A primer for base course, its preparation method, and a composite waterproofing system containing the same

Abstract

The present invention discloses a primer for substrate treatment, its preparation method, and a composite waterproofing system containing the same; the primer for substrate treatment includes carboxyl graft-modified epoxy resin, amine curing agent, active diluent, and accelerator; wherein, the epoxy value of the carboxyl graft-modified epoxy resin is 0.30 - 0.38 eq / 100 g, which is determined by the hydrochloric acid-acetone method; the content of the amine curing agent is determined according to the epoxy value of the carboxyl graft-modified epoxy resin, the number of active hydrogen atoms on the amino group in the amine curing agent molecule, and the molecular weight of the amine curing agent; and, the molar ratio of the amine curing agent, active diluent, and accelerator is 1:(4 - 5):(0.2 - 0.4). The primer for substrate treatment of the present invention can increase the sealing property of the base surface and enhance the adhesion between the waterproof coating and the waterproof membrane and the base surface, thereby making the waterproof effect of the composite waterproofing system stronger.

Description

Technical Field

[0001] The present invention relates to the field of building waterproofing, and particularly to a primer for substrate treatment, a preparation method thereof, and a composite waterproof system containing the same. Background Art

[0002] In recent years, in order to address the problem of building leakage, there has been a "roll-coating integrated composite waterproof technology" which fundamentally solves the defects of traditional waterproof construction. The key core of this technology is to use an asphalt-based non-curing waterproof coating to paste a modified asphalt waterproof coil to form a composite waterproof layer, thereby achieving a good waterproof effect.

[0003] In the above technology, ordinary asphalt-based non-curing waterproof coatings are used, which have a pungent smell, have an adverse impact on the environment and human health, and have insufficient adhesion to polymer coils. Therefore, there is still a need to improve the existing roll-coating integrated composite waterproof system. Summary of the Invention

[0004] In view of this, the present invention provides a primer for substrate treatment, a preparation method thereof, and a composite waterproof system containing the same, which can increase the sealing performance of the base surface and enhance the adhesion between the waterproof coating and the waterproof coil and the base surface, thereby making the waterproof effect of the composite waterproof system stronger and improving the environmental friendliness of the composite waterproof system.

[0005] The present invention provides the following technical solutions:

[0006] A primer for substrate treatment for a composite waterproof system includes a carboxyl graft-modified epoxy resin, an amine curing agent, an active diluent, and an accelerator; wherein, the epoxy value of the carboxyl graft-modified epoxy resin is 0.30 - 0.38 eq / 100 g, determined by the hydrochloric acid-acetone method; the content of the amine curing agent is determined according to the epoxy value of the carboxyl graft-modified epoxy resin, the number of active hydrogen atoms on the amino group in the amine curing agent molecule, and the molecular weight of the amine curing agent; and, the molar ratio of the amine curing agent, the active diluent, and the accelerator is 1:(4 - 5):(0.2 - 0.4).

[0007] Optionally, the carboxyl graft-modified epoxy resin is prepared from a composition including bisphenol A epoxy resin, a carboxyl functional monomer, and a thermal initiator.

[0008] Optionally, the molar ratio of the bisphenol A epoxy resin, the carboxyl functional monomer, and the thermal initiator is 1:(2.2 - 2.4):(0.1 - 0.3).

[0009] Optionally, the carboxyl functional monomer includes one or more of the following substituted or unsubstituted carboxylic acids: C16 - C20 alkenyl carboxylic acid, acrylic acid, maleic anhydride; and / or, the thermal initiator is an azo initiator or an organic peroxide.

[0010] Optionally, the content of the amine curing agent is calculated according to the following formula:

[0011] W=(M / H n )×E×1.15

[0012] In the formula:

[0013] W—the mass of the amine curing agent required for every 100 g of the carboxyl graft-modified epoxy resin;

[0014] M—the molecular weight of the amine curing agent;

[0015] H n —the number of active hydrogen atoms on the amino group in the amine curing agent molecule; and

[0016] E—the epoxy value of the carboxyl graft-modified epoxy resin.

[0017] Optionally, the amine curing agent includes one or more of aliphatic amines, cycloaliphatic amines, aromatic amines, and polyamides; the active diluent is an epoxy or hydroxyl solvent; the accelerator is a phenolic accelerator.

[0018] Optionally, the accelerator includes one or more of phenol, 2,4,6-tris(dimethylaminomethyl)phenol, resorcinol, aminophenol, and halogenated phenol.

[0019] The present invention also provides a method for preparing the base treatment agent as described above, including the following steps: mixing an amine curing agent, an active diluent, and an accelerator to obtain a mixture; mixing the carboxyl graft-modified epoxy resin and the mixture to obtain the base treatment agent.

[0020] The present invention also provides a composite waterproof system, which includes a base treatment layer, a non-bituminous non-curing waterproof coating layer, and an environmentally friendly waterproof coil that are sequentially stacked; wherein the base treatment layer is coated with the base treatment agent as described above.

[0021] Optionally, the environmentally friendly waterproof coil is a non-bituminous self-adhesive waterproof coil or a polymer waterproof coil.

[0022] According to the technical solution of the present invention, the primer of the present invention includes carboxyl grafted modified epoxy resin and is used in combination with other components, which can increase the sealing property of the base surface (such as the concrete surface), improve the moisture-proof property of the base surface, reduce the risk of the waterproof layer bulging caused by water vapor penetration, and enhance the adhesion between the waterproof coating and the waterproof roll and the base surface, so that the waterproof effect of the composite waterproof system is stronger. The preparation method of the primer of the present invention is simple and convenient for industrial production. The composite waterproof system of the present invention is a non-bituminous composite waterproof system. On the base surface treated with the primer of the present invention, a non-bituminous non-curing waterproof coating and an environmentally friendly waterproof roll are sequentially arranged, so that the composite waterproof system has excellent creep property and extensibility, can adapt to the deformation of the base surface, and can automatically heal cracks below 2 mm; and can adapt to the construction environments of low temperature (-15 °C) and high temperature (50 °C), and still achieve the first-class waterproof effect; moreover, there is no obvious flue gas during the construction process, and it has excellent environmental protection performance. Detailed Embodiments

[0023] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below with reference to the embodiments. The preferred embodiments of the present invention are given in the embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0024] In the existing "rolling and coating integrated composite waterproof technology", the traditional asphalt-based non-curing waterproof coating used takes rubber and asphalt as the main components. Among them, the rubber component reduces the high and low temperature performance and ductility of the asphalt-based non-curing waterproof coating itself, and even loses the waterproof effect. Secondly, asphalt has defects such as low equivalent softening point and poor low temperature resistance, and asphalt is prone to volatilize irritating odors at high temperatures, seriously polluting the environment and harming the physical health of construction workers. In addition, when the asphalt-based non-curing waterproof coating is used in combination with a polymer waterproof coil, there are some free oil molecules in the asphalt, and the oil molecules will penetrate into the polymer, damaging the original polymer structure, resulting in the performance attenuation of the polymer waterproof coil. In the long-term use process of this composite waterproof system of asphalt-based non-curing waterproof coating and polymer coil, there is a repulsive force between the two interfaces, and it is difficult to form a skin-like full adhesion construction effect, and there is a risk of water channeling. In the existing rolling and coating composite construction process, there are many pores in the base surface, and there is water vapor in the construction base layer. Bulges will appear during the construction process, thus there is a risk of water channeling. The base treatment agent of the present invention can fill the pores of the construction base surface, increase the base layer sealing property, improve the moisture resistance of the base surface, inhibit the risk of the waterproof layer bulging caused by water vapor penetration, and enhance the adhesion between the waterproof material and the base layer, with a stronger waterproof effect. The composite waterproof system of the present invention is a non-asphalt-based waterproof system. On the base surface treated with the base treatment agent of the present invention, a non-asphalt-based non-curing waterproof coating and an environmentally friendly waterproof coil are sequentially provided. The construction convenience of the non-asphalt-based non-curing waterproof coating is equivalent to that of the traditional asphalt-based non-curing waterproof coating. Its material has excellent creepability and extensibility, can adapt to the deformation of the base layer, and can automatically heal cracks less than 2 mm. There is no obvious smoke during the construction process. This brand-new non-asphalt composite waterproof system is a huge breakthrough in the traditional rolling and coating integrated composite waterproof technology, and is better applicable to areas with higher environmental protection requirements.

[0025] In an embodiment of the present invention, the base treatment agent for the composite waterproof system of the present invention includes carboxyl graft-modified epoxy resin, amine curing agent, active diluent, and accelerator.

[0026] The carboxyl graft-modified epoxy resin is prepared from a composition containing bisphenol A-type epoxy resin, carboxyl functional monomer, and thermal initiator. The molar ratio of bisphenol A-type epoxy resin, carboxyl functional monomer to thermal initiator is 1:(2.2 - 2.4):(0.1 - 0.3), for example 1:(2.2 - 2.4):0.2.

[0027] The bisphenol A type epoxy resin can be commercially available or prepared by methods known to those skilled in the art. For example, it can be prepared by condensing bisphenol A and epichlorohydrin under alkaline conditions, followed by washing with water and refining by solvent removal. The bisphenol A type epoxy resin is usually of the E-51 type, E-44 type or E-42 type of bisphenol A type epoxy resin; its epoxy value is 0.38 - 0.54 eq / 100g, which is determined by the hydrochloric acid-acetone method.

[0028] The carboxyl-functional monomer can include one or more of the following substituted or unsubstituted carboxylic acids: C16-C20 alkenyl carboxylic acids, acrylic acid, maleic anhydride and its derivatives; for example, oleic acid ((Z)-9-octadecenoic acid, CAS No. 112-80-1), palmitoleic acid, cis-9-eicosenoic acid, or maleic anhydride.

[0029] The thermal initiator can be an azo initiator or an organic peroxide, for example, including one or more of the following: azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO).

[0030] The preparation method of the carboxyl graft-modified epoxy resin includes:

[0031] (1) Add the bisphenol A type epoxy resin and the carboxyl-functional monomer into a reaction vessel equipped with a stirring device in a molar ratio of 1:(2.2 - 2.4), and stir evenly at a stirring rate of 400 - 800 r / min at a temperature of 90 - 120 °C, for example, 110 °C, for 5 - 10 min;

[0032] (2) Add the thermal initiator into the reaction vessel in a molar ratio of (in the range of 0.1 - 0.3):1 to the bisphenol A type epoxy resin, stir evenly at a stirring rate of 400 - 800 r / min at a temperature of 90 - 120 °C, for example, 110 °C, for 5 - 10 min, and then continue to stir for 4 - 5 h under the reaction conditions of a temperature of 110 - 120 °C, and the carboxyl graft-modified epoxy resin can be obtained.

[0033] The epoxy value of the carboxyl graft-modified epoxy resin is 0.30 - 0.38 eq / 100g, for example, 0.32 - 0.35 eq / 100g, which is determined by the hydrochloric acid-acetone method.

[0034] The amine curing agent can include one or more of aliphatic amines, cycloaliphatic amines, aromatic amines and polyamides. For example, it can include one or more of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA).

[0035] The content of the amine curing agent is determined according to the epoxy value of the carboxyl graft-modified epoxy resin, the number of active hydrogen atoms on the amino group in the amine curing agent molecule, and the molecular weight of the amine curing agent; for example, the content of the amine curing agent is calculated according to the following formula:

[0036] W = (M / H n ) × E × 1.15

[0037] Where: W—the mass of amine curing agent required for every 100 g of carboxyl grafted modified epoxy resin; M—the molecular weight of amine curing agent; H n —the number of active hydrogen atoms on the amino group in the amine curing agent molecule; E—the epoxy value of carboxyl grafted modified epoxy resin.

[0038] Reactive diluents can promote the curing reaction, usually being epoxy-based and hydroxyl-based solvents, such as allyl glycidyl ether AGE, n-butyl glycidyl ether BGE, benzyl alcohol, epichlorohydrin.

[0039] Accelerators can accelerate the curing reaction and improve the construction efficiency; they are usually phenolic accelerators, for example, may include one or more of phenol, 2,4,6-tris(dimethylaminomethyl)phenol, resorcinol, aminophenol, halogenated phenols such as (o-chlorophenol, p-chlorophenol, 2,5-dichlorophenol, 2,4,5-trichlorophenol, etc.).

[0040] In the embodiment of the present invention, the method for preparing the base treatment agent includes: providing carboxyl grafted modified epoxy resin; mixing amine curing agent, reactive diluent, accelerator to obtain a mixture; mixing the carboxyl grafted modified epoxy resin and the mixture to obtain the base treatment agent.

[0041] In the step of mixing the amine curing agent, reactive diluent, accelerator, the dosage of the amine curing agent is determined according to the amount of carboxyl grafted modified epoxy resin, and at the same time, the amine curing agent, reactive diluent, accelerator are mixed at a molar ratio of 1:(4 - 5):(0.2 - 0.4), for example, usually stirred at room temperature for 20 - 30 min.

[0042] In the step of mixing the carboxyl grafted modified epoxy resin and the mixture, the carboxyl grafted modified epoxy resin and the mixture are usually mixed at a stirring rate of 400 - 600 r / min for 5 - 7 minutes.

[0043] In the embodiment of the present invention, the non-asphalt composite waterproof system of the present invention includes a base treatment layer, a non-asphalt non-curing waterproof coating layer, and an environmentally friendly waterproof coiled material which are sequentially stacked; wherein the base treatment layer is obtained from the above-mentioned base treatment agent.

[0044] In the embodiments of the present invention, the non-bituminous non-curing waterproof coating may include 35-65% of softening oil, 3.5-10% of wax powder, 15-25% of thermoplastic elastomer, 15-25% of resin, 1-3% of coupling agent, 1-5% of antioxidant, 3-6% of dispersant, 2-6% of pigment, and 5-20% of filler, based on the total weight of the non-bituminous non-curing waterproof coating; the sum of the weight percentages of the components in the non-bituminous non-curing waterproof coating is 100%, based on the total weight of the non-bituminous non-curing waterproof coating.

[0045] The softening oil is one or more of low-volatility naphthenic oil, reduced crude oil, paraffin oil, white wax oil, and aromatic oil, where the volatile matter should be ≤8 g / Kg, and the volatile matter is determined according to Section 8.2 of GB / T 34682—2017. It mainly serves as a good solvent for the modifier, reduces the system viscosity, and improves the low-temperature performance. The flash point of the softening oil is 230-300 °C, and it is measured by the closed-cup flash point determination method.

[0046] The wax powder is polyethylene wax or polypropylene wax, which can improve the storage stability of the product, reduce the product viscosity, and improve the high-temperature performance. The softening point of the wax powder is 105-130 °C, and it is measured according to the asphalt softening point determination method.

[0047] The thermoplastic elastomer may include one or more of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and styrene-butadiene rubber (SBR). The main function of the hydrogenation treatment is to break the unstable double bond structure on the original copolymer elastomer chain segment, reduce the content of its own active hydrogen, thereby improving its anti-aging property, so that the modifier can still maintain a good modification effect during the later aging process and provide a certain strength and elongation to the product. Among them, SEBS and SEPS are required to have a Shore A hardness range of 40-80, measured with a Shore hardness tester, and a melt index <1 g / 10 min at 200 °C, tested by a melt index test instrument; SBR is required to have a raw rubber Mooney viscosity of 50-70 ML100°C1+4, measured with a Mooney viscosity meter.

[0048] The resin may include one or more of cold-polymerized C5 hydrogenated petroleum resin, cold-polymerized C9 hydrogenated petroleum resin, alicyclic resin (DCPD), and C5 / C9 copolymer resin. It has good miscibility, a low melting point, and excellent water resistance, and can improve the adhesion effect of the system. The hydrogenation treatment also improves the anti-aging property of the resin itself. The softening point of the resin is 100-130 °C, measured according to the ring method.

[0049] The coupling agent can be a silane coupling agent, usually including one or more of n-octyltriethoxysilane, n-hexyltriethoxysilane, n-decyltrimethoxysilane, etc. The coupling agent mainly reduces the surface energy of the filler, improves the compatibility between the filler and the system, avoids the agglomeration of the fillers with each other, and promotes the dispersion of the filler.

[0050] The pigment can include one or more of iron oxide red, iron oxide yellow, iron oxide brown, chromium oxide green, chrome yellow, iron blue. The function of the dispersant is to promote the dispersion of the pigment and ensure uniform color. The dispersant can be an oil-based dispersant, and can be selected from one or more of KYC-913 and KYC-919 purchased from Keying Chemical. The antioxidant can be a hindered phenol antioxidant, such as pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0051] The filler includes one or several of stone powder, quartz powder, talc powder, and heavy calcium. The filler can comprehensively improve the various properties and storage stability of the coating, and at the same time, the filler can also reduce the production cost of the coating.

[0052] In the embodiments of the present invention, the non-bitumen non-curing waterproof coating is commercially available or can be prepared by methods known to those skilled in the art, for example:

[0053] (1) Add the softening oil into the reactor and heat it to 150 - 160 °C under stirring;

[0054] (2) Add the antioxidant, thermoplastic elastomer and resin, stir and heat to 170 - 175 °C;

[0055] (3) After complete dispersion without obvious particle agglomeration, add the dispersant and keep stirring at 172 - 176 °C for 2 - 2.5 h;

[0056] (4) Add the filler and mix for 0.2 - 0.4 h; then add the coupling agent and stir at 170 - 175 °C for 1 - 1.5 h to ensure uniform dispersion;

[0057] (5) Stop heating, add the wax powder and pigment, and continue to stir for 1 - 1.5 h;

[0058] (6) When the temperature drops to 120 - 130 °C, pack the product into an iron drum, seal it and store it.

[0059] The environmentally friendly waterproof coiled material can be a non-bitumen self-adhesive waterproof coiled material or a polymer waterproof coiled material.

[0060] The non-bituminous self-adhesive waterproofing membrane can be any non-bituminous self-adhesive waterproofing membrane commonly used in the art. For example, it may include 30-55% softening oil, 15-25% thermoplastic elastomer, 15-25% tackifying resin, 1-3% coupling agent, 1-5% antioxidant, 1-5% crosslinking agent, and 10-20% filler, based on the total weight of the non-bituminous self-adhesive waterproofing membrane.

[0061] The softening oil can be low flash point reduced line oil or aromatic oil, which mainly serves as a good solvent for modifiers, reduces viscosity, and improves low temperature performance. The thermoplastic elastomer can include one or more of styrene / butadiene / styrene block copolymer (SBS), SBR, and styrene-isoprene-styrene block copolymer (SIS). The tackifying resin can include one or more of rosin resin, coumarone resin, and terpene resin, which are mainly used to enhance the initial tack of the waterproofing membrane. The coupling agent is a silane coupling agent, usually including one or more of γ-aminopropyltriethoxysilane, n-octyltriethoxysilane, n-hexyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc. The antioxidant can be an antioxidant commonly used in the art, such as pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010). The crosslinking agent is a sulfur- or nitrogen-containing crosslinking agent, usually including one or more of sulfur, vulcanization accelerator (TMTD), and N-oxydiphenyl-N'-isopropyl-p-phenylenediamine (MOR). The crosslinking agent can enhance the crosslinking degree of the polymer in the waterproofing membrane and improve the anti-aging property. The filler is a filler with a high specific surface area, usually calcium hydroxide, vermiculite, kaolin, etc., which can reduce the density of the product and expand the application and construction area. The upper and lower sides of the non-bituminous self-adhesive waterproofing membrane have release films, both of which can use PET release films.

[0062] The non-bituminous self-adhesive waterproofing membrane is commercially available or can be prepared by methods known to those skilled in the art. For example, it includes the following steps:

[0063] (1) Add the softening oil to the reactor and heat it to 160-165°C with stirring.

[0064] (2) Add the antioxidant, thermoplastic elastomer, and tackifying resin in sequence, stir and heat to 170-175°C.

[0065] (3) After complete dispersion without obvious particle agglomeration, add the crosslinking agent, keep stirring at 172-176°C for 2-2.5 h, then add the coupling agent and continue stirring for 30 min.

[0066] (4) Add the filler and stir at 170-175°C for 1-1.5 h to ensure uniform dispersion.

[0067] (5) Use a PET release film for cooling and molding to obtain the non-bituminous self-adhesive waterproofing membrane.

[0068] The polymer waterproof coiled material can be any polymer waterproof coiled material commonly used in the art. For example, it may include 60-70% of ethylene-propylene copolymer, 15-25% of metallocene polyethylene, 8-15% of linear low-density polyethylene (LLDPE), 5-10% of ethylene-octene polymer (POE), 1-3% of antioxidant 1010, and 2-5% of masterbatch, based on the total weight of the polymer waterproof coiled material. The number-average molecular weight of the ethylene-propylene copolymer is 10,000-30,000 g / mol, measured according to the gel permeation chromatography (GPC) method, and is usually EPDM 1230 purchased from DuPont Company of the United States. The metallocene polyethylene is usually 5815 purchased from Dow Chemical Company. The linear low-density polyethylene (LLDPE) is usually 7042 purchased from Guangzhou Petrochemical Company. The ethylene-octene polymer (POE) is usually 8150 purchased from Dow Chemical Company. The masterbatch is usually 1010 purchased from Dongguan Meize Plastic Pigment Co., Ltd.

[0069] The polymer waterproof coiled material is commercially available or can be prepared by methods known to those skilled in the art. For example, 60-70% of ethylene-propylene copolymer, 15-25% of metallocene polyethylene, 8-15% of linear low-density polyethylene (LLDPE), 5-10% of ethylene-octene polymer (POE), 1-3% of antioxidant 1010, and 2-5% of masterbatch can be added to a mixer and stirred and mixed at a stirring rate of 15-30 r / min for 30-60 min, and then calendered and formed to obtain the polymer waterproof coiled material.

[0070] In an embodiment of the present invention, the preparation method of the non-bituminous composite waterproof system of the present invention includes:

[0071] (1) Ensure that there is no surface water on the base surface and perform dust removal on the base surface;

[0072] (2) Coat the base treatment agent of the present invention with a coating thickness of 0.3-0.6 mm to obtain a base treatment layer;

[0073] (3) Scraping the non-bituminous non-curing waterproof coating heated to an easy-to-stir state on the side of the base treatment layer away from the base surface, with a scraping thickness of the non-bituminous non-curing waterproof coating of 1.5-2.0 mm, to obtain a non-bituminous non-curing waterproof coating layer;

[0074] (4) Before the non-bituminous non-curing waterproof coating is completely cooled, lay the environmentally friendly waterproof coiled material on the side of the non-bituminous non-curing waterproof coating layer away from the base treatment layer to obtain the non-bituminous composite waterproof system.

[0075] This composite waterproofing system achieves good waterproofing effects, has a wider construction temperature range, and has excellent environmental protection performance, and can be widely used in buildings, high-speed railways, subways, tunnels or other engineering fields.

[0076] The present invention will be described below through specific embodiments. The embodiments described below are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention. For those technologies or conditions not specified in the embodiments, they shall be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications, or carried out under normal temperature and pressure. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchases.

[0077] Example 1

[0078] The non-bituminous composite waterproofing system includes a primer layer, non-bituminous non-curing waterproof coating, and non-bituminous self-adhesive waterproofing membrane.

[0079] (I) Epoxy primer

[0080] (A) Preparation of carboxyl graft-modified epoxy resin:

[0081] (1) Bisphenol A epoxy resin E51 (368 g, model CYD-128, purchased from Baling Petrochemical) and oleic acid (621.41 g, CAS No. 112-80-1, purchased from Shandong Chuangli New Materials Co., Ltd.) were added to a reactor with a stirring device in a molar ratio of 1:2.2, and uniformly stirred at a stirring rate of 600 r / min at a temperature of 110 °C for 8 min;

[0082] (2) AIBN (32.84 g) was added to the reactor in a molar ratio of 0.2:1 to E51, and uniformly stirred at a stirring rate of 600 r / min at a temperature of 110 °C for 7 min, and then continuously stirred for 5 h under the reaction condition of a temperature of 120 °C to obtain 335.85 g of modified epoxy resin 1.

[0083] The epoxy value of the carboxyl graft-modified epoxy resin 1 is 0.35 eq / 100 g, and its structure was characterized by infrared spectroscopy. An obvious characteristic absorption peak of acid anhydride appeared at 1739.02 cm -1 , indicating that oleic acid has been grafted onto the epoxy resin molecular chain.

[0084] (B) According to the epoxy value and weight of the above carboxyl graft-modified epoxy resin 1, according to the following formula

[0085] W = (M / H n ) × E × 1.15

[0086] The mass of ethylenediamine (EDA) required for every 100 g of the carboxyl grafted modified epoxy resin is 6.04 g (0.1 mol), so the total mass of ethylenediamine (EDA) required for the above carboxyl grafted modified epoxy resin 1 is 20.29 g (0.34 mol).

[0087] Weigh 147.08 g (1.36 mol) of benzyl alcohol and 18.05 g (0.068 mol) of 2,4,6-tris(dimethylaminomethyl)phenol according to the molar ratio of ethylenediamine (EDA):benzyl alcohol:2,4,6-tris(dimethylaminomethyl)phenol of 1:4:0.2. Mix ethylenediamine (EDA), benzyl alcohol and 2,4,6-tris(dimethylaminomethyl)phenol at room temperature at a stirring rate of 500 r / min for 25 min to obtain a mixture;

[0088] (C) Mix the carboxyl grafted modified epoxy resin obtained in (A) and the mixture obtained in (B) at a stirring rate of 500 r / min for 6 minutes to obtain a primer.

[0089] The preparation and composition of the primer for the primer layer are summarized in Table 1.

[0090] (II) Non-bituminous non-curing waterproof coating

[0091] It includes the following parts by weight: 50 parts of aromatic oil (model AL-09, purchased from Guangzhou Dagang Petroleum Technology Co., Ltd.), 5 parts of polyethylene wax (model PEW-0360, purchased from Nanjing Tianshi New Materials Technology Co., Ltd.), 20 parts of thermoplastic elastomer (SEBS:SBR = 4:6) (models are YH502 and SBR1502 respectively, purchased from Baling Petrochemical Company, Sinopec Group), 25 parts of C5 hydrogenated petroleum resin (model H5-1000, purchased from Henghe Materials Technology Co., Ltd.), 2 parts of KH-550, 2 parts of antioxidant 1010, 5 parts of dispersant KYC-913, 3 parts of iron oxide red (model H130, purchased from Henan Huamei Chengde Pigment Co., Ltd.), and 15 parts of filler talc powder.

[0092] (1) Add the aromatic oil into the reactor and heat it to 155 °C under stirring at a stirring rate of 300 r / min;

[0093] (2) Add antioxidant 1010, thermoplastic elastomer and C5 hydrogenated petroleum resin, and heat it to 170 °C under stirring at a stirring rate of 500 r / min;

[0094] (3) After complete dispersion without obvious particle agglomeration, add dispersant KYC-913 and keep stirring at 172 °C for 2 h;

[0095] (4) Add filler talcum powder and mix for 0.2 - 0.4 h; then add coupling agent KH-550 and stir at 170 °C for 1 h to ensure uniform dispersion;

[0096] (5) Stop heating, add polyethylene wax powder and pigment iron oxide red, and continue stirring for 1 h;

[0097] (6) When the temperature naturally cools to 120 °C, put the obtained waterproof coating into an iron bucket, seal it, store it, and set it aside for use.

[0098] (III) The non-bituminous self-adhesive waterproof coiled material comprises the following parts by weight: 45 parts of naphthenic oil, 15 parts of SBS, 15 parts of coumarone resin, 2 parts of KH-550, 2 parts of antioxidant 1010, 1 part of sulfur, and 20 parts of vermiculite.

[0099] (1) Add naphthenic oil into the reactor and heat it to 160 °C with stirring at a stirring rate of 300 r / min;

[0100] (2) Add antioxidant 1010, SBS, and coumarone resin in sequence, stir and heat to 170 °C at a stirring rate of 500 r / min;

[0101] (3) After complete dispersion without obvious particle agglomeration, add crosslinking agent sulfur, keep it at 172 °C and stir at a stirring rate of 500 r / min for 2 h, then add coupling agent KH-550 and continue stirring for 30 min;

[0102] (4) Add filler vermiculite and stir at 170 °C at a stirring rate of 600 r / min for 1 h to ensure uniform dispersion;

[0103] (5) Use PET release film for cooling and forming to obtain the non-bituminous self-adhesive waterproof coiled material.

[0104] (IV) Preparation of non-bituminous composite waterproof system

[0105] (1) Conduct base surface dust removal and ensure that there is no visible water on the base surface;

[0106] (2) Coat the primer prepared in step (A) with a coating thickness of 0.5 mm to obtain a primer layer;

[0107] (3) Scraping the non-bituminous non-curing waterproof coating heated to be easily stirrable on the side of the primer layer away from the base surface, with a scraping thickness of 1.5 mm for the non-bituminous non-curing waterproof coating, to obtain a non-bituminous non-curing waterproof coating layer;

[0108] (4) Immediately after scraping the non-bituminous non-curing waterproof coating, lay the non-bituminous self-adhesive waterproof coiled material on the side of the non-bituminous non-curing waterproof coating layer away from the primer layer to obtain the non-bituminous based composite waterproof system.

[0109] Example 2-20

[0110] Repeat the steps of Example 1, except that the preparation conditions, material composition, and dosage of the (I) base treatment layer are changed; see Table 1 for details.

[0111] Table 1 Preparation and Composition of Base Treatment Agents for Examples 1-20

[0112]

[0113]

[0114] * The molar ratio of the three is the molar ratio of amine curing agent, active diluent, and accelerator.

[0115] Example 21

[0116] Repeat the steps of Example 1, except that in the preparation of the (II) non-asphalt non-curing waterproof coating, the composition of the thermoplastic elastomer is SEBS:SBR = 5:5.

[0117] Example 22

[0118] Repeat the steps of Example 1, except that in the preparation of the (II) non-asphalt non-curing waterproof coating, the composition of the thermoplastic elastomer is SEBS:SEPS = 6:4.

[0119] Example 23

[0120] Repeat the steps of Example 1, except that in the preparation of the (II) non-asphalt non-curing waterproof coating, the composition of the thermoplastic elastomer is SBR:SEPS = 7:3.

[0121] Example 24

[0122] Repeat the steps of Example 1, except that in (III), the non-asphalt self-adhesive waterproof coil is replaced with a polymer waterproof coil, which includes the following parts by weight: ethylene-propylene copolymer: 60 parts, metallocene polyethylene 15 parts, linear low-density polyethylene (LLDPE) 15 parts, ethylene-octene polymer (POE) 7 parts, antioxidant 1010 1 part, masterbatch 2 parts.

[0123] Comparative Example 1

[0124] Repeat the steps of Example 1, except that in (II), the non-asphalt non-curing waterproof coating is replaced with an asphalt-based non-curing waterproof coating, and the asphalt-based non-curing waterproof coating contains: 200# asphalt 50 parts, 90# asphalt 10 parts, SBS 5 parts, SIS 3 parts, SBR 5 parts, polyethylene wax 4 parts, coupling agent KH-550 2 parts, filler vermiculite 21 parts.

[0125] Comparative Example 2

[0126] Repeat the steps of Comparative Example 1, except that in (III), the non-bitumen self-adhesive waterproofing membrane is replaced with the polymer waterproofing membrane in Example 24.

[0127] Comparative Example 3

[0128] Repeat the steps of Example 1, except that step (I) is not carried out and (IV)(2) is omitted, and the non-bitumen non-curing waterproof coating is directly applied to the base surface.

[0129] Comparative Example 4

[0130] Repeat the steps of Example 1, except that in step (I), step (A) is not carried out, that is, bisphenol A epoxy resin E51 is directly used to replace the carboxyl graft-modified epoxy resin 1 in (B) to prepare the base treatment agent.

[0131] Performance Test

[0132] Test the performance of the non-bitumen-based composite waterproofing systems prepared in the above examples and comparative examples. The present invention conducts tests according to the actual application scenarios, and all tests are carried out under the standard environment of room temperature 23°C if not clearly specified.

[0133] Peeling Strength: On the cement base surface, prepare the non-bitumen-based composite waterproofing systems prepared in the above examples and comparative examples with a bonding area of 50 mm × 75 mm. After bonding, apply a 1 kg weight in the center for 10 min. Then place it under the standard conditions of temperature (23 ± 2)°C and relative humidity (30 - 70)% for 24 h. Test according to the GB / T 328.20 - 2007 standard, and it should be placed at the test temperature for 1 h before testing.

[0134] Shearing Force: On the cement base surface, prepare the non-bitumen-based composite waterproofing systems prepared in the above examples and comparative examples with a bonding area of 50 mm × 50 mm. After bonding, apply a 1 kg weight in the center for 10 min. Then place it under the standard conditions of temperature (23 ± 2)°C and relative humidity (30 - 70)% for 24 h. Test according to the GB / T 328.23 - 2007 standard. The length of the specimen should ensure that the initial distance between the clamps is (200 ± 5) mm, the test is carried out at (23 ± 2)°C, and the tensile speed is (100 ± 10) mm / min.

[0135] Water anti-channeling property: Tested according to Section 7.17.1 of JC / T 2428-2017. Specifically, a hole with a diameter of about 10 mm is drilled in the middle of the test piece until the cement base surface is reached. The test piece is installed in a mortar impermeability tester with the coated surface facing the water, pressurized to 1.0 MPa, and maintained for 24 h. After the test, the non-bituminous composite waterproof system is scraped off, and the bonding surface is observed for any visible water. The absence of visible water indicates no water channeling.

[0136] The test results of the composite waterproof systems of each example and comparative example are summarized in Table 2.

[0137] Table 2 Performance of the composite waterproof systems of each example and comparative example

[0138]

[0139]

[0140] The non-bituminous composite waterproof system prepared by the present invention also has a full-bonding construction effect in high-temperature and low-temperature environments, broadens the application range of conventional roll-coated composite waterproof construction, achieves good waterproof effects, and has excellent environmental protection performance.

[0141] The above specific embodiments do not limit the protection scope of the present invention. Those skilled in the art should understand that various modifications, combinations, sub-combinations, and substitutions can occur depending on design requirements and other factors. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composite waterproofing system, characterized in that, It includes a base treatment layer, a non-bituminous and non-curing waterproof coating layer, and an environmentally friendly waterproof coil which are stacked in sequence; wherein the environmentally friendly waterproof coil is a non-bituminous self-adhesive waterproof coil or a polymer waterproof coil; the base treatment layer is formed by coating a base treatment agent. The base treatment agent includes carboxyl grafted modified epoxy resin, amine curing agent, active diluent, and accelerator. Among them, the epoxy value of the carboxyl grafted modified epoxy resin is 0.30 - 0.38eq / 100g, which is measured by the hydrochloric acid-acetone method; the carboxyl grafted modified epoxy resin is prepared from bisphenol A epoxy resin, carboxyl functional monomer, and thermal initiator, and the carboxyl functional monomer includes one or more of the following substituted or unsubstituted carboxylic acids: C16 - C20 alkenyl carboxylic acid, acrylic acid, maleic anhydride; the molar ratio of bisphenol A epoxy resin, carboxyl functional monomer, and thermal initiator is 1:(2.2 - 2.4):(0.1 - 0.3). The content of the amine curing agent is determined according to the epoxy value of the carboxyl grafted modified epoxy resin, the number of active hydrogen atoms on the amino group in the amine curing agent molecule, and the molecular weight of the amine curing agent. Moreover, the molar ratio of the amine curing agent, active diluent, and accelerator is 1:(4 - 5):(0.2 - 0.4).

2. The composite waterproofing system according to claim 1, characterized in that The thermal initiator is an azo initiator or an organic peroxide.

3. The composite waterproofing system according to claim 1 or 2, characterized in that, The content of the amine curing agent is calculated according to the following formula: W = (M / H n ) × E × 1.15 In the formula: W—the mass of the amine curing agent required for every 100g of the carboxyl grafted modified epoxy resin; M—the molecular weight of the amine curing agent; H n — The number of active hydrogen atoms on the amino group in the amine curing agent molecule; and E—the epoxy value of the carboxyl grafted modified epoxy resin.

4. The composite waterproofing system according to claim 1 or 2, characterized in that, The amine curing agent includes one or more of aliphatic amine, cycloaliphatic amine, aromatic amine, and polyamide; the active diluent is an epoxy or hydroxyl solvent; the accelerator is a phenolic accelerator.

5. The composite waterproofing system according to claim 4, characterized in that, The accelerator includes one or more of phenol, 2,4,6-tris(dimethylaminomethyl)phenol, resorcinol, aminophenol, and halogenated phenol.

6. The composite waterproof system according to claim 1 or 2, wherein the method for preparing the base treatment agent includes the following steps: Mix the amine curing agent, active diluent, and accelerator to obtain a mixture. Mix the carboxyl grafted modified epoxy resin and the mixture to obtain the base treatment agent.

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