Preparation method of nano-penetrating reaction adhesive polymer waterproofing membrane

Abstract

The application provides a preparation method of a nano-penetrating reaction-adhesive high-molecular waterproof roll material and belongs to the technical field of waterproof roll materials. The nano-penetrating reaction-adhesive high-molecular rubber material is prepared by taking asphalt, naphthenic oil, epoxy resin, polysulfide rubber, a bitumen modifier, petroleum resin, a ketone imine curing agent, a silane coupling agent and calcium carbonate as raw materials, and then the nano-penetrating reaction-adhesive high-molecular rubber material is compounded with a carcass layer and a release film to obtain the nano-penetrating reaction-adhesive high-molecular waterproof roll material. The synergistic mechanism of 'chemical bonding + physical anchoring + ultrahigh cohesive strength' is used to improve the peeling strength with cement mortar.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, and in particular to a method for preparing a nano-permeable reactive adhesive polymer waterproof membrane. Background Technology

[0002] Currently, high-performance, environmentally friendly asphalt-based wet-laid roofing membranes are more favored by the market and have gained recognition from green building standards. With technological advancements and increasingly stringent environmental requirements, new construction methods such as wet-laying are replacing traditional hot-melt SBS processes. Their core advantages lie in: Environmentally friendly and safe, driven by policy: The wet laying method is a cold construction method without open flame, which avoids the environmental pollution and safety hazards of traditional hot-melt SBS rolls and is more in line with the current environmental protection policy.

[0003] Highly adaptable and ensuring project completion: It has low requirements for the dryness of the substrate; construction can proceed even when the substrate is damp but without standing water. This greatly reduces the impact of weather on the project schedule and improves construction efficiency.

[0004] Reliable adhesion and good waterproofing: The cement mortar achieves full adhesion to the substrate, effectively eliminating the "water seepage layer". Even if there is local damage, water will not flow freely, making it easy to repair and providing a relatively reliable waterproofing effect.

[0005] However, the asphalt-based wet-laid membranes currently on the market still have some problems in construction and application, such as: 1. Sensitivity to extreme temperatures. At high temperatures, the adhesive layer may soften, creep, or flow, causing the membrane to slip or the joints to shift. At low temperatures, the viscosity of the adhesive layer decreases, resulting in insufficient adhesion during construction and difficulty in effective bonding; 2. Long drying and curing time. Cement slurry requires time to cure, and the bonding strength between the adhesive layer and cement slurry is often affected by the environment and the viscosity of the adhesive itself. In long-term immersion in water, swelling, performance degradation, or detachment from the substrate often occur, affecting the durability of the waterproof layer.

[0006] Therefore, it is necessary to develop a super-strong bonding material that can adapt to extreme temperatures, quickly gain strength with cement mortar, and also ensure durability. Through experimental verification and comparison, it was found that epoxy asphalt has better bonding strength than ordinary modified asphalt. At the same time, to address the shortcomings of epoxy asphalt, corresponding performance improvements were made by introducing curing agents, polysulfide rubber, resin tackifiers, and silane coupling agents. Summary of the Invention

[0007] In view of this, the purpose of this invention is to provide a method for preparing a nano-permeable reactive adhesive polymer waterproof membrane, which improves the peel strength from cement mortar through a synergistic mechanism of "chemical bonding + physical anchoring + ultra-high cohesive strength".

[0008] The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane includes the following steps: (1) Mix asphalt and naphthenic oil in sequence according to the proportion, and stir at low speed until uniform; heat to 170-180℃, add epoxy resin, polysulfide rubber, asphalt modifier, petroleum resin and ketimide curing agent, and stir at high temperature and high speed for 2-3 hours to obtain the rubber compound. (2) Add silane coupling agent to the adhesive and stir at high temperature and high speed for 2-2.5h; add calcium carbonate and stir at high speed for 1-1.5h to obtain nano-penetrating reactive adhesive polymer adhesive, and send it to the coating production line after cooling to 170-180℃. (3) Coat both sides of the substrate with the polymer adhesive obtained in step (2), then coat the surface of the adhesive with a PP high barrier anti-sticking membrane, cool and roll up to obtain the nano-permeable reactive adhesive polymer waterproof membrane.

[0009] Preferably, the low-speed stirring frequency in step (1) is 15-20Hz and the time is 2-3h; the high-temperature high-speed stirring frequency is 40-45Hz and the temperature is 170-180℃.

[0010] Preferably, the high-temperature high-speed stirring frequency in step (2) is 40-45Hz and the temperature is 170-180℃.

[0011] Preferably, the tire body layer in step (3) is a polyester tire or a polyethylene high-strength film with surface treatment; the thickness of the tire body layer in step (3) is 0.07-0.075mm, the thickness of the rubber compound is 0.70-0.72mm, and the thickness of the PP high-barrier anti-sticking release film is 0.02-0.03mm.

[0012] Preferably, the nano-permeable reactive adhesive polymer comprises the following raw materials in parts by weight: 90-100 parts asphalt, 10-20 parts naphthenic oil, 20-25 parts epoxy resin, 4-5 parts ketimide curing agent, 2-3 parts polysulfide rubber, 6-8 parts SBR asphalt modifier, 2-4 parts petroleum resin, 1-3 parts silane coupling agent, and 50-55 parts calcium carbonate.

[0013] More preferably, the asphalt is 70# asphalt or 90# asphalt.

[0014] More preferably, the polysulfide rubber is liquid polysulfide rubber.

[0015] More preferably, the asphalt modifier is an SBR asphalt modifier.

[0016] More preferably, the petroleum resin is a C7-C9 petroleum resin.

[0017] More preferably, the calcium carbonate has a particle size of 350-400 mesh.

[0018] The purpose of this invention is to provide a method for preparing a nano-permeable reactive adhesive polymer waterproof membrane. Compared with the prior art, this invention has the following advantages: 1. Extremely strong chemical adhesion Epoxy resins contain highly reactive epoxy groups, which can form strong chemical bonds with the hydroxyl groups (-OH) on the surface of cement mortar hydration products (such as calcium hydroxide and calcium silicate gel), creating chemical bonds that are much stronger than those formed by physical adsorption. This is the most fundamental difference between it and ordinary asphalt (which relies solely on physical adsorption and van der Waals forces).

[0019] 2. Excellent penetration and anchoring capabilities Epoxy asphalt has a low viscosity in the initial stage after mixing, allowing it to penetrate deeply into the microcracks and pores of cement mortar. After curing, these penetrated portions act like countless "miniature chemical anchors," mechanically locking the two together.

[0020] 3. Extremely high cohesive strength Cured epoxy asphalt material has extremely high tensile strength (>10 MPa), far exceeding that of ordinary asphalt (approximately 1-2 MPa). In peel tests, failure often does not occur at the bonding interface, but rather transfers to the interior of the cement mortar base layer or the epoxy asphalt layer (cohesive failure), indicating that its interfacial bond strength has exceeded part of the material's own strength.

[0021] 4. Excellent weather resistance and stability Fully cured epoxy asphalt is a thermosetting material that does not soften or become brittle with temperature changes. It maintains extremely high bond strength and modulus within a temperature range of -20℃ to 60℃, avoiding the bond failure caused by ordinary asphalt softening in summer and becoming brittle in winter. Detailed Implementation

[0022] This invention provides a nano-permeable reactive adhesive polymer waterproof membrane, the raw materials of which are as follows: 90-100 parts asphalt, 10-20 parts naphthenic oil, 20-25 parts epoxy resin, 4-5 parts ketimide curing agent, 2-3 parts polysulfide rubber, 6-8 parts SBR asphalt modifier, 2-4 parts petroleum resin, 1-3 parts silane coupling agent, and 50-55 parts calcium carbonate.

[0023] Preferably, the asphalt is 70# asphalt.

[0024] Preferably, the naphthenic oil is KN4010 purchased from Guangzhou Wanshun Chemical Co., Ltd. Naphthenic oil can quickly restore the elasticity and toughness of rubber and resist aging caused by ultraviolet rays and temperature changes.

[0025] Preferably, the epoxy resin is E-51, which is a key material for chemical bonding.

[0026] Preferably, the ketimide curing agent is FT-335 purchased from Jining Baichuan Chemical Co., Ltd. The ketimide curing agent is moisture-activated, which ensures that the epoxy asphalt adhesive is inert at room temperature. During construction, the final irreversible curing reaction is triggered by moisture, and a strong chemical bond is formed with the hydroxyl groups (-OH) on the surface of cement mortar hydration products (such as calcium hydroxide and calcium silicate gel), forming a chemical bond that is much stronger than physical adsorption.

[0027] Preferably, the polysulfide rubber is liquid polysulfide rubber JLY-121, purchased from Kandis Chemical (Hubei) Co., Ltd. Polysulfide rubber directly solves the inherent shortcomings of epoxy asphalt systems being too hard and brittle. Through chemical reaction, it embeds its own flexible genes into the rigid epoxy network. Without significantly sacrificing strength, adhesion and chemical resistance, it miraculously endows epoxy asphalt materials with excellent flexibility, impact resistance and low-temperature performance, thus opening up the technical path for applying this super-strong bonding material to the field of roll materials that require bending, deformation and impact.

[0028] Preferably, the asphalt modifier is an SBR asphalt modifier. In a specific embodiment of the present invention, it is 95% GSBR, purchased from Shandong Gaoshi Science and Technology Co., Ltd. Through its compliant molecular chain, it effectively solves the problem of asphalt brittleness at low temperatures at a relatively low cost, and significantly improves the adhesion and ductility of the material.

[0029] Preferably, the petroleum resin is C9 (carbon nine) petroleum resin SJY-90, purchased from Sanjiangyuan Chemical (Henan) Co., Ltd., and is used to improve the initial tack during construction.

[0030] Preferably, the silane coupling agent is SK-500 silane coupling agent, which enhances the chemical adhesion to the substrate.

[0031] Preferably, the calcium carbonate has a particle size of 400 mesh and is added as a filler.

[0032] The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane includes the following steps: (1) Mix asphalt and naphthenic oil in sequence according to the proportion, stir at low speed (15-20Hz, 10min) until uniform; heat to 170-180℃, add epoxy resin, polysulfide rubber, asphalt modifier, petroleum resin and ketimide curing agent, stir at high temperature and high speed (40-45Hz, 170-180℃) for 2-3h to obtain the rubber compound; (2) Add silane coupling agent to the adhesive and stir at high temperature and high speed (40-45Hz, 170-180℃) for 2-2.5h; add calcium carbonate and stir at high speed for 1-1.5h to obtain nano-penetrating reactive adhesive polymer adhesive. After cooling to 170-180℃, send it to the coating production line. (3) Coat both sides of the base layer with the polymer adhesive obtained in step (2), then coat the surface of the adhesive with a PP high barrier anti-sticking membrane, cool and roll up to obtain the nano-penetrating reactive adhesive polymer waterproof membrane; the thickness of the base layer is 0.075mm, the thickness of the adhesive is 0.72mm, and the thickness of the PP high barrier anti-sticking membrane is 0.03mm.

[0033] In a specific embodiment of the present invention, the body layer is a high-strength polyethylene film with surface treatment (Cangzhou Zhaoyang Paper & Plastic Packaging Co., Ltd., transparent PET PETZY103); the PP high-barrier anti-sticking release film is manufactured by Cangzhou Zhaoyang Paper & Plastic Packaging Co., Ltd., anti-sticking barrier silicone oil film PP ZY102.

[0034] The present invention will be further described below with reference to the embodiments.

[0035] Example 1 Different nano-permeable reactive adhesive polymers were prepared by adjusting the raw material composition. The raw materials are shown in Table 1.

[0036] Table 1

[0037] The steps for preparing nano-permeable reactive adhesive polymer waterproof membrane using the above four methods are as follows: (1) Mix asphalt and naphthenic oil in sequence according to the proportion, stir at low speed (15Hz, 10min) until uniform; heat to 180℃, add epoxy resin, polysulfide rubber, asphalt modifier, petroleum resin and ketimide curing agent, stir at high temperature and high speed (40Hz, 180℃) for 3h to obtain rubber compound. (2) Add silane coupling agent to the adhesive and stir at high temperature and high speed (40Hz, 180℃) for 2h; add calcium carbonate and stir at high speed (40Hz) for 1h to obtain nano-penetrating reactive adhesive polymer adhesive, and send it to the coating production line after cooling to 175℃. (3) Coat both sides of the base layer with the polymer adhesive obtained in step (2), then coat the surface of the adhesive with a PP high barrier anti-sticking membrane, cool and roll up to obtain the nano-penetrating reactive adhesive polymer waterproof membrane; the thickness of the base layer is 0.075mm, the thickness of the adhesive is 0.72mm, and the thickness of the PP high barrier anti-sticking membrane is 0.03mm.

[0038] The performance of the waterproof membrane was tested (the test methods for tackiness and peel strength from aluminum plate are GB23441-2009 Self-adhesive polymer modified bitumen waterproof membrane; the test methods for heat resistance, low temperature flexibility, lap peel strength and peel strength from post-poured concrete are GB / T35467-2017 Wet-laid waterproof membrane), and the results are shown in Table 2.

[0039] Table 2

[0040] Scheme 1, using the conventional modified asphalt wet-lay mix ratio, serves as a control group; Option 2 abandons the application of adhesive powder, mainly considering the improvement of the material's aging resistance, while improving the low-temperature resistance of the adhesive and the adhesion between the adhesive and cement mortar. Option 3 verifies the strength improvement of the adhesive and its bond peel strength with cement mortar from the perspective of epoxy asphalt modification. Scheme 4 involves the reaction of the polymer adhesive prepared in this invention with cement mortar, with the main focus on improving the bonding strength.

[0041] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a nano-permeable reactive adhesive polymer waterproof membrane, characterized in that, Includes the following steps: (1) Mix asphalt and naphthenic oil in sequence according to the proportion, and stir at low speed until uniform; heat to 170-180℃, add epoxy resin, polysulfide rubber, asphalt modifier, petroleum resin and ketimide curing agent, and stir at high temperature and high speed for 2-3 hours to obtain the rubber compound. (2) Add silane coupling agent to the adhesive and stir at high temperature and high speed for 2-2.5h; add calcium carbonate and stir at high speed for 1-1.5h to obtain nano-penetrating reactive adhesive polymer adhesive, and send it to the coating production line after cooling to 170-180℃. (3) Coat both sides of the substrate with the polymer adhesive obtained in step (2), then coat the surface of the adhesive with a PP high barrier anti-sticking membrane, cool and roll up to obtain the nano-permeable reactive adhesive polymer waterproof membrane.

2. The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane according to claim 1, characterized in that, The low-speed stirring in step (1) has a frequency of 15-20Hz and a time of 2-3h; the high-temperature high-speed stirring has a frequency of 40-45Hz and a temperature of 170-180℃.

3. The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane according to claim 1, characterized in that, The high-temperature high-speed stirring in step (2) has a frequency of 40-45Hz and a temperature of 170-180℃.

4. The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane according to claim 1, characterized in that, The tire body layer in step (3) is a polyester tire or a polyethylene high-strength film with surface treatment; the thickness of the tire body layer in step (3) is 0.07-0.075mm, the thickness of the rubber compound is 0.70-0.72mm, and the thickness of the PP high-barrier anti-sticking release film is 0.02-0.03mm.

5. The method for preparing the nano-permeable reactive adhesive polymer waterproof membrane according to claim 1, characterized in that, The nano-permeable reactive adhesive polymer comprises the following raw materials in parts by weight: 90-100 parts asphalt, 10-20 parts naphthenic oil, 20-25 parts epoxy resin, 4-5 parts ketimide curing agent, 2-3 parts polysulfide rubber, 6-8 parts SBR asphalt modifier, 2-4 parts petroleum resin, 1-3 parts silane coupling agent, and 50-55 parts calcium carbonate.

6. The method for preparing the nano-permeable reactive adhesive polymer waterproof membrane according to claim 5, characterized in that, The asphalt is either 70# or 90# asphalt.

7. The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane according to claim 5, characterized in that, The polysulfide rubber is liquid polysulfide rubber.

8. The method for preparing the nano-permeable reactive adhesive polymer waterproof membrane according to claim 5, characterized in that, The asphalt modifier is an SBR asphalt modifier.

9. The preparation method of the nano-permeable reactive adhesive polymer waterproof membrane according to claim 5, characterized in that, The petroleum resin is a C7-C9 petroleum resin.

10. The method for preparing the nano-permeable reactive adhesive polymer waterproof membrane according to claim 5, characterized in that, The calcium carbonate has a particle size of 350-400 mesh.

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