A waterproof adhesive composition, a waterproof adhesive layer, a preparation method of the waterproof adhesive layer, an ultra-low-temperature-resistant waterproof roll and a preparation method and application thereof

Abstract

This invention relates to the field of building waterproofing materials technology, and discloses a waterproof adhesive composition, a waterproof adhesive layer and its preparation method, an ultra-low temperature resistant waterproof membrane and its preparation method and application. The composition contains: 45-65 wt% hydroxyl-terminated polybutadiene, 2-5 wt% dioctyl sebacate, and 0.5-1.5 wt% polyethylene oxide. The ultra-low temperature resistant waterproof membrane provided by this invention exhibits excellent ultra-low temperature resistance, adhesion performance, mechanical properties, waterproof performance, aging resistance and stability, and raw material compatibility.

Description

Technical Field

[0001] This invention relates to the field of building waterproofing materials technology, specifically to a composition for a waterproof adhesive layer, a waterproof adhesive layer and its preparation method, an ultra-low temperature resistant waterproof membrane and its preparation method and application. Background Technology

[0002] Currently, waterproof membranes used in domestic engineering projects are mainly divided into three categories: bitumen-based, traditional polymer, and modified ordinary rubber. Waterproof membranes for low-temperature environments are mostly simple modifications of conventional raw materials. The existing core technical solutions are as follows: Low-temperature modified bitumen waterproof membrane: Rubber modifiers such as SBS are added to petroleum bitumen to improve low-temperature flexibility. The low-temperature resistance limit of conventional products is about -20℃ to -30℃, and some high-end modified products can withstand -40℃, but still cannot meet the requirements for use in ultra-low temperature environments.

[0003] Traditional polymer waterproof membranes: These membranes use HDPE (high-density polyethylene), PVC (polyvinyl chloride), and TPO (thermoplastic polyolefin elastomer / polyolefin thermoplastic elastomer) as core raw materials. They are modified with plasticizers to improve flexibility and have better low-temperature resistance than asphalt-based membranes. However, they will become brittle and deformed below -50°C, and are prone to water seepage and edge curling.

[0004] Ordinary rubber-based waterproof membranes: Made of EPDM rubber and butyl rubber, they have a certain degree of low-temperature flexibility, but their cross-linked structure is easily damaged at ultra-low temperatures, resulting in a significant decrease in elasticity and adhesion. In addition, the raw material cost is high, and their aging resistance is insufficient, leading to a short service life in ultra-low temperature environments.

[0005] Existing technologies have made some attempts to use liquid rubber modified waterproof membranes, but most of them are simple blending processes without designing a special crosslinking system for ultra-low temperatures. The glass transition temperature of the base material is too high, making it impossible to achieve stable waterproofing at ultra-low temperatures of -50℃ and below. In addition, the raw material compatibility is poor, and the membrane is prone to delamination and blistering.

[0006] In summary, the existing technical solutions have the following main drawbacks: (1) Insufficient resistance to ultra-low temperature: The temperature resistance limit of conventional low temperature waterproof membranes is mostly -20℃ to -30℃. They are prone to cracking and deformation below -50℃ and cannot meet the waterproof requirements of extremely cold low temperature environments.

[0007] (2) Imbalance between flexibility and adhesion: Modification with a single plasticizer can easily lead to the precipitation of plasticizer. While the flexibility of the roll material decreases, the adhesion strength with the base layer also decreases significantly, which can easily lead to debonding and water seepage problems.

[0008] (3) Poor compatibility of raw materials and poor structural density: The base material and filler of the existing modification process are easy to separate, resulting in voids and delamination inside the roll material, which damages the waterproof density and has poor resistance to cold and heat cycles. Summary of the Invention

[0009] The purpose of this invention is to overcome the problems of insufficient bonding performance, mechanical properties, and aging resistance of existing waterproof membranes in ultra-low temperature environments below -50℃, as well as poor structural stability and material compatibility.

[0010] To achieve the above objectives, a first aspect of the present invention provides a composition for a waterproof adhesive layer, the composition comprising a main agent and an auxiliary agent; Based on the total mass of the composition, the main agent contains: 45-65 wt% hydroxyl-terminated polybutadiene, 2-5 wt% dioctyl sebacate, and 1.5-4.5 wt% polyethylene oxide; The glass transition temperature of the hydroxyl-terminated polybutadiene is -90°C to -70°C, and the viscosity at 40°C is 4-5 Pa. s, hydroxyl value is 40-50mgKOH / g.

[0011] A second aspect of the present invention provides a method for preparing a waterproof adhesive layer, the method comprising using the components of the composition described in the first aspect, including: The components of the main agent and the components of the auxiliary agent in the composition are brought into contact, mixed, and shaped to obtain the waterproof adhesive layer.

[0012] A third aspect of the present invention provides a waterproof adhesive layer prepared by the method described in the second aspect.

[0013] A fourth aspect of the present invention provides an ultra-low temperature resistant waterproof membrane, which comprises a release membrane layer, an ultra-low temperature adhesive layer, a reinforcing layer and a waterproof adhesive layer stacked sequentially. The waterproof adhesive layer is the same as the waterproof adhesive layer described in the third aspect.

[0014] A fifth aspect of the present invention provides a method for preparing the ultra-low temperature resistant waterproof membrane described in the fourth aspect, the method comprising: S1: Apply the waterproof adhesive material of the waterproof adhesive layer to one side surface of the pretreated carcass reinforcement layer to obtain the intermediate; S2: The intermediate is cured and aged sequentially to obtain a waterproof adhesive layer; an ultra-low temperature adhesive layer and a release film layer are sequentially applied to the other side surface of the reinforcing layer to obtain the ultra-low temperature resistant waterproof membrane.

[0015] The sixth aspect of the present invention provides the application of the ultra-low temperature resistant waterproof membrane described in the fifth aspect in waterproofing projects and seepage prevention construction projects.

[0016] Compared with existing low-temperature modified bitumen waterproof membranes and ordinary rubber waterproof membranes, this invention solves the problem that existing waterproof membranes cannot withstand ultra-low temperatures below -50℃ through HTPB-DOS-PEO synergistic modification, formula optimization, structural design, and process innovation. This allows the waterproof membrane to maintain good flexibility and structural integrity in ultra-low temperature environments. Simultaneously, it also addresses the problems of poor structural stability and insufficient aging resistance of waterproof membranes in ultra-low temperature environments, improving the membrane's resistance to thermal cycling and UV radiation; thus achieving a breakthrough improvement in ultra-low temperature waterproof performance.

[0017] The present invention provides an ultra-low temperature resistant waterproof membrane with at least the following significant technical advantages: 1) A qualitative breakthrough in ultra-low temperature resistance: Through the synergistic effect of dioctyl sebacate, hydroxyl-terminated polybutadiene, and ultra-low temperature toughening agent, the glass transition temperature of the core adhesive layer is reduced to below -65℃. The waterproof membrane can stably withstand ultra-low temperatures below -50℃, which is far superior to the temperature resistance limit of existing membranes from -20℃ to -40℃. Moreover, dioctyl sebacate is a long-lasting plasticizer with no precipitation, and the ultra-low temperature performance is long-lasting and stable.

[0018] 2) Excellent raw material compatibility and structural density: Polyethylene oxide is introduced as a compatibility thickener, and an alcohol solution dispersion process is used to improve its dispersibility, which effectively solves the problems of separation and delamination of existing roll material base material and filler. With the addition of silane coupling agent modification, the internal cross-linking of the roll material is uniform and the structure is dense, resulting in significant waterproof and seepage prevention effects.

[0019] 3) Perfect balance between mechanical properties and low-temperature performance: room temperature tensile strength ≥9.0MPa, ultra-low temperature tensile strength ≥6.5MPa, solving the problem that existing technologies reduce mechanical strength when improving low-temperature flexibility.

[0020] 4) Significantly improved aging resistance and service life: Hydroxyl-terminated polybutadiene itself has excellent aging resistance and good compatibility with various raw materials. After 100 cycles of thermal cycling from -60℃ to 50℃, the mechanical properties are still retained at ≥78%, which extends the service life of the material in ultra-low temperature environments and reduces the later maintenance costs.

[0021] 5) Scientifically designed formula with long-term stable performance: The combination of dioctyl sebacate and epoxidized soybean oil avoids the performance degradation caused by the precipitation of a single plasticizer; the functions of each additive are complementary, and the performance of the roll material does not significantly decrease during long-term use, with excellent stability. Detailed Implementation

[0022] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] As previously described, a first aspect of the present invention provides a composition for a waterproof adhesive layer, the composition comprising a main agent and an auxiliary agent; Based on the total mass of the composition, the main agent contains: 45-65 wt% hydroxyl-terminated polybutadiene, 2-5 wt% dioctyl sebacate, and 1.5-4.5 wt% polyethylene oxide; The glass transition temperature of the hydroxyl-terminated polybutadiene is -90°C to -70°C, and the viscosity at 40°C is 4-5 Pa. s, hydroxyl value is 40-50mgKOH / g.

[0024] In this invention, the inventors discovered that by synergistically compounding dioctyl sebacate (DOS), polyethylene oxide (PEO), and hydroxyl-terminated polybutadiene (HTPB), the long-lasting plasticizing effect of DOS and the compatibility thickening effect of PEO can achieve a triple improvement in the ultra-low temperature flexibility, adhesion, and density of the waterproof membrane provided by this invention from the raw material level, thus solving the defects of single modification in existing technologies. At the same time, a special crosslinking modification system for HTPB-DOS-PEO was designed to reduce the glass transition temperature of the core adhesive layer to below -65°C, enabling ultra-low temperature tolerance of -50°C.

[0025] Preferably, in the main agent, the molecular weight of the hydroxyl-terminated polybutadiene is 3000-4500.

[0026] Preferably, in the main agent, the polyethylene oxide has a molecular weight of 150,000-250,000, a melting point of 65-67°C, and a crystallinity of 75-85%. Under this preferred condition, the waterproof membrane provided by the present invention has excellent ultra-low temperature resistance, adhesion, mechanical properties, waterproof performance, aging resistance and stability, and compatibility.

[0027] More preferably, in the main agent, the polyethylene oxide has a molecular weight of 200,000.

[0028] Preferably, based on the total mass of the composition, the additive contains 9-16 wt% isocyanate crosslinking agent, 4-8 wt% toughening agent, 12-22 wt% inorganic filler, 0.6-1.2 wt% silane coupling agent, and 1-3 wt% plasticizer.

[0029] Preferably, in the additive, the isocyanate crosslinking agent is selected from at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0030] Preferably, in the additives, the toughening agent is selected from at least one of polypropylene glycol PPG-3000, polypropylene glycol PPG-4000, and polytetrahydrofuran ether glycol PTMEG-2000.

[0031] Preferably, in the additive, the inorganic filler is selected from at least one of nano-talc powder, nano-mica powder, and nano-montmorillonite; Preferably, in the additive, the silane coupling agent is selected from at least one of KH-560, KH-550, and KH-580; Preferably, in the additives, the plasticizer is an epoxy plasticizer, and the epoxy plasticizer is selected from at least one of epoxidized soybean oil and epoxidized castor oil.

[0032] In this invention, the inventors discovered that dioctyl sebacate has excellent low-temperature flexibility and no precipitation. By compounding dioctyl sebacate with epoxidized soybean oil, the precipitation of plasticizers is avoided. Polyoxyethylene optimizes compatibility and has good compatibility and thickening properties. The waterproof membrane provided by this invention can achieve a synergistic balance of ultra-low temperature flexibility, bonding strength, mechanical strength and aging resistance.

[0033] As previously described, a second aspect of the present invention provides a method for preparing a waterproof adhesive layer, the method comprising using the components of the composition described in the first aspect, including: The components of the main agent and the components of the auxiliary agent in the composition are brought into contact, mixed, and shaped to obtain the waterproof adhesive layer.

[0034] Preferably, the contact mixing operation includes: (1) The hydroxyl-terminated polybutadiene is pretreated to obtain pretreated hydroxyl-terminated polybutadiene; (2) Dioctyl sebacate, toughening agent, plasticizer and the pretreated hydroxyl-terminated polybutadiene are mixed in the first mixture to obtain mixture I; (3) Mixture I is mixed with polyethylene oxide and inorganic filler to obtain mixture II; (4) Mix the mixture II and the isocyanate crosslinking agent in a third mixing to obtain the waterproof adhesive to be molded.

[0035] Preferably, the pretreatment is carried out under vacuum drying conditions; the vacuum drying conditions include: a temperature of 60-80℃, preferably 65℃; and a time of 2-4 hours, preferably 2.5 hours.

[0036] More preferably, the pretreatment conditions are controlled such that the moisture content of the pretreated hydroxyl-terminated polybutadiene is ≤0.1wt%.

[0037] More preferably, the conditions for the first mixing include: a rotation speed of 500-800 rpm, preferably 600 rpm; a temperature of 55-65°C; and a time of 0.5-2.5 h, preferably 1 h.

[0038] Preferably, the inorganic filler is surface modified with a silane coupling agent before use.

[0039] More preferably, the surface modification treatment is carried out in a high-speed mixer, and the conditions for the surface modification treatment include: a rotation speed of 800-1000 rpm, preferably 900 rpm; and a time of 30-60 min, preferably 40 min.

[0040] Preferably, the polyethylene oxide is formulated into an alcohol solution containing polyethylene oxide. In this preferred embodiment, dispersing polyethylene oxide (PEO) in an alcohol solution improves its dispersibility and compatibility with other raw materials.

[0041] More preferably, the alcohol is ethanol.

[0042] More preferably, the mass ratio of the polyethylene oxide to the ethanol is 1:4-6; more preferably 1:5.

[0043] More preferably, the conditions for the second mixing include: a rotation speed of 1000-1300 rpm, preferably 1100 rpm; a temperature of 55-65°C; and a time of 1.5-4.5 h, preferably 2 h.

[0044] More preferably, the conditions for the third mixing include: a rotation speed of 100-400 rpm, preferably 300 rpm; a temperature of 40-45°C; and a time of 30-60 min, preferably 40 min.

[0045] As previously stated, a third aspect of the present invention provides a waterproof adhesive layer prepared by the method described in the second aspect.

[0046] As mentioned above, the fourth aspect of the present invention provides an ultra-low temperature resistant waterproof membrane, which contains a release membrane layer, an ultra-low temperature adhesive layer, a reinforcing layer and a waterproof adhesive layer stacked sequentially. The waterproof adhesive layer is the same as the waterproof adhesive layer described in the third aspect.

[0047] Preferably, the thickness of the isolation membrane layer is 0.03-0.05 mm; the thickness of the ultra-low temperature adhesive layer is 0.3-0.5 mm; the thickness of the carcass reinforcement layer is 1.0-1.5 mm; and the thickness of the waterproof adhesive layer is 1.5-2.0 mm.

[0048] Preferably, the total thickness of the ultra-low temperature resistant waterproof membrane is 3.0-4.0 mm.

[0049] More preferably, the total thickness of the ultra-low temperature resistant waterproof membrane is 3.0-3.5 mm.

[0050] Preferably, the separator layer is selected from at least one of silicone-coated polyethylene film, polyester film, and aluminized polyester film.

[0051] Preferably, the ultra-low temperature adhesive layer is a modified polyisobutylene protective layer.

[0052] Preferably, the adhesive of the ultra-low temperature bonding layer is composed of polyisobutylene, terpene resin, ethylene-vinyl acetate grafted maleic anhydride and nano-montmorillonite.

[0053] More preferably, based on the total mass of the adhesive compound in the ultra-low temperature adhesive layer, the amount of polyisobutylene is 10-20 wt%; the amount of terpene resin is 35-50 wt%; the amount of ethylene-vinyl acetate grafted maleic anhydride is 10-15 wt%; and the amount of nano-montmorillonite is 15-25 wt%.

[0054] More preferably, the ultra-low temperature adhesive layer is prepared by the following method: adding polyisobutylene to a metal container, heating to 130-150℃, and stirring at a rate of 300-400 rpm; adding terpene resin and ethylene-vinyl acetate grafted maleic anhydride, maintaining the temperature at 130-150℃, stirring at a rate of 300-400 rpm, and mixing for 30-50 min; adding nano-montmorillonite, maintaining the temperature at 130-150℃, stirring at a rate of 300-400 rpm, and mixing for 30-50 min to obtain an adhesive, which is then coated and molded.

[0055] Preferably, the carcass reinforcement layer is selected from at least one of polyester nonwoven fabric, fiberglass mesh fabric, and polyester fiberglass fabric.

[0056] More preferably, the polyester nonwoven fabric is a high-toughness polyester nonwoven fabric.

[0057] More preferably, the basis weight of the carcass reinforcement layer is 220-300 g / m². 2 .

[0058] In this invention, the ultra-low temperature resistant waterproof membrane provided by this invention is a four-layer composite layered structure with precise thickness ratio of each layer to achieve a synergistic effect of structural strength and ultra-low temperature performance; among them, the waterproof adhesive layer is an ultra-low temperature elastic gel system, which forms a three-dimensional network structure after cross-linking and curing. It is the core functional layer of this invention and the key to achieving ultra-low temperature waterproofing, adhesion and density.

[0059] As previously described, the fifth aspect of the present invention provides a method for preparing the ultra-low temperature resistant waterproof membrane described in the fourth aspect, the method comprising: S1: Apply the waterproof adhesive material of the waterproof adhesive layer to one side surface of the pretreated carcass reinforcement layer to obtain the intermediate; S2: The intermediate is cured and aged sequentially to obtain a waterproof adhesive layer; an ultra-low temperature adhesive layer and a release film layer are sequentially applied to the other side surface of the reinforcing layer to obtain the ultra-low temperature resistant waterproof membrane.

[0060] In a preferred embodiment, the carcass reinforcement layer is pretreated before use. The pretreatment steps include: immersing the carcass reinforcement layer in a 5wt% KH-560 ethanol solution for 6 minutes, and then drying it at 85°C for 40 minutes.

[0061] Preferably, in step S2, the curing is constant temperature curing.

[0062] More preferably, in step S2, the curing conditions include: a temperature of 45-55°C and a time of 20-30 hours.

[0063] Preferably, in step S2, the aging process is performed at room temperature.

[0064] More preferably, in step S2, the ripening conditions include: a temperature of 20-30°C and a time of 40-60 hours.

[0065] In this invention, the inventors discovered that the invention adopts an integrated coating-crosslinking curing process, which is carried out at 23-85℃ throughout the process. It does not require high-end special equipment, has strong process controllability, uniform crosslinking, and is suitable for continuous industrial production. The step-by-step curing process of "low temperature constant temperature curing + room temperature curing" can ensure uniform crosslinking inside the waterproof membrane, without bubbles or delamination, and improve the waterproof density.

[0066] As mentioned above, the sixth aspect of the present invention provides the application of the ultra-low temperature resistant waterproof membrane described in the fifth aspect in waterproofing projects and seepage prevention construction projects.

[0067] Preferably, the ultra-low temperature resistant waterproof membrane is suitable for a temperature range of -60℃ to -50℃.

[0068] The ultra-low temperature resistant waterproof membrane provided by this invention can withstand ultra-low temperature environments and is suitable for waterproofing and seepage prevention construction in cold regions with temperatures ranging from -40℃ to -50℃, and in extremely cold municipal engineering projects in northern regions.

[0069] The present invention will be described in detail below through embodiments. Unless otherwise specified, all instruments and materials used in the following embodiments are commercially available products.

[0070] In the following examples, unless otherwise specified, each part by weight represents 1g.

[0071] HTPB-1 (hydroxyl-terminated polybutadiene): purchased from Tianyuan Aviation Materials (Yingkou) Technology Co., Ltd., CAS No. 69102-90-5, purity 99wt%, viscosity at 40℃ 4.3Pa. s, glass transition temperature is -80℃; molecular weight is 3700, hydroxyl value is 45mgKOH / g.

[0072] HTPB-2 (hydroxyl-terminated polybutadiene): purchased from Tianyuan Aviation Materials (Yingkou) Technology Co., Ltd., CAS No. 69102-90-5, purity 99wt%, viscosity at 40℃ 3.5Pa. s, glass transition temperature is -75℃; molecular weight is 2900, hydroxyl value is 45mgKOH / g.

[0073] HTPB-3 (hydroxyl-terminated polybutadiene): purchased from Shandong Qilong Chemical Co., Ltd., CAS No. 69102-90-5, purity 99wt%, viscosity at 40℃ 6Pa. s, glass transition temperature is -65℃; molecular weight is 3500, hydroxyl value is 38mgKOH / g.

[0074] DOS (dioctyl sebacate): purchased from Qilu Petrochemical, industrial grade, purity 99.5 wt%.

[0075] PEO-1 (polyethylene oxide): purchased from Dow Chemical, with a molecular weight of 200,000, a melting point of 66°C, a crystallinity of 80%, and industrial grade.

[0076] PEO-2 (polyethylene oxide): purchased from Wuhan Jiyesheng Chemical Co., Ltd., with a molecular weight of 220,000, a melting point of 65℃, a crystallinity of 70%, and is of industrial grade.

[0077] Toughening agent: Polypropylene glycol (PPG-3000) was purchased from Shandong Xinheng Chemical Co., Ltd.

[0078] Polypropylene glycol (PPG-4000) was purchased from Shandong Hengxin Chemical Co., Ltd.

[0079] Polytetrahydrofuran ether diol PTMEG-2000 was purchased from Sinopec Great Wall Energy Chemical Co., Ltd.

[0080] Plasticizer: Epoxidized soybean oil, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0081] Epoxidized castor oil, purchased from Shandong Kexing Chemical Co., Ltd.

[0082] Inorganic packing: Nano talc powder, purchased from Yingkou Sanzhe New Materials.

[0083] Nano mica powder, purchased from Shijiazhuang Chenxing Industry.

[0084] Nano-montmorillonite was purchased from Zhejiang Fenghong New Materials.

[0085] Silane coupling agents: KH-560 was purchased from Nanjing Shuguang Silane Chemical Co., Ltd.

[0086] KH-580 was purchased from Nanjing Shuguang Silane Chemical Co., Ltd.

[0087] Isocyanate crosslinking agents: diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) were all purchased from Jinan Jinhao Chemical.

[0088] Carcass reinforcement layer: polyester nonwoven fabric, with a basis weight of 230g / m² 2 It has a thickness of 1.1mm and was purchased from Hubei Youbu.

[0089] Ultra-low temperature adhesive layer: Modified polyisobutylene protective layer, 0.4 mm thick, self-made, preparation process is as follows: Add 15 wt% polyisobutylene to a metal can, heat to 140℃, and stir at 300 rpm; add 50 wt% terpene resin and 10 wt% ethylene-vinyl acetate grafted maleic anhydride, maintain the temperature at 150℃, stir at 300 rpm, and mix for 30 min; add 25 wt% nano-montmorillonite, maintain the temperature at 150℃, stir at 400 rpm, and mix for 50 min to obtain the adhesive, which is then coated and molded.

[0090] Separating film layer: Specifically, it is a PET separating film (polyester film) with a thickness of 0.03mm, purchased from Shanghai Qunqi.

[0091] Example 1 Raw material pretreatment: (1) The hydroxyl-terminated polybutadiene was vacuum dried at 65°C for 2.5 h (i.e., pretreatment) to remove moisture (moisture content ≤ 0.1%) and prevent the crosslinking reaction from generating bubbles, thus obtaining the pretreated hydroxyl-terminated polybutadiene. Nano-talc powder (i.e., inorganic filler) and silane coupling agent (KH-560) were mixed in a high-speed mixer at 900 rpm for 40 min to perform surface modification treatment on the filler. Polyoxyethylene was dissolved in anhydrous ethanol (mass ratio 1:5) to prepare an alcohol solution containing polyoxyethylene for later use, which improved the dispersibility of polyoxyethylene with other raw materials.

[0092] Preparation of the core adhesive material in the waterproof adhesive layer: (2) Add pretreated hydroxyl-terminated polybutadiene to a sealed reactor, heat to 60°C, and add dioctyl sebacate, epoxidized soybean oil (i.e., plasticizer), and polypropylene glycol PPG-3000 (i.e. toughening agent) in sequence. Stir at low speed of 600 rpm for 1 hour (i.e., first mixing) until uniformly mixed to obtain mixture I. (3) Add an alcohol solution containing polyethylene oxide and modified nano talc powder to mixture I, and stir at high speed of 1100 rpm for 2 hours (i.e., the second mixing) to obtain a mixture II with a uniform base material; (4) Cool down to 45°C, add MDI (i.e., isocyanate crosslinking agent) to mixture II, stir at low speed of 300 rpm for 40 min (i.e., the third mixing) to prevent bubbles from being generated by stirring too fast, and obtain the waterproof adhesive to be molded for later use.

[0093] Waterproof membrane preparation: S1: Pretreatment of carcass reinforcement layer: Immerse the polyester nonwoven fabric in 5% KH-560 ethanol solution for 6 minutes, take it out and dry it at 85℃ for 40 minutes to improve its adhesion to the core rubber material and prevent delamination, thus obtaining the pretreated carcass reinforcement layer. Coating and molding: Using a scraper-type continuous coating process, the core waterproof adhesive to be molded is evenly coated on the surface of the pretreated carcass reinforcement layer, and the thickness of the adhesive layer is controlled at 1.7mm to obtain the intermediate body; S2: Cross-linking and curing: The intermediate roll material is placed in a constant temperature curing chamber at 45℃ and cured at a constant temperature for 24 hours to allow the hydroxyl-terminated polybutadiene and the cross-linking agent to fully cross-link and form a stable three-dimensional network elastomer; then it is cured at room temperature (25±5℃) for 48 hours to complete the cross-linking reaction and obtain a waterproof adhesive layer; then a modified polyisobutylene protective layer (i.e., ultra-low temperature adhesive layer) is coated on the lower surface of the substrate, with the thickness controlled at 0.4mm, and a PET isolation protective film (i.e., isolation film layer) is applied to obtain the finished ultra-low temperature resistant waterproof roll material.

[0094] Examples 2-5 The same process as in Example 1 was used, except that the amount of raw materials used was different, as shown in Table 1.

[0095] Table 1

[0096] Comparative Example 1 The same procedure as in Example 1 was used, except that in this comparative example, "dioctyl sebacate" was replaced with an equal part by weight of "dioctyl adipate".

[0097] Comparative Example 2 The same procedure as in Example 1 was used, except that the amount of dioctyl sebacate was adjusted from "2 parts by weight" to "1.5 parts by weight", and the amount of nano talc was adjusted from "22 parts by weight" to "22.5 parts by weight".

[0098] Comparative Example 3 The same procedure as in Example 1 was used, except that in this comparative example, "polyethylene oxide" was replaced with an equal part by weight of "polyethylene glycol".

[0099] Comparative Example 4 The same procedure as in Example 1 was followed, except that the amount of polyethylene oxide was adjusted from "4 parts by weight" to "5 parts by weight" and the amount of nano talc was adjusted from "22 parts by weight" to "21 parts by weight".

[0100] Comparative Example 5 The same procedure as in Example 1 was used, except that in this comparative example, "hydroxyl-terminated polybutadiene (HTPB-1)" was replaced with an equal part by weight of "hydroxyl-terminated polybutadiene (HTPB-3)".

[0101] Test case Core performance tests were conducted on the samples from the above embodiments and comparative examples.

[0102] The test method for ultra-low temperature tolerance is: bending at -50℃, according to GB / T 328.15-2007.

[0103] The test method for adhesion performance is as follows: peel strength test refers to GB / T 35467-2017.

[0104] The test methods for mechanical properties are as follows: tensile strength and elongation at break are tested in accordance with GB / T 328.9-2007.

[0105] The test method for waterproof performance is as follows: the impermeability test refers to GB / T 35467-2017.

[0106] The test method for aging resistance and stability is as follows: After cold and hot cycling treatment, the test is completed according to GB / T 328.9-2007. The tensile strength retention rate and elongation at break retention rate can be calculated by comparing the treated performance value with the initial value.

[0107] The test results are shown in Table 2 below.

[0108] Table 2

[0109] As can be seen from the results in Table 2, the ultra-low temperature resistant waterproof membrane provided by this invention uses hydroxyl-terminated polybutadiene as the core base material, synergistically compounded with dioctyl sebacate, polyethylene oxide modifier, and isocyanate crosslinking agent, functional filler, and anti-aging compound system to prepare a four-layer composite structure ultra-low temperature resistant waterproof membrane; it has excellent ultra-low temperature resistance, bonding performance, mechanical properties, waterproof performance, aging resistance and stability, and compatibility.

[0110] Specifically, the ultra-low temperature resistant waterproof membrane provided by this invention, after being placed at a constant temperature of -50℃ for 24 hours and then repeatedly bent 180° five times, shows no cracks, no embrittlement, and no deformation; at room temperature, the peel strength at the overlap edge is ≥3.0 N / mm, and the peel strength to the concrete substrate is ≥3.5 N / mm; at -50℃, the peel strength at the overlap edge is ≥2.5 N / mm, and the peel strength to the concrete substrate is ≥2.0 N / mm; at room temperature, the tensile strength is ≥9.0 MPa, and the elongation at break is ≥ 700%; tensile strength at -50℃ ≥6.5MPa, elongation at break ≥420%; under constant pressure of 0.3MPa water for 120min, no leakage, no water permeability, and no deformation of the roll material; after 100 cycles of hot and cold cycling from -60℃ to 50℃, the tensile strength retention rate is ≥87%, the elongation at break retention rate is ≥79%, with no delamination, no bulging, and no plasticizer exudation; and all raw materials are uniformly dispersed, with no voids or filler agglomeration inside the adhesive layer, and excellent structural density.

[0111] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composition for a waterproof adhesive layer, characterized in that, The composition consists of a main agent and an auxiliary agent; Based on the total mass of the composition, the main agent contains: 45-65 wt% hydroxyl-terminated polybutadiene, 2-5 wt% dioctyl sebacate, and 1.5-4.5 wt% polyethylene oxide; The hydroxyl-terminated polybutadiene has a glass transition temperature of -90°C to -70°C and a viscosity of 3.5-5 Pa at 40°C. s, hydroxyl value is 40-50mgKOH / g.

2. The composition according to claim 1, characterized in that, In the main agent, the number-average molecular weight of the hydroxyl-terminated polybutadiene is 3000-4500; And / or, in the main agent, the polyethylene oxide has a viscosity-average molecular weight of 150,000-250,000; a melting point of 65-67°C; and a crystallinity of 75-85%.

3. The composition according to claim 1 or 2, characterized in that, Based on the total mass of the composition, the additive contains 9-16 wt% isocyanate crosslinking agent, 4-8 wt% toughening agent, 12-22 wt% inorganic filler, 0.6-1.2 wt% silane coupling agent, and 1-3 wt% plasticizer; And / or, in the additives, the toughening agent is selected from at least one of polypropylene glycol PPG-3000, polypropylene glycol PPG-4000, and polytetrahydrofuran ether glycol PTMEG-2000; And / or, in the additives, the plasticizer is an epoxy plasticizer, and the epoxy plasticizer is selected from at least one of epoxidized soybean oil and epoxidized castor oil.

4. A method for preparing a waterproof adhesive layer, characterized in that, This method involves preparing the composition using any one of the components described in claims 1-3, comprising: The components of the main agent and the components of the auxiliary agent in the composition are brought into contact, mixed, and shaped to obtain the waterproof adhesive layer.

5. The method according to claim 4, characterized in that, The contact mixing operation includes: (1) The hydroxyl-terminated polybutadiene is pretreated to obtain pretreated hydroxyl-terminated polybutadiene; (2) Dioctyl sebacate, toughening agent, plasticizer and the pretreated hydroxyl-terminated polybutadiene are mixed in the first mixture to obtain mixture I; (3) Mixture I is mixed with polyethylene oxide and inorganic filler to obtain mixture II; (4) Mix the mixture II and the isocyanate crosslinking agent in a third mixing to obtain the waterproof adhesive to be molded.

6. The method according to claim 5, characterized in that, The conditions for the first mixing include: a rotation speed of 500-800 rpm, a temperature of 55-65℃, and a time of 0.5-2.5 h; And / or, the conditions for the second mixing include: a rotation speed of 1000-1300 rpm, a temperature of 55-65°C, and a time of 1.5-4.5 h; And / or, the conditions for the third mixing include: a rotation speed of 100-400 rpm, a temperature of 40-45°C, and a time of 30-60 min.

7. A waterproof adhesive layer prepared by the method according to any one of claims 4-6.

8. A waterproof membrane resistant to ultra-low temperatures, characterized in that, This ultra-low temperature resistant waterproof membrane contains a release membrane layer, an ultra-low temperature adhesive layer, a reinforcing layer, and a waterproof adhesive layer stacked in sequence. The waterproof adhesive layer is the waterproof adhesive layer described in claim 7; Preferably, the thickness of the isolation membrane layer is 0.03-0.05 mm; the thickness of the ultra-low temperature adhesive layer is 0.3-0.5 mm; the thickness of the carcass reinforcement layer is 1.0-1.5 mm; and the thickness of the waterproof adhesive layer is 1.5-2.0 mm.

9. A method for preparing the ultra-low temperature resistant waterproof membrane according to claim 8, characterized in that, The method includes: S1: Apply the waterproof adhesive material of the waterproof adhesive layer to one side surface of the pretreated carcass reinforcement layer to obtain the intermediate; S2: The intermediate is cured and aged sequentially to obtain a waterproof adhesive layer; an ultra-low temperature adhesive layer and a release film layer are sequentially applied to the other side surface of the reinforcing layer to obtain the ultra-low temperature resistant waterproof membrane.

10. The application of the ultra-low temperature resistant waterproof membrane according to claim 8 in waterproofing projects and seepage prevention construction projects.

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