproofing membrane, including waterproof layer and the modification layer being arranged in at least one surface of the waterproof layer;The modification layer includes the functional polymer with surface tension of 30-50 dyn / cm, and the functional polymer is selected from acrylate polymer and / or polyurethane polymer.The waterproofing membrane of the present application is set by modification layer, so that the waterproofing membrane shows the bonding strength comparable to traditional self-adhesive type polymer waterproofing membrane containing adhesive layer, and does not need to carry out subsequent operations such as gluing and coating isolation material or isolation film, and is more suitable for application in roll-coating composite, pre-paving, wet paving and other various construction scenarios.

Description

Technical Field

[0001] This invention belongs to the field of waterproofing and relates to a waterproof membrane. Background Technology

[0002] Traditional pre-applied and self-adhesive waterproof membranes are mainly used in building walls, roofs, floors, and tunnels to resist external rainwater and groundwater seepage. They are flexible building materials that can be rolled up and serve as a leak-proof connection between the foundation and the building, acting as the first line of defense for waterproofing the entire project and playing a crucial role in the overall project.

[0003] Currently, SBS bitumen waterproof membrane is the most widely used type. It consists of a base made of materials such as polyester felt, fiberglass felt, or fiberglass-reinforced polyester felt, an asphalt layer impregnated on the surface of the base, and isolation material layers on the upper and lower surfaces. Bitumen-based self-adhesive waterproof membranes have a lower cost, but their mechanical properties, temperature resistance, and aging resistance are all poor, and they are prone to generating harmful gases during the production process.

[0004] In recent years, high-performance, energy-saving, and environmentally friendly polymer waterproof membranes have seen wider development. Self-adhesive polymer waterproof membranes typically consist of polymer sheets (such as PVC, PE, EVA, ECB, TPO, TPR, etc.), self-adhesive materials, and release agents. Fabric reinforcement can be added to the polymer sheets as needed. Since the sheets themselves are not adhesive to various architectural coatings or adhesives, in waterproofing applications, the membrane is primarily bonded to concrete or other building structures using adhesives.

[0005] However, existing self-adhesive polymer rolls still have several drawbacks. On the one hand, there is a risk of separation between the adhesive layer and the polymer sheet layer. Once both are damaged, the waterproofing reliability of the project cannot be guaranteed. On the other hand, to prevent sticking during pre-laying, an anti-stick coating or cement mortar needs to be applied to the adhesive layer surface, which increases the complexity of the production process and the construction process. Furthermore, the adhesive layer usually requires solvent-free conditions to bond firmly, which makes it difficult to apply in wet-laying processes. It is necessary to wait for the coating to dry before pasting, thus limiting the application scenarios of waterproof rolls. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a waterproof membrane that, through the addition of a modified layer, exhibits bonding strength comparable to traditional self-adhesive polymer waterproof membranes containing adhesive layers. Furthermore, it eliminates the need for subsequent operations such as applying adhesive or sealing materials or films, making it more suitable for various construction scenarios including roll-coating, pre-laying, and wet-laying.

[0007] The present invention provides a waterproof membrane, comprising a waterproof layer and a modified layer disposed on at least one surface of the waterproof layer;

[0008] The modified layer comprises a functional polymer with a surface tension of 30 to 50 dyn / cm, wherein the functional polymer is selected from acrylate polymers and / or polyurethane polymers.

[0009] Figure 1 This is a schematic diagram of a waterproof membrane structure according to an embodiment of the present invention. Figure 2 This is a schematic diagram of a waterproof membrane structure according to another embodiment of the present invention. Please refer to... Figure 1 and Figure 2 The waterproof membrane of the present invention includes a waterproof layer 11 and a modified layer 12 disposed on the surface of the waterproof layer. The modified layer 12 may be disposed on only one surface of the waterproof layer 11 or on both surfaces of the waterproof layer 11. Specifically, the modified layer may be disposed on one or both surfaces of the waterproof layer 11 depending on the actual application scenario.

[0010] The waterproof membrane provided by the present invention includes a waterproof layer and a modified layer disposed on one surface of the waterproof layer. In order to obtain good waterproof performance, conventional waterproof layers usually require the selection of polymers with low surface energy, high crystallinity and low polarity as waterproof materials.

[0011] However, low surface energy makes it difficult for liquid coatings or adhesives to penetrate its surface, thus preventing subsequent adhesion; high crystallinity makes it difficult for the waterproof layer to swell and dissolve, and the dense arrangement of surface molecules makes it difficult to form an effective bond with coatings and building materials; low polarity molecular surfaces can only form weak dispersion forces, lacking orientation and induction forces, resulting in poor adhesion performance.

[0012] These characteristics make it difficult for the waterproof layer to bond effectively with waterproof coatings, concrete, cement, and other components. Traditional self-adhesive polymer waterproof membranes usually have a hot melt adhesive or butyl rubber adhesive layer added to their surface. However, the high viscosity of the adhesive layer itself means that a protective layer or release film is required for applications such as pre-laying and roll coating. Furthermore, the adhesive layer must be used in a dry environment, making it unsuitable for wet-laying applications.

[0013] This invention uses a non-adhesive modified layer instead of an adhesive layer. The functional polymers in the modified layer are selected from acrylate polymers and / or polyurethane polymers, which have high polarity and suitable surface tension, and can effectively bond to coatings and waterproofed structures without the need for an adhesive layer.

[0014] Therefore, the modified layer of the present invention can serve as a connecting bridge between the waterproof layer and the waterproof coating or other waterproof structures. It not only has good adhesion strength with the waterproof layer, but also has good adhesion strength with conventional waterproof coatings (such as water-based acrylic coatings, polyurea coatings, and asphalt coatings) and commonly used building materials (cement, epoxy mortar, and concrete).

[0015] This invention enables waterproof membranes to exhibit bonding strength comparable to traditional self-adhesive polymer waterproof membranes with adhesive layers through the setting of modified layers, without the need for subsequent operations such as applying adhesive or applying release materials or release films. It is more suitable for various construction scenarios such as roll coating, pre-laying, and wet laying.

[0016] In a preferred embodiment, the acrylate polymer is selected from acrylate block copolymers with alternating soft and hard segments;

[0017] The glass transition temperature of the soft segment is -100℃ to -30℃; the glass transition temperature of the hard segment is 40℃ to 120℃.

[0018] Studies have shown that the aforementioned soft-hard bonded acrylate block copolymers have good viscoelasticity, which is beneficial for enhancing the adhesion strength between the modified layer and coatings and building materials.

[0019] To further improve the viscoelastic properties of acrylate block copolymers, the inventors conducted optimization experiments on the content of soft and hard segments and the specific structural unit types of soft and hard segments. The results showed that, based on the relative molecular mass of the acrylate block copolymers, when the mass content of the soft segments is 50% to 90% and the mass content of the hard segments is 10% to 50%, the viscoelasticity can meet the product requirements.

[0020] Furthermore, the soft segment is selected from polybutyl acrylate or a copolymer of polybutyl acrylate and 2-ethyl acrylate, and the hard segment is selected from polymethacrylate.

[0021] The present invention does not specifically limit the source of the above-mentioned acrylate block copolymers, which can be prepared by the manufacturer or obtained commercially. For example, commercially available acrylate block copolymers can be selected from Kuraray LK9211, LK9243, LA2270, LA2330, etc.

[0022] In a preferred embodiment, the acrylate polymer is selected from one or more of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-acrylate-maleic anhydride terpolymer, and organosilicon acrylic resin. The ethylene-acrylate-glycidyl methacrylate terpolymer may be selected from... AX8900 and ethylene-acrylate-maleic anhydride terpolymer are optional. 4700 3410, etc., ethylene-acrylate-maleic anhydride or glycidyl methacrylate terpolymers can be selected from... AX8700, silicone acrylic resin options include Zixin Yue KR9706, etc.

[0023] In a preferred embodiment, the polyurethane polymer is selected from polyurethane block copolymers comprising a first block and a second block;

[0024] The first block is selected from polyurethane, and the second block is selected from silicone and / or hydrogenated polystyrene copolymer.

[0025] The first block provides high polarity, while the second block provides high polarity to improve water resistance and chemical stability, thereby giving the polyurethane block copolymer good adhesion and strength.

[0026] In one specific embodiment, the hydrogenated polystyrene copolymer is a copolymer of hydrogenated polystyrene and a polyolefin, specifically, the polyolefin may be one or more of polyethylene, polypropylene, polybutadiene, and polyisoprene.

[0027] Furthermore, the mass content of the first block is 50% to 90%, and the mass content of the second block is 10% to 50%.

[0028] The polyurethane block copolymers that meet the above characteristics can be prepared in-house or commercially available. Among them, the commercially available polyurethane block copolymers can be Kuraray TU-S5265 or Meirui New Materials V165.

[0029] In another preferred embodiment, the polyurethane polymer is selected from thermoplastic polyurethane elastomers. Thermoplastic polyurethane elastomers have good wettability, and their -NCO groups are very reactive and can react with alcohols, water, organic amines, etc., which is beneficial for forming good adhesive strength with coatings, etc.

[0030] The aforementioned polyurethane elastomer can be selected from Pearlcoat. TM DIPP 119, Pearlbond TM TPU 500, Pearlbond TM TPU 580, etc.

[0031] Furthermore, the functional polymer has a Shore hardness of 20A to 60D. Using a functional polymer with such hardness can enable the modified layer to have good elasticity and toughness.

[0032] Furthermore, the melt flow index of the functional polymer is 0.5–100 g / 10 min. Melt flow index, also known as melt index, is a numerical value representing the fluidity of a polymer during processing. Selecting a functional polymer with the above melt flow index is beneficial for preparing modified and waterproof layers through co-extrusion processing.

[0033] Furthermore, the crystallinity of the functional polymer is 0-30%. Functional polymers with the above crystallinity exhibit low crystallinity, which is beneficial for achieving higher adhesive strength in the modified layer.

[0034] Furthermore, the glass transition temperature of the functional polymer is -60 to 30°C, more preferably -50 to -10°C. Using a functional polymer with the above glass transition temperature can meet the low-temperature application performance requirements of polymer roll materials, ensuring that the modified layer maintains good elasticity from low temperature to room temperature.

[0035] Furthermore, the melting temperature of the functional polymer is 40–180°C, more preferably 50–110°C. Selecting a functional polymer with a melting temperature within this range is beneficial for the extrusion casting of the modified layer.

[0036] In one specific embodiment, when the functional polymer accounts for 30% to 80% of the mass content of the modified layer, it is beneficial to enable the modified layer to have a strong adhesive strength with the coating and building materials.

[0037] In one specific embodiment, the modified layer further includes a first inorganic filler, which is a modified inorganic filler with surface grafting and / or coupling of organic matter.

[0038] Most inorganic fillers have hydrophilic and polar surfaces, which easily adsorb moisture and can improve the adhesion between the modified layer and water-based coatings or water-containing building materials. However, the functional polymers in waterproof membranes are hydrophobic and have poor compatibility with conventional inorganic fillers. By using organic materials to graft and / or couple the surface of inorganic fillers, it is beneficial to improve the compatibility between inorganic fillers and functional polymers in the modified layer.

[0039] Furthermore, the oil absorption value of the first inorganic filler is 10–60 mL / 100 g, preferably 20–40 mL / 100 g. The oil absorption value, also known as the resin adsorption capacity, is a parameter used to express the amount of resin absorbed by the filler. Within the above oil absorption value range, it is beneficial for the first inorganic filler to have better compatibility with the functional polymer.

[0040] In one specific embodiment, the organic compound is selected from one or more of polyacrylic acid and its copolymers, polyvinyl alcohol, polymaleic acid, organosilicon, epoxy resin, aminosilane, epoxysilane, and methylpropyloxysilane.

[0041] In one specific embodiment, the first inorganic filler is selected from one or more of the following: organically modified calcium carbonate, silica, wollastonite, kaolin, montmorillonite, spherical clay, magnesia, and diatomaceous earth.

[0042] In one specific embodiment, the particle size of the first inorganic filler is 0.1–150 μm, preferably 0.1–1 μm. Setting the particle size of the first inorganic filler within the above range is beneficial to the dispersion and stability of the filler, and also enables the modified layer to have good mechanical properties.

[0043] In one specific embodiment, the first inorganic filler accounts for 10% to 50% of the mass content of the modified layer. For example, the mass content of the first inorganic filler in the modified layer can be 10%, 20%, 30%, 40%, 50%, or any two of these values.

[0044] In one specific embodiment, the modified layer further includes a second inorganic filler, which is selected from one or more of calcium carbonate, silicon dioxide, quartz, wollastonite, quartzite, feldspar, kaolin, titanium dioxide, magnesium hydroxide, alumina, spherical clay, bentonite, cement, magnesia, and diatomaceous earth.

[0045] In a preferred embodiment, the modified layer further includes a compatibilizer selected from one or more of maleic anhydride graft copolymers, glycidyl methacrylate graft polymers, polystyrene block polymers, chlorinated polyethylene, tackifying resins, ethylene-vinyl acetate copolymers, and ethylene-acrylate copolymers. The addition of the compatibilizer increases the compatibility between the highly polar functional polymer and the less polar waterproof polymer in the waterproof layer, resulting in a tight bond between the waterproof layer and the modified layer.

[0046] Furthermore, the compatibilizer accounts for 5% to 50% of the mass content of the modified layer. For example, the compatibilizer accounts for any two values ​​of 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or more of the mass content of the modified layer.

[0047] In one specific embodiment, the waterproof layer comprises a hydrophobic thermoplastic resin. The hydrophobic thermoplastic resin not only enables the waterproof membrane to possess good waterproof performance, but also ensures good adhesion between the waterproof layer and the modified layer, preventing the modified layer from detaching from the waterproof layer.

[0048] This invention does not specifically limit the hydrophobic thermoplastic resin, which can be selected from hydrophobic thermoplastic resins commonly used in the art, including but not limited to one or more of polyethylene, polypropylene, polyvinyl chloride, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polyolefin thermoplastic elastomer, styrene thermoplastic elastomer, and polyurethane thermoplastic elastomer.

[0049] Furthermore, in addition to hydrophobic thermoplastic resin, the waterproof layer of the present invention may also include fillers, antioxidants, lubricants and other components.

[0050] The present invention does not impose any particular limitation on the thickness of the waterproof layer and the thickness of the modified layer. When the thickness is too large, the waterproof performance will not be further increased. When the thickness is too small, it is difficult to guarantee the mechanical strength and waterproof performance of the waterproof membrane. Preferably, the thickness of the waterproof layer is 500-2000 μm; and / or the thickness of the modified layer is 50-500 μm.

[0051] In one specific embodiment, the modified layer further includes a processing aid selected from one or more of antioxidants, heat stabilizers, foaming agents, coupling agents, lubricants, slip agents, anti-sticking agents, or toughening agents. The addition of the processing aid can further improve the processing performance of the waterproof membrane.

[0052] Furthermore, the mass content of processing aids in the modified layer is 0.1% to 5%.

[0053] This invention does not specifically limit the preparation method of the waterproof membrane, which can be prepared using methods conventionally used in the art for preparing multilayer polymer materials. For example, the raw materials for the waterproof layer and the modified layer can be obtained by co-extrusion casting / calendering.

[0054] When the modified layer includes a first inorganic filler and / or a second inorganic filler, since it has a powder structure, in order to make it better for co-extrusion processing, the raw material of the modified layer can be granulated first, so that it can be better co-extruded in granular form.

[0055] Furthermore, in order to ensure the stability of the co-extrusion process of the modified layer and the waterproof layer, the melt index of the modified layer and the waterproof layer can be controlled between 1.0 and 6.0 g / 10 min, and the difference between the melt indexes of the two can be within 2 g / 10 min.

[0056] The implementation of this invention has at least the following beneficial effects:

[0057] The waterproof membrane of the present invention includes a waterproof layer and a modified layer disposed on at least one surface of the waterproof layer. The present invention enables the waterproof membrane to exhibit bonding strength comparable to that of traditional self-adhesive polymer waterproof membranes containing adhesive layers through the provision of the modified layer, and eliminates the need for subsequent operations such as applying adhesive or applying release materials or release films, making it more suitable for various construction scenarios such as roll coating, pre-laying, and wet laying. Attached Figure Description

[0058] Figure 1 This is a schematic diagram of a waterproof membrane structure according to an embodiment of the present invention;

[0059] Figure 2 This is a schematic diagram of a waterproof membrane structure according to another embodiment of the present invention.

[0060] Explanation of reference numerals in the attached figures:

[0061] 11-Waterproof layer; 12-Modified layer. Detailed Implementation

[0062] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0063] The waterproof membrane provided by the present invention will be described in detail below with reference to specific embodiments.

[0064] In the following embodiments, unless otherwise specified, all raw materials can be obtained by commercial purchase or conventional methods. Experimental methods without specific conditions shall be performed in accordance with conventional methods and conditions in the art, or according to the product instructions.

[0065] Example 1

[0066] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0067] 1. Functional polymer acrylate block copolymer (LK9243, KURARAY CO.,LTD), compatibilizer C9 petroleum resin, inorganic filler calcium carbonate (CARB-5JI, Omia), and second inorganic filler silica (… 200 (Degussa) and anti-sticking talc powder (800 mesh, Zhanteng Minerals) were added to a kneader at a mass ratio of 64:6:18:10:2 and stirred at high speed for 3-10 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃, and 170℃ respectively to obtain modified layer granules.

[0068] 2. The waterproof layer mixture is obtained by mixing ethylene-vinyl acetate copolymer (EVA28005, LG Chem), ethylene-vinyl acetate copolymer (EVA2005C0, Saudi National Petrochemical), and low-density polyethylene LDPE (DFDA7042, Guangzhou Petrochemical) in a mass ratio of 15:55:30.

[0069] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0070] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0071] Example 2

[0072] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0073] 1. Functional polymer acrylate block copolymer (LK9243, KURARAY CO.,LTD), compatibilizer C9 petroleum resin, and second inorganic filler silica ( 200 (Degussa) and anti-sticking talc powder (800 mesh, Zhanteng Minerals) were added to a kneader at a mass ratio of 64:6:28:2 and stirred at high speed for 3-10 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃ and 170℃ respectively to obtain modified layer granules.

[0074] 2. EVA (28005, LG Chem), EVA (2005CO, Saudi National Petrochemical), and LDPE (DFDA7042, Guangzhou Petrochemical) are mixed in a mass ratio of 15:55:30 to obtain the waterproof layer mixture.

[0075] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0076] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0077] Example 3

[0078] This embodiment provides a waterproof membrane, the structure and preparation method of which are basically the same as those in Embodiment 1, except that the thickness of the modified layer is set to 100 μm.

[0079] Example 4

[0080] This embodiment provides a waterproof membrane, the structure and preparation method of which are basically the same as those in Example 1. The difference is that the functional polymer is replaced by an acrylate block copolymer (LK9243, KURARAY CO.,LTD) containing polybutyl acrylate blocks with acrylate block copolymer (LA2330, KURARAY CO.,LTD) containing poly(n-butyl acrylate / 2-ethylhexyl acrylate) blocks.

[0081] Example 5

[0082] This embodiment provides a waterproof membrane, the structure and preparation method of which are the same as those in Example 4. The difference lies in the addition of functional polymer acrylate block copolymer (LA2330, KURARAY CO.,LTD), compatibilizer ethylene-vinyl acetate copolymer (EVA28005, LG Chem), compatibilizer C9 petroleum resin, inorganic filler calcium carbonate (CARB-5JI, Omia), and second inorganic filler silica (…). Add 200 (Degussa) and anti-sticking agent talc powder (800 mesh, Zhanteng Minerals) in a mass ratio of 20:55:8:5:10:2 to a kneader and mix at high speed for 3-10 minutes. Then, granulate the mixed material through a twin-screw extruder. The extruder is heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃, and 170℃ respectively to obtain modified layer granules.

[0083] Example 6

[0084] This embodiment provides a waterproof membrane, the preparation method of which includes the following steps:

[0085] 1. Functional polymer acrylate block copolymer (LA2330, KURARAY CO.,LTD), EVA (28005, LG Chem), compatibilizer C9 petroleum resin, and inorganic filler montmorillonite (D 50 =25um, Jiheng Mining), the second inorganic filler silica ( 200 (Degussa) and foaming agent (SAFOAM FPE-20, Reedy International Corporation) were added to a kneader at a mass ratio of 50:10:6:5:28:1 and stirred at high speed for 3-10 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃, and 170℃ respectively to obtain modified layer granules.

[0086] 2. EVA (28005, LG Chem), EVA (2005CO, Saudi National Petrochemical), POE (Engage8480, Dow Chemical), and LDPE (DFDA7042, Guangzhou Petrochemical) are mixed in a mass ratio of 15:35:20:30 to obtain the waterproof layer mixture.

[0087] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0088] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0089] Example 7

[0090] This embodiment provides a waterproof membrane, the preparation method of which includes the following steps:

[0091] 1. Functional polymer acrylate block copolymer (LA2330, KURARAY CO.,LTD), EVA (28005, LG Chem), compatibilizer C9 petroleum resin, and inorganic filler montmorillonite (D 50 =25um, Jiheng Mining), second inorganic filler wollastonite (BK930, Sepson), foaming agent (SAFOAM FPE-20, Reedy International Corporation) were added to a kneader at a mass ratio of 56:8:6:5:25:0.5 and stirred at high speed for 3-10 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃ and 170℃ respectively to obtain modified layer granules.

[0092] 2. EVA (28005, LG Chem), EVA (2005CO, Saudi National Petrochemical), POE (Engage8480, Dow Chemical), and LDPE (DFDA7042, Guangzhou Petrochemical) are mixed in a mass ratio of 15:35:20:30 to obtain the waterproof layer mixture.

[0093] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0094] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0095] Example 8

[0096] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0097] 1. The functional polymer ethylene-acrylate-maleic anhydride terpolymer ( 3410, SK), compatibilizer ethylene-vinyl acetate copolymer (EVA18J3, Yanshan Petrochemical), first inorganic filler modified silica, second inorganic filler cement, foaming agent foaming masterbatch ( FPE-20 was added to a kneader at a mass ratio of 50:10:20:19:1 and stirred at high speed for 3-10 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃, and 170℃ respectively to obtain modified layer granules.

[0098] 2. The waterproof layer mixture is obtained by mixing ethylene-vinyl acetate copolymer (EVA18J3, Yanshan Petrochemical), ethylene-vinyl acetate copolymer (2005CO, Saudi National Petrochemical), and titanium dioxide in a mass ratio of 15:84:1.

[0099] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0100] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0101] Example 9

[0102] This embodiment provides a waterproof membrane, the structure and preparation method of which are basically the same as those in Embodiment 6, except that the thickness of the modified layer is set to 80 μm and the thickness of the waterproof layer is set to 1020 μm.

[0103] Example 10

[0104] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0105] 1. Add acetic acid to water to adjust its pH to 3.0–4.5 to obtain acidified water; add 0.2% wt aminosilane to the acidified water and stir until fully dissolved to obtain a modified solution; spray the modified solution onto pre-dried heavy calcium carbonate powder (D 50 =5μm) surface is mixed and stirred at 90-100℃ for more than 15 minutes to obtain D 50 Modified calcium carbonate with a particle size of 6 μm.

[0106] 2. Functional polymer ethylene-acrylate elastomer ( AEM G), compatibilizer ethylene-vinyl acetate copolymer (EVM50M27, Yunnan Zhengbang), first inorganic filler modified calcium carbonate, and second inorganic filler calcium carbonate (CARB-5JI, Omia) were added to a kneader at a mass ratio of 65:5:25:5 and stirred at high speed for 5 minutes. The mixed material was then granulated by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 160℃, 170℃, 170℃, 170℃, and 170℃ respectively to obtain modified layer granules.

[0107] 3. The waterproof layer mixture is obtained by mixing ethylene-vinyl acetate copolymer (EVA28005, LG Chem), ethylene-vinyl acetate copolymer (EVA2005C0, Saudi National Petrochemical), and maleic anhydride grafted polyethylene (PE-g-MAH4700, SK Chem) in a mass ratio of 30:40:20.

[0108] 4. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0109] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0110] Example 11

[0111] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0112] 1. Adjust the pH of water to 3.0–4.5 by adding acetic acid to obtain acidified water; add 0.2% wt epoxy silane to the acidified water and stir until fully dissolved to obtain a modified solution; spray the modified solution onto silica (D 50After surface mixing of particles with a diameter of 1 μm, stir at 90–100 °C for at least 15 minutes to obtain D. 50 Modified silica with a particle size of 1.2 μm.

[0113] 2. Functional polymer organosilicon-acrylate graft copolymer (Shin-Etsu KR9706), compatibilizer ethylene-methyl acrylate-maleic anhydride terpolymer (Lotader 3140, SK Chemicals), first inorganic filler modified silica, and anti-sticking agent talc powder (800 mesh, Zhanteng Minerals) are added to a kneader at a mass ratio of 60:10:27:3 and stirred at high speed for 5 minutes. The mixed material is then granulated through a twin-screw extruder at temperatures of 180℃, 190℃, 190℃, 190℃, and 190℃ respectively to obtain modified layer granules.

[0114] 3. The waterproof layer mixture is obtained by mixing ethylene-vinyl acetate copolymer (EVA28005, LG Chem), ethylene-vinyl acetate copolymer (EVA2005C0, Saudi National Petrochemical), and maleic anhydride grafted polyethylene (PE-g-MAH4700, SK Chem) in a mass ratio of 15:55:30.

[0115] 4. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0116] The extruder temperature is set to 180℃, 190℃, and 190℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 200μm and 1000μm, respectively.

[0117] Example 12

[0118] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0119] 1. Add functional polymer thermoplastic polyurethane elastomer (Pearlcoat DIPP 119TPU, Lubrizol), compatibilizer maleic anhydride-grafted styrene thermoplastic elastomer (FG1901, Kertész), and inorganic filler calcium carbonate (CARB-5JI, Omia) to a kneader at a mass ratio of 70:20:10 and mix at high speed for 3-10 minutes. Then, granulate the mixed material underwater through a twin-screw extruder. The extruder is heated in 5 sections with temperatures set at 180℃, 190℃, 190℃, 190℃, and 190℃ respectively.

[0120] 2. A waterproof layer mixture is prepared by mixing styrene-ethylene-butene-styrene block copolymer (SEBSG1657V, Kronen), ethylene-octene copolymer (Engage POE8150, Dow), linear low-density polyethylene (DFDA7042, Sinopec), white oil (KN4006, Hebei Wantai Chemical), calcium carbonate (CARB-5JI, Omia), and antioxidant (1010, BASF) in a mass ratio of 20:20:40:8:12:1.

[0121] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion casting / calendering to obtain the waterproof membrane;

[0122] The extruder temperature is set to 170℃, 180℃, and 180℃, the main and auxiliary machine speed ratio is set to 1:1.2, and the thicknesses of the modified layer and the waterproof layer are set to 100μm and 1000μm, respectively.

[0123] Example 13

[0124] This embodiment provides a waterproof membrane, including a waterproof layer and a modified layer disposed on the upper surface of the waterproof layer, and its preparation method includes the following steps:

[0125] 1. A functional polymer polyurethane block copolymer (TU-S5265, Kuraray), a compatibilizer maleic anhydride-grafted styrene thermoplastic elastomer (FG1901, Kraton), and D... 50 The first inorganic filler, organic montmorillonite (WSG-PN06, Shanghai Wanzhao), with a particle size of 0.5μm, was added to a kneader at a mass ratio of 70:20:10 and stirred at high speed for 3-10 minutes. The mixed material was then granulated underwater by a twin-screw extruder. The extruder was heated in 5 sections with temperatures set at 180℃, 190℃, 190℃, 190℃, and 190℃ respectively.

[0126] 2. A waterproof layer mixture is obtained by mixing styrene-ethylene-butene-styrene block copolymer (SEBSG1645V, Kraton), ethylene-octene copolymer (Engage POE8150, Dow), linear low-density polyethylene (DFDA7042, Sinopec), calcium carbonate (CARB-5JI, Omia), and antioxidant (1010, BASF) in a mass ratio of 20:20:40:20:1.

[0127] 3. The waterproof layer mixture and the modified layer granules are fed into two independent extruders for double-layer co-extrusion calendering to obtain the waterproof membrane;

[0128] The extruder temperature is set to 190℃, 200℃, and 200℃, the main and auxiliary machine speed ratio is set to 1:1.1, and the thickness of the modified layer and the waterproof layer is set to 180μm and 1000μm, respectively.

[0129] Example 14

[0130] This embodiment provides a waterproof membrane, the structure and preparation method of which are basically the same as those in Example 13. The difference is that the functional polymer is replaced by an organosilicon-polyurethane block copolymer (TU-S5265, Kuraray) with an organosilicon-polyurethane copolymer (V165, Meirui New Materials).

[0131] Example 15

[0132] The structure and preparation method of the waterproof membrane in this embodiment are basically the same as those in Example 10. The difference is that the compatibilizer ethylene-vinyl acetate copolymer (EVM50M27, Yunnan Zhengbang) is omitted in the modified layer, and the functional polymer ethylene-acrylate elastomer ( The mass ratio of AEM G), first inorganic filler modified calcium carbonate, and second inorganic filler calcium carbonate (CARB-5JI, Omia) is 65:10:25.

[0133] Example 16

[0134] The structure and preparation method of the waterproof membrane in this embodiment are basically the same as those in Example 11. The difference is that the compatibilizer ethylene-methyl acrylate-maleic anhydride terpolymer (Lotader 3140, SK Chemicals) is omitted, and the mass ratio of functional polymer organosilicon-acrylate graft copolymer (Shin-Etsu KR9706), first inorganic filler modified silica, and anti-adhesive talc powder (800 mesh, Zhan Teng Minerals) is 70:27:3.

[0135] Comparative Example 1

[0136] This comparative example provides a waterproof membrane whose structure and preparation method are basically the same as those in Example 1. The difference is that the functional polymer acrylate block copolymer in step 2 is replaced with linear low-density polyethylene (DFDA7042, Guangzhou Petrochemical).

[0137] Comparative Example 2

[0138] This comparative example provides a waterproof membrane, the structure and preparation method of which are basically the same as those in Example 1, except that the functional polymeric acrylate block copolymer is replaced with ethylene-acrylic acid copolymer (Escort). TM EAA5050 (ExxonMobil).

[0139] I. Testing of physical properties of waterproof membrane raw materials

[0140] A. The following parameters were tested on the functional polymers used in the preparation of the above waterproof membrane:

[0141] 1. Shore hardness: Tested according to GB / T 2411-2008;

[0142] 2. Surface tension: Tested according to ASTM D7490-2008;

[0143] 3. Melt flow index: Tested according to GB / T 3682.1~2-2018;

[0144] 4. Crystallinity: Calculated by XRD, the formula is K=(I / S) / (2Bcosθ), where K is the crystallinity, I is the peak area of ​​the diffraction peak, S is the sample weight, B is the width of the diffraction peak, and θ is the wavelength of the diffraction peak.

[0145] 5. Glass transition temperature Tg: Tested according to GB / T 19466.1-2004;

[0146] 6. Melting temperature: Tested according to GB / T 21781-2008.

[0147] The test results for the above parameters are shown in Table 1.

[0148] B. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy were performed on the polymer selected as the functional polymer in the preparation of the waterproof membrane. 1 The acrylate block copolymer was analyzed using ¹H NMR, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The results were combined to determine the types, contents, and glass transition temperatures of the soft and hard segments. The analytical results are shown in Table 2.

[0149] C. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy were performed on the polyurethane block copolymer used as the functional polymer in the preparation of the waterproof membrane. 1 The polyurethane block copolymer was analyzed using 1H NMR, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA), and the block types and contents were determined based on the test results. The analysis results are shown in Table 3.

[0150] D. The oil absorption value of the first inorganic filler used in the preparation of the above waterproof membrane was tested. The test method was in accordance with ISO 787-5:1980. The test results are shown in Table 4.

[0151] Table 1

[0152]

[0153]

[0154] Table 2

[0155]

[0156] Table 3

[0157]

[0158] In Table 3, -60℃ in the Tg of the second block of the polyurethane block copolymer TU-S5265 is the glass transition temperature of the polybutadiene block, and 60℃ is the glass transition temperature of the hydrogenated polystyrene block.

[0159] Table 4

[0160] Oil absorption value (mL / 100g) 20 40 50

[0161] II. Peel strength testing of waterproof membranes under different construction scenarios

[0162] The waterproof membranes prepared in the above embodiments and comparative examples, as well as existing waterproof materials in the art, including commercially available PE geomembranes, PME-EVA waterproof boards, PMT-TPO sheets, and self-adhesive polymer membranes (PMH3041, Oriental Yuhong), were applied to roll-coating composite scenarios, pre-laying scenarios, and wet-laying scenarios, respectively. The peel strength of the waterproof materials under different construction scenarios was tested. (It should be noted that the adhesive layer of self-adhesive polymer membrane PMH3041 cannot play an adhesive role in the wet-laying scenario, making it unsuitable for use in wet-laying scenarios. Therefore, peel strength tests were only conducted on self-adhesive polymer membrane PMH3041 in roll-coating composite and pre-laying scenarios.) The details are as follows:

[0163] 1. Coil-coated composite peel strength

[0164] Test method: Apply the coating to the surface of the waterproof material using a 1mm applicator, and cover with a mesh fabric as a reinforcement layer. After drying, apply a second coat. After curing according to the corresponding coating standard, test the peel strength of the specimens, referring to GB2792. The test results are shown in Table 5.

[0165] 2. Pre-lay peel strength

[0166] Test method: Sample preparation and testing were carried out according to section 6.20 of GB / T 23457-2017. The test results are shown in Table 6.

[0167] 3. Wet-laid peel strength

[0168] Test method: A 1.5mm thick layer of paint or mortar was applied to a 50mm×200mm mortar board, and then a waterproof material sample of the corresponding size was laid on top. After curing, a peel strength test was conducted. The test results are shown in Table 7.

[0169] Table 5

[0170]

[0171]

[0172] Table 6

[0173]

[0174]

[0175] Table 7

[0176]

[0177]

[0178] The following conclusions can be drawn from Tables 5 to 7:

[0179] 1) The test results of waterproof membranes, PE geomembranes, PME-EVA waterproof boards, PMT-TPO sheets, and self-adhesive polymer membranes PMH3041 in Examples 1-16 show that, compared with unmodified PE geomembranes, PME-EVA waterproof boards, and PMT-TPO sheets, the waterproof membranes with modified layers in Examples 1-18 have good adhesion strength with different types of coatings in roll-coating, pre-laying, and wet-laying applications, and are not easily peeled off. Compared with self-adhesive polymer membranes PMH3041 with adhesive layers, the waterproof membranes in Examples 1-16 have the advantage of still having good adhesion strength in wet-laying scenarios. In roll-coating and pre-laying scenarios, although their peel strength is weaker than that of adhesive layers, it is sufficient to meet the construction requirements of waterproof materials.

[0180] 2) As can be seen from the comparison of Examples 1, 10 and 11, when the content of functional polymer or the content of the first inorganic filler in the modified layer is too low, it will have an adverse effect on the adhesive performance of the modified layer. The peel strength of the obtained waterproof membrane is reduced in the scenarios of roll coating, pre-laying and wet laying.

[0181] 3) By comparing Example 1, Comparative Example 1, and Comparative Example 2, it can be seen that when the modified layer does not include the functional polymer of this application, it will obviously be detrimental to the adhesive performance of the modified layer, and the peel strength of the obtained waterproof membrane is significantly reduced in the scenarios of roll coating, pre-laying, and wet laying.

[0182] 4) By comparing Examples 10 and 15, and Examples 11 and 16, it can be seen that when the modified layer does not contain a compatibilizer, it will also affect the bonding strength of the waterproof membrane. The peel strength of the obtained waterproof membrane in roll coating, pre-laying and wet laying scenarios is slightly lower than that of the examples containing compatibilizer.

[0183] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A waterproof membrane, characterized in that, The system includes a waterproof layer and a non-adhesive modified layer disposed on at least one surface of the waterproof layer; wherein the waterproof layer comprises a hydrophobic thermoplastic resin; and the non-adhesive modified layer is used in place of an adhesive layer. The modified layer comprises a functional polymer with a surface tension of 30~50 dyn / cm, wherein the functional polymer is selected from acrylate polymers and / or polyurethane polymers; The acrylate polymer is selected from acrylate block copolymers with alternating soft and hard segments; the soft segments are selected from polybutyl acrylate or copolymers of polybutyl acrylate and 2-ethylhexyl acrylate, and the hard segments are selected from polymethacrylate; or... The acrylate polymer is selected from one or more of the following: ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-acrylate-maleic anhydride terpolymer, and organosilicon acrylic resin; or... The acrylate polymer is selected from ethylene-acrylate elastomers; The glass transition temperature of the soft segment is -100℃ to -30℃; the glass transition temperature of the hard segment is 40℃ to 120℃. The polyurethane polymer is selected from polyurethane block copolymers including a first block and a second block; The first block is selected from polyurethane, and the second block is selected from silicone and / or hydrogenated polystyrene copolymer; The polyurethane polymer is selected from thermoplastic polyurethane elastomers.

2. The waterproof membrane according to claim 1, characterized in that, Based on the total mass of the acrylate block copolymer, the mass content of the soft segment is 50% to 90%, and the mass content of the hard segment is 10% to 50%.

3. The waterproof membrane according to claim 1, characterized in that, Based on the relative molecular mass of the polyurethane block copolymer, the mass content of the first block is 50% to 90%, and the mass content of the second block is 10% to 50%.

4. The waterproof membrane according to any one of claims 1-3, characterized in that, The functional polymer has a Shore hardness of 20A to 60D; And / or, the melt index of the functional polymer is 0.5~100g / 10min; And / or, the crystallinity of the functional polymer is 0-30%; And / or, the glass transition temperature of the functional polymer is -60~30℃; And / or, the melting temperature of the functional polymer is 40~180℃.

5. The waterproof membrane according to any one of claims 1-3, characterized in that, The functional polymer accounts for 30% to 80% of the mass content of the modified layer.

6. The waterproof membrane according to claim 5, characterized in that, The modified layer further includes a first inorganic filler, which is a modified inorganic filler with surface grafting and / or coupling of organic matter.

7. The waterproof membrane according to claim 6, characterized in that, The oil absorption value of the first inorganic filler is 10~60mL / 100g.

8. The waterproof membrane according to claim 6 or 7, characterized in that, The organic compound is selected from one or more of polyacrylic acid and its copolymers, polyvinyl alcohol, polymaleic acid, organosilicon, epoxy resin, aminosilane, epoxysilane, and methylpropyloxysilane.

9. The waterproof membrane according to any one of claims 6-7, characterized in that, The first inorganic filler is selected from one or more of the following: organic modified calcium carbonate, silica, wollastonite, kaolin, montmorillonite, spherical clay, magnesia, and diatomaceous earth.

10. The waterproof membrane according to any one of claims 6-7, characterized in that, The D50 particle size of the first inorganic filler is 0.1~150μm.

11. The waterproof membrane according to any one of claims 6-7, characterized in that, The first inorganic filler accounts for 10% to 50% of the mass content of the modified layer.

12. The waterproof membrane according to claim 1, characterized in that, The modified layer further includes a second inorganic filler, which is selected from one or more of calcium carbonate, silicon dioxide, quartz, wollastonite, quartz, feldspar, kaolin, montmorillonite, titanium dioxide, magnesium hydroxide, aluminum hydroxide, spherical clay, bentonite, cement, magnesia, and diatomaceous earth.

13. The waterproof membrane according to claim 1, characterized in that, The modified layer further includes a compatibilizer selected from one or more of maleic anhydride graft copolymers, glycidyl methacrylate graft polymers, polystyrene block polymers, chlorinated polyethylene, tackifying resins, ethylene-vinyl acetate copolymers, and ethylene-acrylate copolymers.

14. The waterproof membrane according to claim 13, characterized in that, The compatibilizer accounts for 5% to 30% of the mass content of the modified layer.

15. The waterproof membrane according to claim 1, characterized in that, The hydrophobic thermoplastic resin is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, styrene-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

16. The waterproof membrane according to claim 1, characterized in that, The thickness of the waterproof layer is 500~2000μm; and / or, the thickness of the modified layer is 50~500μm.

Images