CPS (Chlorinated Polystyrene) reaction sticky waterproof coiled material capable of quickly reacting with concrete base

Abstract

The invention belongs to the technical field of waterproof coiled materials, and particularly relates to a CPS reaction bonding waterproof coiled material capable of rapidly reacting with a concrete base layer, and the waterproof coiled material is formed by jointly compounding a two-stage rapid reaction bonding layer, a reinforced tire (core) layer and a sulphoaluminate cement-early strength agent composite rapid reaction isolation layer; wherein the two-stage rapid reaction bonding layer is formed by taking matrix asphalt as a base material and compounding coumarone-indene active resin, a bisphenol A type epoxy prepolymer, a diphenylmethane diisocyanate prepolymer, an SBS (Styrene Butadiene Styrene) elastic modifier, a functional aid and a physical mortise and tenon material; the sulphoaluminate cement-early strength agent composite isolation layer replaces a traditional isolation protection layer, the procedure of tearing off an isolation protection layer material in the product construction process is omitted, generation of construction waste is reduced, more importantly, hydration is fast in the wet paving construction process, and stable 50-70 DEG C medium-temperature reaction conditions are provided for two-stage cross-linking reaction.

Description

Technical Field

[0001] This invention belongs to the field of waterproof membrane technology, specifically relating to a CPS reactive adhesive waterproof membrane that can react rapidly with concrete substrates. Background Technology

[0002] In the field of building waterproofing engineering, wet-laid waterproof membranes are widely used in underground projects, roofing projects, and kitchen and bathroom waterproofing due to their ease of construction. The bonding and fixing of these membranes to the concrete substrate primarily employs the wet-laying method. Currently, the mainstream technology in the industry relies on a cement slurry layer on the back of the membrane for hydration and curing. The bonding between the two is achieved through the physical embedding of the cement slurry with the concrete surface, forming a waterproof layer. To optimize construction efficiency, some existing technologies add early-strength agents to the cement slurry to accelerate the cement's curing rate. However, the overall approach still adheres to the core principle of physical bonding driven by cement hydration and curing, and has long been recognized as the fundamental solution for wet-laid waterproof membrane construction.

[0003] However, the aforementioned existing technical solutions have certain shortcomings, which can affect project quality and construction efficiency. First, the bonding waiting period is too long. The cement slurry usually takes 1-14 days to fully cure. During this period, the waterproof layer cannot withstand being stepped on, and inspection and subsequent procedures cannot be carried out. This can easily lead to delays for projects with tight schedules. Secondly, it is highly sensitive to the environment. When the construction temperature is below 5℃, the cement hydration reaction will stop and the bonding strength cannot grow normally. When it rains, the uncured cement paste is easily washed away by rainwater or the strength will be reduced due to rainwater seepage. Additional heat preservation and rainproof measures are required, which not only increases the construction cost, but may also affect the bonding quality due to inadequate measures. Finally, the bonding reliability is insufficient. The bonding method, which relies solely on physical embedding, is prone to causing the waterproof layer to become hollow or detach when the temperature changes or the substrate is slightly deformed, which greatly increases the risk of leakage in the later stage. The improved solution of adding early strength agent can only speed up the cement curing speed, but does not fundamentally get rid of the dependence on cement hydration. Moreover, excessive use of early strength agent will increase the brittleness of the bonding layer, which will reduce the durability of the waterproof layer and fail to meet the requirements of long-term use of buildings.

[0004] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to provide a CPS reactive adhesive waterproof membrane that can react rapidly with concrete substrates, so as to solve the problems existing in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A CPS reactive adhesive waterproof membrane that can rapidly react with concrete substrates is disclosed. The waterproof membrane is composed of two-stage rapid-reaction adhesive layers, a reinforcing core layer, and a sulfoaluminate cement-early-strength agent composite rapid-reaction isolation layer. The two-stage rapid-reaction adhesive layers use asphalt as the base material and are compounded with coumarone-indene reactive resin, bisphenol A type epoxy prepolymer, diphenylmethane diisocyanate prepolymer, SBS elastic modifier, functional additives, and physical tenon and mortise materials. The sulfoaluminate cement-early-strength agent composite isolation layer replaces the traditional isolation and protective layer, eliminating the need to remove the isolation and protective layer material during construction, reducing construction waste. More importantly, it rapidly hydrates during wet-laying, providing stable 50-70℃ medium-temperature reaction conditions for the two-stage cross-linking reaction.

[0007] Furthermore, by weight, the specific amounts of each component in the two-stage rapid reaction adhesive layer are as follows: base asphalt 35-50%, coumarone-indene reactive resin 8-15%, bisphenol A type epoxy prepolymer 6-12%, diphenylmethane diisocyanate prepolymer 3-8%, SBS elastic modifier 4-10%, functional additives 5-10%, physical tenon and mortise material 0.3%-5%, and inorganic filler 17-38%; Furthermore, by weight, the functional additives comprise 0.5-1.5% of a rapid crosslinking initiator, 1-2% of a penetrant, 0.3-1.0% of a medium-temperature crosslinking accelerator, 0.5-1.5% of an anti-aging stabilizer, and 2-4% of a tackifying resin; Furthermore, the rapid crosslinking initiator is a compound of benzoyl peroxide and N,N-dimethylaniline; Furthermore, the intermediate-temperature crosslinking accelerator is a compound of thiol compounds and triethylamine; Furthermore, the nano-calcium carbonate has a particle size of 50-100 nm; the graphene nanosheets have a thickness of 0.5-2 nm and a diameter of 5-10 μm; and the modified nano-silica has a particle size of 20-50 nm.

[0008] Furthermore, by weight, the specific amounts of each component in the sulfoaluminate cement-early strength agent composite isolation layer are: sulfoaluminate cement 80-95%, early strength agent 5-20%.

[0009] Furthermore, the early strength agent is selected from at least one of triethanolamine, calcium formate, lithium sulfate, and lithium carbonate.

[0010] Furthermore, the preparation method of the CPS reactive adhesive waterproof membrane that can rapidly react with concrete substrate is characterized by comprising the following steps: S1. Raw material pretreatment: Heat the base asphalt to 100-140℃ and keep it at that temperature for 30-60 minutes to dehydrate until no bubbles are present; heat the bisphenol A type epoxy prepolymer and diphenylmethane diisocyanate prepolymer to 55-65℃ and stir until melted; mix the sulfoaluminate cement and early strength agent evenly in proportion, preheat to 80-100℃, remove surface impurities and moisture, and prepare the isolation layer dry powder material; S2. Preparation of two-stage rapid reaction adhesive layer: Dehydrated asphalt is transferred to a high-speed shear reactor and cooled to 90-130℃. Coumarone-indene active resin, penetrant, tackifying resin, and crosslinking initiator are added. Shearing is performed at 3000-5000 r / min for 15-25 min. The mixture is then allowed to stand at room temperature for 10-30 min to complete the first-stage rapid interfacial anchoring reaction, resulting in pre-crosslinked asphalt rubber. The pre-crosslinked asphalt rubber is heated to 160℃ at a rate of 2-3℃ / min. A medium-temperature crosslinking accelerator, SBS elastic modifier, anti-aging stabilizer, and physical interlocking material are added. The rotation speed is adjusted to 1000-2000 r / min, and the mixture is stirred for 30-60 min to complete the second-stage deep crosslinking, forming a dense interpenetrating polymer network (IPN) structure adhesive. S3. Coil composite molding: ① Heat the two-stage fast-reaction adhesive to 140-180℃ and apply it evenly to the surface of the reinforcing (core) layer using a coating roller, with a coating thickness of 0.4-3.0 mm; ② Apply the dry powder of the isolation layer evenly to the upper surface of the two-stage fast-reaction adhesive layer using a scraper roller, with a coating thickness of 0.1-0.5 mm, to form a sulfoaluminate cement-early strength agent composite fast-reaction isolation layer; S4. Slitting and winding: The composite roll material is slitting into standard widths using a slitting machine, then wound up and packaged to obtain the finished product.

[0011] The construction method of the CPS reactive adhesive waterproof membrane that can rapidly react with concrete substrates according to the present invention specifically includes the following steps: a. Grassroots handling Clean the concrete base surface of floating dust and oil stains, and remove standing water. For local pits and uneven areas, use special repair mortar to level the surface until the flatness is ≤5mm. b. Detailed node processing Make the inside and outside corners into 50mm rounded arcs to reduce stress concentration; first apply waterproof sealant (100mm wide) to the pipe root, apply the sealant evenly, and control the thickness to 1-2mm, then add a 500mm wide roll material reinforcement layer, and press it with a scraper to ensure that the sealant is tightly bonded to the roll material and the base layer. c. Roll material installation Remove the release film from the roll material and lay the roll material along the axial direction. With the fast-reaction adhesive layer of the roll material facing the concrete base, align the laying position and use a rubber scraper to roll from the center outwards to expel air. During the rolling process, pay attention to controlling the force of the scraper to ensure that the fast-reaction adhesive layer is in complete contact and adheres to the concrete base. d. Curing and solidification Curing can be carried out naturally at 25℃ for 0.5-2 hours. During the curing period, no covering is required in case of light rain. After the rain stops, check the adhesive layer for any signs of erosion. At low temperatures of 5-10℃, curing can be assisted by heating. Turn on the infrared heater and control the auxiliary heating temperature at 15-20℃. Adjust the heating time according to the ambient temperature to ensure that the adhesive layer temperature is not lower than 15℃. After heating for at least 2 hours, turn off the heater and allow it to cool naturally to room temperature. e. Acceptance and subsequent construction After curing, the "scratch, peel, and pry" method is used for inspection: Five random scratches (each 100mm long) are made, and the bonded surface is observed to show no delamination; peeling is performed from the scratches and corners, and the bonded surface is firmly bonded with a continuous sealing layer visible; the pipe roots, internal and external corners, and other detailed nodes are pried open, and no hollow areas or curling are found; the bond strength is then sampled and tested every 1000m. 2 Three samples were taken, and the peel strength between the roll material and the concrete substrate at all three test points met the requirement of ≥1.0 N / mm. After passing the acceptance test, subsequent procedures such as backfilling and reinforcing bar binding can be carried out.

[0012] Compared with the prior art, the present invention has the following beneficial effects: (1) The core innovation of this invention lies in the synergistic reaction mechanism of primary rapid anchoring and reactive cross-linking, and the secondary cross-linking at a medium temperature of 50-70℃ with self-supplied heat of hydration of the isolation layer, as detailed below: First-order rapid anchoring response: ① Free radical oxidative crosslinking: Benzoyl peroxide decomposes under the action of N,N-dimethylaniline to generate free radicals, which initiate the polymerization of coumarone-indene resin double bonds to form an elastic colloidal network: (C6H5COO)2 2C6H5COO· nCH2=CH-C9H7 -[CH2-CH(C9H7)] - n ② Epoxy ring-opening condensation: The epoxy prepolymer undergoes a condensation reaction with the calcium hydroxide in the concrete substrate, achieving chemical anchoring. At the same time, the penetrant drives the adhesive to penetrate into the capillaries, forming a mechanical interlocking. nC 21 H 24 O4 + Ca(OH)2 [-O-CH2-CH(OH)-CH2-O-C6H4-C(CH3)2-C6H4 - ]nO-Ca-O-[-C6H4-C(CH3)2-C6H4-O-CH2-CH(OH)-CH2-] - n ③ Isocyanate moisture curing: Isocyanate groups undergo addition and ureation reactions with moisture on the concrete substrate to form a polyurea cross-linked structure. R-NCO + H2O —— R-NH2 + CO2↑ 2R-NCO + R-NH2 ——R-NH-CO-NH-R + R-NH-CO-NH-R Secondary intermediate-temperature deep crosslinking reaction When the sulfoaluminate cement-early strength agent composite isolation layer comes into contact with a damp substrate, a rapid hydration reaction occurs, releasing a large amount of heat of hydration. The reaction equation is as follows: 3CaO·3Al2O3·CaSO4 + 26H2O CaO·Al₂O₃·2H₂O + 2(CaSO₄·2H₂O) + heat This heat of hydration can stably maintain the temperature at the interface between the roll material and the substrate at 50-70℃, providing a continuous and stable medium-temperature environment for secondary crosslinking without the need for additional heating equipment. At this temperature, the active groups copolymerize: the primary residual groups copolymerize with the asphalt aromatics to form a preliminary interpenetrating network; the copolymerization and bonding reactions continue, the crosslinking density increases, and a stable composite bonding system is formed.

[0013] Bonding mechanism with cement substrate: The bonding between the roll material and the cement substrate is the result of the synergistic effect of chemical anchoring, mechanical interlocking, and penetrating filling: chemical anchoring achieves molecular-level bonding, mechanical interlocking prevents interlayer slippage, and penetrating filling repairs micro-cracks in the substrate, completely eliminating the risk of water seepage.

[0014] Fast bonding speed and high construction efficiency: Through the catalysis of a rapid cross-linking initiator, subsequent processes can be carried out quickly after construction.

[0015] (2) The present invention uses a sulfoaluminate cement-early strength agent composite isolation layer to replace the traditional polyester film (PET) and polyethylene film (PE) polymer isolation protective layer, eliminating the need to remove the isolation protective layer material during the product construction process, reducing the generation of construction waste. More importantly, it can quickly hydrate during wet laying construction, providing stable 50-70℃ medium temperature reaction conditions for the two-stage cross-linking reaction.

[0016] The roll material of this invention is suitable for waterproofing projects such as underground garages, tunnels, subways, and roofs, and is especially suitable for green building fields with high requirements for waterproofing and durability. Detailed Implementation

[0017] The technical solution of this invention patent will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0018] Example 1 Secondary fast-reaction adhesive layer (mass fraction): 90# base asphalt 45%, coumarone-indene reactive resin 5%, bisphenol A type epoxy prepolymer (E-51) 7.5%, diphenylmethane diisocyanate prepolymer 5%, SBS elastic modifier (linear 301) 7%, functional additives 10% (alkylphenol polyoxyethylene ether 1.5%, 1,6-hexanedithiol-triethylamine crosslinking accelerator 2%, antioxidant 1010-UV-531 stabilizer 1%, terpene resin 5%), nano calcium carbonate 1.0%, talc powder 20%; Sulfoaluminate cement-early strength agent composite isolation layer: 90% sulfoaluminate cement, 10% calcium formate early strength agent; Reinforced core layer: 0.1mm PET base; Preparation steps: S1. 90# base asphalt dehydrated at 130℃ for 45 min; epoxy prepolymer and isocyanate prepolymer melted at 60℃; polyester nonwoven fabric preheated at 80℃; mixed isolation layer dry powder.

[0019] S2. Cool the dehydrated asphalt to 110℃, add active resin, penetrant, initiator, etc., shear at 4000r / min for 20min, and let stand at room temperature for 20min to complete the first-stage reaction; heat to 160℃, add crosslinking accelerator, SBS, etc., and stir at 1500r / min for 40min to complete the crosslinking reaction.

[0020] S3. The adhesive is applied to the PET base surface at 100°C with a thickness of 1.3 mm; the dry powder of the release layer is applied to the adhesive surface with a thickness of 0.2 mm.

[0021] S4. Cooling, slitting, and winding of the roll material.

[0022] Example 2 Second-order fast-reaction adhesive layer (mass fraction): 70# base asphalt 43.5%, coumarone-indene reactive resin 8%, bisphenol A type epoxy prepolymer (E-44) 6%, diphenylmethane diisocyanate prepolymer 4%, SBS elastic modifier (star-shaped 4303) 5%, functional additives 8%, modified nano silica 0.5%, heavy calcium carbonate powder 25%; Sulfoaluminate cement-early strength agent composite isolation layer: 80% sulfoaluminate cement, 20% sodium sulfate early strength agent; Reinforced core layer: 110g / m 2 Fiberglass mesh; Preparation steps: Same as in Example 1.

[0023] Example 3 Second-order fast-reaction adhesive layer (mass fraction): 90# base asphalt 58%, coumarone-indene reactive resin 12%, bisphenol A type epoxy prepolymer (E-51) 10%, diphenylmethane diisocyanate prepolymer 6%, SBS elastic modifier (linear 791) 10%, functional additives 4%, graphene 0.5%, heavy calcium carbonate powder 17%; Sulfoaluminate cement-early strength agent composite isolation layer: 85% sulfoaluminate cement, 15% triethanolamine early strength agent; Reinforced core layer: 140g / m 2 Polyester fiberglass cloth composite layer; Preparation steps: basically the same as in Example 1.

[0024] Comparative Example Traditional wet-laid waterproof membrane (PET release liner) 1.3 Performance Testing The test items are shown in Table 2, and the test results are shown in Table 3.

[0025] Table 2. Test Items, Test Methods, Basis and Explanation

[0026] Table 3. Effects of different fast-reaction adhesive layers on the performance of wet-laid waterproof membranes

[0027] Performance testing: No cracks at -20℃ low temperature; 92% retention rate of strength during water aging; peel strength from concrete: 2.5 N / mm.

[0028] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A CPS reactive adhesive waterproof membrane capable of rapidly reacting with a concrete substrate, comprising a two-stage rapid-reaction adhesive layer, a reinforcing core layer, and a sulfoaluminate cement-early-strength agent composite rapid-reaction isolation layer, characterized in that, in, By mass fraction, the two-stage rapid-reaction adhesive layer comprises: 35-50% base asphalt, 8-15% coumarone-indene reactive resin, 6-12% bisphenol A type epoxy prepolymer, 3-8% diphenylmethane diisocyanate prepolymer, 4-10% SBS elastic modifier, 5-10% functional additives, 0.3%-5% physical tenon and mortise material, and 17-38% inorganic filler; The functional additives include 0.5-1.5% rapid crosslinking initiator, 1-2% penetrant, 0.3-1.0% medium-temperature crosslinking accelerator, 0.5-1.5% anti-aging stabilizer, and 2-4% tackifying resin; The rapid crosslinking initiator is a compound of benzoyl peroxide and N,N-dimethylaniline; The intermediate-temperature crosslinking accelerator is a compound of thiol compounds and triethylamine; The physical mortise and tenon material is composed of one or more of nano-calcium carbonate, graphene nanosheets, and modified nano-silica. The inorganic filler is composed of one or more of the following: heavy calcium carbonate powder, talc powder, and fly ash; The sulfoaluminate cement-early strength agent composite isolation layer, by mass fraction, consists of 80-95% sulfoaluminate cement and 5-20% early strength agent.

2. The CPS reactive waterproof membrane that can rapidly react with concrete substrates according to claim 1, characterized in that, The base asphalt is 70# or 90# road petroleum asphalt with a penetration of 60-100 (0.1mm) and a softening point of 45-55℃; the reinforcing tire (core) is a polymer reinforcing base such as PET or PE, polyester nonwoven fabric, fiberglass mesh, polyester fiberglass fabric composite layer, or a core-skin structure reinforcing base. According to claim 1, the CPS reactive waterproof membrane that can react rapidly with concrete substrate is characterized in that the penetrant is alkylphenol polyoxyethylene ether, which can drive the adhesive layer to penetrate 3-5mm into the capillary pores of the concrete substrate within 10-20 minutes; the anti-aging stabilizer is a compound of antioxidant 1010 and ultraviolet absorber UV-531; the tackifying resin is terpene resin or C5 petroleum resin; and the early strength agent of the sulfoaluminate cement-early strength agent composite isolation layer can be selected from one or two of calcium formate, sodium sulfate, triethanolamine, lithium sulfate, and lithium carbonate.

3. A method for preparing a CPS reactive adhesive waterproof membrane capable of rapid reaction with a concrete substrate as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. Raw material pretreatment: Heat the base asphalt to 100-140℃ and keep it at that temperature for 30-60 minutes to dehydrate until no bubbles are present; heat the bisphenol A type epoxy prepolymer and diphenylmethane diisocyanate prepolymer to 55-65℃ and stir until melted; mix the sulfoaluminate cement and early strength agent evenly in proportion, preheat to 80-100℃, remove surface impurities and moisture, and prepare the isolation layer dry powder material; S2. Preparation of two-stage rapid reaction adhesive layer: Dehydrated asphalt is transferred to a high-speed shear reactor and cooled to 90-130℃. Coumarone-indene active resin, penetrant, tackifying resin, and crosslinking initiator are added. Shearing is performed at 3000-5000 r / min for 15-25 min. The mixture is then allowed to stand at room temperature for 10-30 min to complete the first-stage rapid interfacial anchoring reaction, resulting in pre-crosslinked asphalt rubber. The pre-crosslinked asphalt rubber is heated to 160℃ at a rate of 2-3℃ / min. A medium-temperature crosslinking accelerator, SBS elastic modifier, anti-aging stabilizer, and physical interlocking material are added. The rotation speed is adjusted to 1000-2000 r / min, and the mixture is stirred for 30-60 min to complete the second-stage deep crosslinking, forming a dense interpenetrating polymer network (IPN) structure adhesive. S3. Coil composite molding: ① Heat the two-stage fast-reaction adhesive to 140-180℃ and apply it evenly to the surface of the reinforcing (core) layer using a coating roller, with a coating thickness of 0.4-3.0 mm; ② Apply the dry powder of the isolation layer evenly to the upper surface of the two-stage fast-reaction adhesive layer using a scraper roller, with a coating thickness of 0.1-0.5 mm, to form a sulfoaluminate cement-early strength agent composite fast-reaction isolation layer; S4. Slitting and winding: The composite roll material is slitting into standard widths using a slitting machine, then wound up and packaged to obtain the finished product.

4. The preparation method according to claim 4, characterized in that, In step S2, three major reactions occur simultaneously during the primary rapid interface anchoring reaction: ① The rapid crosslinking initiator decomposes to generate free radicals, initiating the addition polymerization of unsaturated double bonds in the coumarone-indene active resin; ② The bisphenol A type epoxy prepolymer undergoes a ring-opening condensation reaction with calcium hydroxide, a hydration product of the concrete substrate; ③ The diphenylmethane diisocyanate prepolymer undergoes an addition and ureaization reaction with moisture on the substrate surface; the sulfoaluminate cement-early strength agent composite isolation layer releases heat of hydration during wet-laying construction, providing the medium-temperature environment required for the secondary crosslinking reaction.

5. The preparation method according to claim 4, characterized in that, In step S2, the secondary deep crosslinking reaction is carried out in two steps: ① The primary residual active groups and the asphalt aromatics undergo a copolymerization reaction to form a preliminary interpenetrating network; ② The SBS elastic modifier polybutadiene block double bonds undergo a covalent bonding reaction with the IPN network; the isolation layer can also prevent the adhesive layer surface from sticking and improve the convenience of roll material transportation and construction.

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