Silane modified polyether waterproof coating, preparation method and waterproof product

Abstract

The invention provides a silane modified polyether waterproof coating, a preparation method and a waterproof product. The coating comprises the following components in parts by weight: 100 parts of Wacker alkoxy-terminated polyether; based on 100 parts of Wacker alkoxy terminated polyether as a reference, 65 to 96 parts of clock alkoxy terminated polyether; 45 to 80 parts of epoxy modified organic silicon resin; 8-17 parts of modified epoxy resin, wherein the modified epoxy resin comprises an alkoxy silane group, an epoxy group and an acrylic acid chain link; 250 to 380 parts of an epoxy plasticizer; 5-24 parts of a latent curing agent; 430 to 780 parts of pigment and filler; and 8-20 parts of an additive. The modified epoxy resin in the coating contains an alkoxy silane group, an epoxy group and an acrylic acid chain link, so that the bonding performance and stripping performance of the waterproof roll and a base plane can be improved.

Description

Technical Field

[0001] The present application belongs to the field of waterproof coatings, and specifically relates to a silane-modified polyether waterproof coating, a preparation method and a waterproof product. Background Art

[0002] Silane-modified polyether waterproof coating is a one-component, solvent-free waterproof coating made of modified polyether resin as the base polymer, functional additives, fillers, pigments and catalysts. It has the advantages of high elongation, high tensile strength, good low-temperature flexibility and low water absorption.

[0003] Silane polyether resin, also known as terminal silane modified polyether resin or silicone modified polyether resin, initially appeared mainly in the form of terminal silane polyether sealant, which is also known as MS sealant, silicone modified polyether sealant and modified silicone sealant. Silane polyether architectural waterproof coating is mainly used for waterproofing and moisture-proofing in kitchens, bathrooms, balconies and other places. When used, it is coated on the base layer and solidified by reaction with moisture to form a continuous and seamless polymer elastic waterproof membrane. Silane modified polyether waterproof coating can be used on roofs, exterior walls and other parts with the application of an appropriate protective layer. The coating can be scraped, rolled, brushed or sprayed, and can be applied to the designed thickness in one go, saving time and construction costs.

[0004] In the field of building waterproofing, silane-modified polyether waterproof coatings can be applied to cold construction of some waterproofing membranes to form a second waterproof layer. Silane-modified polyether waterproof coatings and the surface of waterproofing membranes can form a good bonding interface, showing excellent bonding performance. The formed coating membrane bonding layer has excellent bonding performance, the bonding layer is tight and impermeable, has excellent performance, excellent overall waterproof effect, and long service life. It has been promoted as a new type of waterproof coating.

[0005] However, the peel strength of the waterproof roll formed by compounding the silane-modified polyether waterproof coating with the roll material is low, and the adhesion performance of the silane-modified polyether waterproof coating to the cement-based surface is low, which makes it difficult to meet the construction progress requirements and waterproofing requirements. Summary of the invention

[0006] The present application provides a silane-modified polyether waterproof coating, a preparation method and a waterproof product, aiming to improve the peel strength of the silane-modified polyether waterproof coating after being composited with a coiled material, as well as its bonding performance.

[0007] The first aspect of the present application provides a silane-modified polyether waterproof coating, which includes the following components in parts by weight: 100 parts of Wacker alkoxy-terminated polyether; and the following components, all based on 100 parts of Wacker alkoxy-terminated polyether: 65-96 parts of alkoxy-terminated polyether; 45-80 parts of epoxy-modified silicone resin; 8-17 parts of modified epoxy resin, which includes alkoxysilane groups, epoxy groups and acrylic chain segments; 250-380 parts of epoxy plasticizer; 5-24 parts of latent curing agent; 430-780 parts of pigments and fillers; and 8-20 parts of additives.

[0008] In a feasible implementation manner of the first aspect of the present application, the epoxy equivalent of the modified epoxy resin ranges from 300 g / eq to 410 g / eq.

[0009] In a feasible implementation of the first aspect of the present application, the modified epoxy resin includes a structure shown in Formula 1 below:

[0010]

[0011] In formula 1, n is an integer of 1 to 25, X is an integer of 1 to 3; R1 is not less than 2 methylene groups or phenyl groups, R2 is an alkyl group of 1 to 3 carbon atoms, R3 is a straight chain or branched alkyl group of 1 to 3 carbon atoms, and m1+m2=3.

[0012] In a feasible embodiment of the first aspect of the present application, the Wacker alkoxy-terminated polyether includes one or more of STP-E35, STP-E30, STP-E15 and STP-E10.

[0013] In a feasible embodiment of the first aspect of the present application, the potassium alkoxy terminated polyether includes one or more of SAX227, SAX327, SAX220 and SAX750.

[0014] In a feasible implementation of the first aspect of the present application, the epoxy-modified silicone resin includes one or a combination of SH-023 and SH-9614.

[0015] In a feasible implementation manner of the first aspect of the present application, the epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil and epoxy sunflower oil.

[0016] In a feasible implementation of the first aspect of the present application, the latent curing agent includes one or more of an aldimine curing agent, a ketimine curing agent and an oxazolidine curing agent.

[0017] In a feasible implementation manner of the first aspect of the present application, the pigment filler includes one or more of fumed silica, nano calcium carbonate, heavy calcium carbonate, modified heavy calcium carbonate, nano clay, carbon black and modified clay.

[0018] In a feasible implementation of the first aspect of the present application, the additive includes one or more of a dehydrating agent, a promoter and a catalyst.

[0019] Optionally, the dehydrating agent includes one or more of vinyl trimethoxy silane, vinyl triacetoxy silane and vinyl triethoxy silane.

[0020] Optionally, the accelerator includes one or more of triacetoxyethylsilane, vinyltriacetoxysilane, and diethyldiacetoxysilane.

[0021] Optionally, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and a chelated tin catalyst.

[0022] The second aspect of the present application provides a method for preparing the silane-modified polyether waterproof coating provided in the first aspect of the present application, comprising:

[0023] Mixing predetermined weight portions of Wacker silane-modified polyether, Kalium-modified silane-modified polyether, epoxy plasticizer, and pigment and filler under a first condition to obtain a first reactant;

[0024] Mixing the first reactant, epoxy-modified silicone resin, modified epoxy resin and latent curing agent under a second condition to obtain a second reactant;

[0025] The second reactant and the additive are mixed under catalytic conditions to obtain a silane-modified polyether waterproof coating.

[0026] In a feasible implementation of the second aspect of the present application, in the step of mixing the first reactant and the epoxy-modified silicone resin, the modified epoxy resin and the latent curing agent under a second condition to obtain the second reactant, the modified epoxy resin is formed by a polymerization reaction of an epoxy resin, an acrylic monomer having an epoxy group and an aminosilane coupling agent.

[0027] The third aspect of the present application provides a waterproof product, comprising: a waterproof coating and an asphalt waterproof roll covering the waterproof coating, wherein the waterproof coating is formed by the silane-modified polyether waterproof coating provided in the first aspect of the present application.

[0028] The modified epoxy resin in the coating of the present application contains multiple epoxy groups and alkoxysilane groups, and the epoxy groups thereof can realize cross-linking reaction together with the epoxy groups in the epoxy plasticizer and the epoxy-modified silicone resin and the hydrolyzed latent curing agent. The combined use of the three components containing epoxy groups can increase the speed and cross-linking density of the epoxy ring-opening cross-linking reaction, improve the adhesion and peeling properties to waterproof membranes and cement-based surfaces, and make the system free of free plasticizers after curing, thereby avoiding the migration of plasticizers and improving the compatibility with waterproof membranes, peeling strength and adhesion properties.

[0029] At the same time, the modified epoxy resin also contains alkoxy silane groups. After hydrolysis, the alkoxy silane groups can undergo condensation cross-linking reactions with alkoxy-terminated polyethers, thereby improving the adhesion through cross-linking reactions with active groups such as hydroxyl groups on the cement base and hydroxyl groups and carboxyl groups in the coil matrix. It can also improve the problem that silane-modified polyether waterproof coatings have high requirements for base dryness and poor adhesion on wet concrete bases. The introduction of the Si-O-Si main chain in the epoxy-modified silicone resin can improve the heat resistance and wettability of the coating.

[0030] Moreover, the modified epoxy resin also contains acrylic acid chain segments. The large number of polar groups contained in acrylic acid, such as hydroxyl and carboxyl groups, have good hydrophilicity and good affinity to the base surface. They can interact with the polar groups on the surface of the base surface to form intermolecular forces and enhance adhesion. The acrylic acid-modified epoxy resin can also increase the molecular weight of the polymer, making the cured polymer molecular chain longer and denser, and the molecular cohesion stronger, thereby enhancing the strength and toughness of the bonding layer between the waterproof coating and the substrate. DETAILED DESCRIPTION

[0031] In order to make the invention purpose, technical scheme and beneficial technical effect of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application, not for limiting the present application.

[0032] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0033] In the description herein, when a composition is described as containing, comprising or including specific components, or when a process is described as containing, comprising or including specific process steps, it is expected that the composition of the present application also consists essentially of or consists of the components, and the process of the present application also consists essentially of or consists of the process steps.

[0034] The use of the terms "including," "comprising," "containing," and "having" should generally be interpreted as open ended and non-limiting unless expressly stated otherwise.

[0035] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number itself, and the “multiple” in “one or more” means more than two.

[0036] The above-mentioned summary of the invention of the present application is not intended to describe each disclosed embodiment or each implementation in the present application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided by a series of examples, which can be used in various combinations. In each example, enumeration is only used as a representative group and should not be interpreted as exhaustive.

[0037] Traditional silane-modified polyether waterproof coatings have compatibility problems with waterproof coiled materials due to the migration of plasticizers. The migration of plasticizers causes swelling of waterproof coiled materials, especially waterproof coiled materials composed of components such as asphaltene and butyl gum, which reduces the cohesive force and adhesive peeling performance of the coiled material components themselves to varying degrees. In addition, traditional silane-modified polyether waterproof coatings are not ideal for cement-based surfaces, have low adhesive performance, and have certain requirements for the dryness of the base surface. They cannot be applied on wet concrete base surfaces. The coating has poor wettability, poor adhesive effect, and a significant decrease in adhesive strength, which cannot meet the construction progress and waterproofing requirements. Therefore, how to prepare a silane-modified polyether waterproof coating that has excellent adhesion, does not cause compatibility problems such as plasticizer migration on waterproof coiled materials, and can be directly applied on wet base surfaces has become a technical problem that urgently needs to be solved.

[0038] In view of this, the inventors provide a silane-modified polyether waterproof coating, a preparation method and a waterproof product in the present application, which can improve the peel strength of the silane-modified polyether waterproof coating and the coiled material after compounding, as well as its bonding performance.

[0039] In an embodiment of the first aspect of the present application, a silane-modified polyether waterproof coating is provided, and the silane-modified polyether waterproof coating includes the following components in parts by weight: 100 parts of Wacker alkoxy-terminated polyether; and based on 100 parts of Wacker alkoxy-terminated polyether: 65-96 parts of potassium-modified alkoxy-terminated polyether; 45-80 parts of epoxy-modified silicone resin; 8-17 parts of modified epoxy resin, wherein the modified epoxy resin includes alkoxysilane groups, epoxy groups and acrylic chain segments; 250-380 parts of epoxy plasticizer; 5-24 parts of latent curing agent; 430-780 parts of pigments and fillers; and 8-20 parts of additives.

[0040] The modified epoxy resin in the coating of the present application contains multiple epoxy groups and alkoxysilane groups, and the epoxy groups thereof can realize cross-linking reaction together with the epoxy groups in the epoxy plasticizer and the epoxy-modified silicone resin and the hydrolyzed latent curing agent. The combined use of the three components containing epoxy groups can increase the speed and cross-linking density of the epoxy ring-opening cross-linking reaction, improve the adhesion and peeling properties to the waterproof membrane and the base surface, and make the system free of free plasticizer after curing, thereby avoiding the migration of the plasticizer and improving the compatibility with the waterproof membrane, the peeling strength and the adhesion performance.

[0041] At the same time, the modified epoxy resin also contains alkoxy silane groups. After hydrolysis, the alkoxy silane groups can undergo condensation cross-linking reactions with alkoxy-terminated polyethers, and the adhesion is improved by cross-linking reactions with active groups such as hydroxyl groups on the base surface and hydroxyl groups and carboxyl groups in the coil matrix. It can also improve the problem that silane-modified polyether waterproof coatings have high requirements for base dryness and poor adhesion on wet concrete base surfaces. The introduction of the Si-O-Si main chain in the epoxy-modified silicone resin can improve the heat resistance and wettability of the coating.

[0042] Moreover, the modified epoxy resin also contains acrylic acid chain segments. The large number of polar groups contained in acrylic acid, such as hydroxyl and carboxyl groups, have good hydrophilicity and good affinity to the base surface. They can interact with the polar groups on the surface of the base surface to form intermolecular forces and enhance adhesion. The acrylic acid-modified epoxy resin can also increase the molecular weight of the polymer, making the cured polymer molecular chain longer and denser, and the molecular cohesion stronger, thereby enhancing the strength and toughness of the bonding layer between the waterproof coating and the substrate.

[0043] In some embodiments, the epoxy equivalent of the modified epoxy resin ranges from 300 g / eq to 410 g / eq.

[0044] The modified epoxy resin of the present application also has a suitable epoxy equivalent range, especially the modified epoxy resin within the above range not only has high activity, fast crosslinking speed, and high crosslinking density, which can improve the peeling strength and bonding performance of the waterproof membrane, but also can further take into account the heat resistance and mechanical strength of the coating, such as tensile strength, tear strength, etc.

[0045] In some embodiments, the molar amount of epoxy groups in the modified epoxy resin can be greater than the molar amount of alkoxysilane groups. The relatively larger proportion of epoxy groups can increase the speed and crosslinking density of the epoxy ring-opening crosslinking reaction, and further improve the bonding performance and peeling strength to the waterproof membrane and the base surface.

[0046] Bisphenol epoxy resin contains multiple epoxy groups, a rigid structure of double benzene rings, and good activity. Using bisphenol epoxy resin as a skeleton structure and introducing acrylic chain segments with epoxy groups and alkoxysilane groups can further improve the strength of the coating, such as bonding strength, tensile strength, and tear strength. In some embodiments, the modified epoxy resin may include a structure shown in Formula 1 below:

[0047]

[0048] In formula 1, n is an integer of 1 to 25, X is an integer of 1 to 3; R1 is not less than 2 methylene groups or phenyl groups, R2 is an alkyl group of 1 to 3 carbon atoms, R3 is a straight chain or branched alkyl group of 1 to 3 carbon atoms, and m1+m2=3.

[0049] The plasticizer selected in the present application is a plasticizer with an epoxy group. It is precisely because it contains an epoxy group that it can undergo a ring-opening crosslinking reaction with the polyepoxy groups in the modified epoxy resin, the epoxy groups in the epoxy-modified silicone, and the amino groups released by the hydrolysis of the latent curing agent, thereby fixing the plasticizer in the coating film, preventing it from migrating and penetrating into the coiled material, and increasing the speed and crosslinking density of the ring-opening crosslinking reaction of the epoxy group. In some embodiments, the epoxy plasticizer may include one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, and epoxy sunflower oil.

[0050] The curing agent selected in the present application is a latent curing agent that can hydrolyze and release amino groups, so that a cross-linking reaction can occur with the component with epoxy groups in the coating, reducing the swelling influence of free components in the system on the waterproof coiled material, and improving the curing speed of the coating. In some embodiments, the latent curing agent can include one or more of aldimine curing agents, ketimine curing agents and oxazolidine curing agents. Optionally, one or more of aldimine, ketimine and oxazolidine can be included.

[0051] The polyether selected in the present application has an alkoxy end group, and the alkoxy end group in the polyether can undergo a dehydration reaction with the silanol group after the hydrolysis of the alkoxysilane group to form a new silicon oxygen bond (Si-O-Si), thereby enhancing the heat resistance and adhesion properties of the coating. In some embodiments, the Wacker alkoxy-terminated polyether may include one or more of STP-E35, STP-E30, STP-E15, and STP-E10. In some embodiments, the Kalkan alkoxy-terminated polyether may include one or more of SAX227, SAX327, SAX220, and SAX750.

[0052] The present application can also obtain a silane-modified polyether waterproof coating with more ideal comprehensive performance by selecting epoxy silicone resin with good water resistance, weather resistance and heat resistance. In some embodiments, the epoxy-modified silicone resin can include one or a combination of SH-023 and SH-9614.

[0053] In addition, different additives can be selected according to the needs to obtain coatings suitable for different occasions. In some embodiments, the pigment filler can include one or more of fumed silica, nano calcium carbonate, heavy calcium carbonate, modified heavy calcium carbonate, nano clay, carbon black and modified clay; 400 parts by weight of heavy calcium carbonate and 160-260 parts by weight of nano calcium carbonate can be selected.

[0054] The additive may include one or more of a water remover, a promoter and a catalyst. Optionally, the water remover may include one or more of vinyl trimethoxysilane, vinyl triacetoxysilane, and vinyl triethoxysilane. Optionally, the promoter may include one or more of triacetoxyethyl silane, vinyl triacetoxysilane, and diethyl diacetoxy silane. Optionally, the catalyst may include one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and a chelated tin catalyst.

[0055] In an embodiment of the second aspect of the present application, there is provided a method for preparing the silane-modified polyether waterproof coating provided in the first aspect of the present application, comprising:

[0056] Predetermined weight portions of Wacker silane-modified polyether, silane-modified polyether, epoxy plasticizer and pigment are mixed under a first condition to obtain a first reactant; the first reactant and epoxy-modified silicone resin, modified epoxy resin and latent curing agent are mixed under a second condition to obtain a second reactant; the second reactant and additives are mixed under catalytic conditions to obtain a silane-modified polyether waterproof coating.

[0057] Specifically, in the step of mixing predetermined weight portions of Wacker silane-modified polyether, kalkonium silane-modified polyether, epoxy plasticizer and pigments and fillers under a first condition to obtain a first reactant, the preparation of the first reactant may include adding Wacker silane-modified polyether, kalkonium silane-modified polyether and epoxy plasticizer into a reactor, mixing and stirring, heating to 90°C to 100°C, and adding pigments and fillers while stirring; after the powder is completely stirred, heating to 100°C to 110°C, evacuating, and dehydrating for 3h to 4h to obtain the first reactant.

[0058] Specifically, in the step of mixing the first reactant and the epoxy-modified silicone resin, the modified epoxy resin and the latent curing agent under the second condition to obtain the second reactant, the preparation of the second reactant can include cooling the first reactant to 60°C to 70°C, adding the epoxy-modified silicone resin, the modified epoxy resin and the latent curing agent, and vacuum stirring for 0.5h to 1h to obtain the second reactant.

[0059] Specifically, the step of mixing the second reactant and the additive under catalytic conditions to obtain the silane-modified polyether waterproof coating can include cooling the second reactant to 50°C to 60°C, adding a desiccant and a promoter, vacuuming and stirring for 0.5h to 1h, then maintaining the temperature at 50°C to 60°C, adding a catalyst, vacuuming and continuing to stir for 0.5h to 1h, cooling to below 50°C, filling with nitrogen for protection, and discharging.

[0060] The modified epoxy resin can be formed by polymerization of epoxy resin, acrylic monomer with epoxy group and aminosilane coupling agent. Specifically, the modified epoxy resin can be prepared by the following method:

[0061] S01: Add a calculated amount of dried bisphenol A epoxy resin E44 into a reactor, add a mixed solvent of n-butanol and N,N-dimethylformamide (volume ratio is 1:1), the amount of the mixed solvent of n-butanol and N,N-dimethylformamide is 10% to 15% of the total mass of the reaction, start stirring until the epoxy resin is completely dissolved, control the material temperature to 90°C to 110°C, then gradually drip a calculated amount of aminosilane coupling agent into the reactor at a certain dropping speed, react at a constant temperature for 2h to 3h under nitrogen protection, and obtain reactant A.

[0062] The bisphenol A epoxy resin E44 may include a structure as shown in Formula 2. The aminosilane coupling agent may include a structure as shown in Formula 3. The reactant A may include a structure as shown in Formula 4.

[0063]

[0064]

[0065] In Formula 2, Formula 3 and Formula 4, n can be an integer of 1 to 25; R1 can be an alkyl group or phenyl group with not less than 2 methylene groups, R2 can be an alkyl group with 1 to 3 carbon atoms, R3 can be a straight chain or branched chain alkyl group with 1 to 3 carbon atoms, and m1+m2=3.

[0066] S02: Continue stirring under nitrogen protection, control the material temperature to 80℃~85℃; then drop calculated amount of glycidyl methacrylate or 3,4-epoxyhexyl methacrylate and benzoyl peroxide into the reactor, control a certain drop reaction speed, continue heating and stirring to react, control the temperature to 90℃~95℃, keep constant temperature reaction for 6h~7h, then evacuate, and distill under reduced pressure for 0.5h~1h to obtain modified epoxy resin (which can be the structure shown in Formula 1 above). Benzaldehyde peroxide is 0.3%~0.5% of the total mass of the reaction.

[0067] The molar ratio of the epoxy resin E44, the aminosilane coupling agent and the glycidyl methacrylate is 2:(1-1.05):(1-3).

[0068] In an embodiment of the third aspect of the present application, a waterproof product is provided, comprising: a waterproof coating and an asphalt waterproof roll covering the waterproof coating, wherein the waterproof coating is formed by the silane-modified polyether waterproof coating provided in the first aspect of the present application.

[0069] Example

[0070] The following examples more specifically describe the disclosure of the present application, which are intended for illustrative purposes only, as it will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the disclosure of the present application. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing, and the instruments used in the examples are commercially available.

[0071] The sources of the raw materials used in the following examples and comparative examples are as follows: Wacker silane-modified polyether: STP-E35, purchased from Wacker Chemical (China) Co., Ltd.; Kaneka silane-modified polyether: SAX750, purchased from Kaneka Trading (Shanghai) Co., Ltd.; epoxy-modified silicone resin: SH-023, purchased from Hubei Xinsihai Chemical Co., Ltd.; catalyst: chelated tin U303, purchased from Guangzhou Jianyi Chemical Import and Export Co., Ltd. Aldimine curing agent XY-401, purchased from Suzhou Xiangyuan New Materials Co., Ltd. Dibutyl phthalate, purchased from Shandong Hongxin Chemical Co., Ltd. Other raw materials not specifically stated are common commercial products.

[0072] Preparation Example 1

[0073] The modified epoxy resin 1 of this preparation example was prepared by the following method:

[0074] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and N,N-dimethylformamide (volume ratio of 1:1), the amount of the mixed solvent of n-butanol and N,N-dimethylformamide is 15% of the total mass of the reaction, start stirring until the epoxy resin is completely dissolved, control the material temperature to 100°C, and then control a certain dropwise addition speed to gradually drop a calculated amount of γ-aminopropyltrimethoxysilane purchased from Hubei New Blue Sky New Materials Co., Ltd. into the reactor, and react at a constant temperature for 3 hours under nitrogen protection to obtain reactant A.

[0075] S02: Continue stirring under nitrogen protection and control the material temperature to 80°C; then add the calculated amount of glycidyl methacrylate and benzoyl peroxide to the reactor, control the dropwise reaction rate to a certain level, continue heating and stirring the reaction, control the temperature to 95°C, react at a constant temperature for 7 hours, then evacuate and distill under reduced pressure for 1 hour to obtain modified epoxy resin 1 (structure as shown in Formula 1 above, epoxy equivalent is 340 g / eq).

[0076] The amount of benzaldehyde peroxide is 0.4% of the total mass of the reaction, and the molar ratio of epoxy resin E44, aminosilane coupling agent and glycidyl methacrylate is 2:1.05:2.

[0077] Preparation Example 2

[0078] The preparation process of the modified epoxy resin 2 in this preparation example is basically the same as that of the preparation example 1, except that the molar ratio of the epoxy resin E44, the aminosilane coupling agent and the glycidyl methacrylate is 1:2:1, and the epoxy equivalent is 950 g / eq.

[0079] Preparation Example 3

[0080] The preparation process of the modified epoxy resin 3 in this preparation example is basically the same as that in preparation example 1, except that the molar ratio of epoxy resin E44, aminosilane coupling agent and glycidyl methacrylate is 2:1.05:4, and the epoxy equivalent is 274 g / eq.

[0081] Comparative Preparation Example 1

[0082] The preparation process of the modified epoxy resin D1 in this preparation example is basically the same as that in Preparation Example 1, except that only step S01 is performed.

[0083] Wherein, the molar ratio of epoxy resin E44 to aminosilane coupling agent is 2:2.02.

[0084] The molar amount of the alkoxysilane group of the modified epoxy resin D1 is greater than the molar amount of the epoxy group, and the structural formula is shown in Formula 5 below, wherein n is an integer of 1 to 25, and m1+m2=3.

[0085]

[0086] Comparative Preparation Example 2

[0087] The modified epoxy resin D2 of this preparation example was prepared by the following method:

[0088] S01: Add a calculated amount of dried bisphenol A epoxy resin E44 into a reactor, add a mixed solvent of n-butanol and N,N-dimethylformamide (volume ratio is 1:1), the amount of the mixed solvent of n-butanol and N,N-dimethylformamide is 15% of the total mass of the reaction, and stir until the epoxy resin is completely dissolved;

[0089] S02: Continue stirring under nitrogen protection and control the material temperature to 80°C; then add the calculated amount of glycidyl methacrylate and benzoyl peroxide to the reactor, control the dropwise reaction speed to a certain level, continue heating and stirring the reaction, control the temperature to 90°C to 95°C, react at a constant temperature for 7 hours, then evacuate and distill under reduced pressure for 1 hour to obtain modified epoxy resin D2.

[0090] The amount of benzaldehyde peroxide is 0.4% of the total mass of the reaction; and the molar ratio of epoxy resin E44 to glycidyl methacrylate is 1:2.

[0091] Example 1

[0092] The silane-modified polyether waterproof coating of this embodiment includes the following components in parts by weight:

[0093] STP-E35, 100 parts by weight; SAX750, 75 parts by weight; SH-023, 58 parts by weight; epoxidized soybean oil, 350 parts by weight; heavy calcium, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1 (Preparation Example 1, epoxy equivalent is 340g / eq), 15 parts by weight; aldimine curing agent XY-401, 22 parts by weight; vinyltrimethoxysilane, 8 parts by weight; triacetoxyethylsilane, 2 parts by weight; U303, 1.4 parts by weight.

[0094] The preparation method of the silane-modified polyether waterproof coating of this embodiment comprises the following steps:

[0095] (1) Add predetermined weight portions of Wacker silane-modified polyether STP-E35, silane-modified polyether SAX750, and epoxidized soybean oil into a reaction kettle, start stirring, heat to 95° C., and add pigment filler heavy calcium and nano calcium carbonate while stirring; after the powder is completely stirred, heat to 105° C., evacuate, and dehydrate for 3.5 hours to obtain a first reactant;

[0096] (2) cooling the first reactant to 65° C., adding SH-023, modified epoxy resin and aldimine latent curing agent, and stirring under vacuum for 0.5 h to obtain a second reactant;

[0097] (3) The second reactant is cooled to 55°C, and a dehydrating agent, vinyl trimethoxysilane, and a accelerator, triacetoxyethyl silane, are added, and the mixture is stirred under vacuum for 0.5 h. The temperature is maintained at 55°C, and a catalyst, U303, is added, and the mixture is stirred under vacuum for 0.5 h. The mixture is then cooled to below 50°C, and nitrogen is filled for protection. The mixture is discharged to obtain a silane-modified polyether waterproof coating.

[0098] Example 2

[0099] The silane-modified polyether waterproof coating of this embodiment includes the following components in parts by weight:

[0100] STP-E35, 100 parts by weight; SAX750, 75 parts by weight; SH-023, 58 parts by weight; epoxidized soybean oil, 350 parts by weight; heavy calcium, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1, 8 parts by weight; aldimine curing agent XY-401, 22 parts by weight; vinyltrimethoxysilane, 8 parts by weight; triacetoxyethylsilane, 2 parts by weight; U303, 1.4 parts by weight.

[0101] The preparation process of the silane-modified polyether waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0102] Example 3

[0103] The silane-modified polyether waterproof coating of this embodiment includes the following components in parts by weight:

[0104] STP-E35, 100 parts by weight; SAX750, 75 parts by weight; SH-023, 58 parts by weight; epoxidized soybean oil, 350 parts by weight; heavy calcium, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1, 17 parts by weight; aldimine curing agent XY-401, 22 parts by weight; vinyltrimethoxysilane, 8 parts by weight; triacetoxyethylsilane, 2 parts by weight; U303, 1.4 parts by weight.

[0105] The preparation process of the silane-modified polyether waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0106] Example 4

[0107] The silane-modified polyether waterproof coating of this embodiment includes the following components in parts by weight:

[0108] STP-E35, 100 parts by weight; SAX750, 75 parts by weight; SH-023, 58 parts by weight; epoxidized soybean oil, 250 parts by weight; heavy calcium, 400 parts by weight; nano calcium carbonate, 160 parts by weight; modified epoxy resin 1, 17 parts by weight; aldimine curing agent XY-401, 22 parts by weight; vinyltrimethoxysilane, 8 parts by weight; triacetoxyethylsilane, 2 parts by weight; U303, 1.4 parts by weight.

[0109] The preparation process of the silane-modified polyether waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0110] Example 5

[0111] The composition and preparation process of the silane-modified polyether waterproof coating of this embodiment are similar to those of Example 1, except that the modified epoxy resin is replaced by modified epoxy resin 2 (Preparation Example 2).

[0112] Example 6

[0113] The composition and preparation process of the silane-modified polyether waterproof coating of this embodiment are similar to those of Example 1, except that the modified epoxy resin is replaced by modified epoxy resin 3 (Preparation Example 3).

[0114] Comparative Example 1

[0115] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that SH-023 in Example 1 is removed and replaced by an equal weight portion of a common plasticizer, dibutyl phthalate.

[0116] Comparative Example 2

[0117] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that the epoxy soybean oil in Example 1 is removed and replaced with an equal weight portion of a common plasticizer, dibutyl phthalate.

[0118] Comparative Example 3

[0119] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that the modified epoxy resin in Example 1 is removed and replaced by an equal weight portion of aldimine curing agent XY-401.

[0120] Comparative Example 4

[0121] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that SH-023 and modified epoxy resin in Example 1 are removed and replaced by equal parts by weight of common plasticizer dibutyl phthalate and aldimine curing agent XY-401, respectively.

[0122] Comparative Example 5

[0123] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that the modified epoxy resin is replaced by modified epoxy resin D1, and the structural formula is shown in Formula 5, wherein n is an integer of 1 to 25, and m1+m2=3.

[0124]

[0125] Comparative Example 6

[0126] The composition and preparation process of the silane-modified polyether waterproof coating in this comparative example are similar to those of Example 1, except that the modified epoxy resin is replaced by modified epoxy resin D2.

[0127] Performance Testing

[0128] The performance of the silane-modified polyether waterproof coatings prepared in the embodiments and comparative examples was tested, and the test performance is shown in Table 1.

[0129] (1) The coating performance tests in Table 1 were conducted in accordance with the test standards in T / CBMF 105-2021 / T / CWA 203-2021 and GB / T16777-2008, and were carried out under the curing test conditions specified in the standards to obtain the surface drying time, actual drying time, tensile strength, elongation at break and bonding strength.

[0130] (2) The test method of the composite peel strength of the roll material is as follows: the prepared coating layer is overlapped with the asphalt waterproofing roll material, and the 180° peel strength is tested after the overlap. Specifically, the silane-modified polyether waterproofing coating is applied to the base surface by cold construction, and the coating thickness is 1.5±0.2mm. After the coating is completed, the asphalt waterproofing roll material is laid and covered on the coating layer during the coating adaptation period, so that the roll material and the coating are in a fully adhered state. After curing for 168 hours, the 180° peel strength is tested. The specific test steps are as follows:

[0131] The size and preparation method of the test piece: 1. Cut the asphalt waterproofing membrane and keep the bonding surface size at the preset size, which is 70*50mm; 2. Apply the silane-modified polyether waterproofing coating to the base surface; 3. Then directly lay the cut membrane with isolation film on the silane-modified polyether waterproofing coating and compact it to make it fully adhered; 4. Cure the prepared test piece under standard curing conditions for 168 hours.

[0132] Test method: Install the cement mortar block surface in the above test piece on the fixture at one end of the electronic tensile tester, and bend the non-bonded surface of the coiled material in the above test piece opposite to the bonding surface by 180° and clamp it in the fixture at the other end of the tester. Pay attention to accurately position the test piece between the chucks to ensure that the applied tensile force is evenly distributed over the width of the test piece. Start the testing equipment and set the tensile speed to 100mm / min.

[0133] (3) The test method for the adhesive strength of wet substrates shall be carried out in accordance with the provisions of GB / T16777-2008.

[0134]

[0135] From the data in the table, it can be seen from the comparison between Examples 1 to 6 and Comparative Examples 1 to 6 that the coatings in Examples 1 to 5 have better performance in terms of bonding strength, wet base bonding strength, composite peeling strength with coils, peeling failure forms, etc., and the bonding and peeling properties of Example 4 are reduced after the amount of nano-calcium carbonate used is reduced; the bonding properties of the coatings in Comparative Examples 1 to 6 and the composite peeling strength of the coils are significantly lower than those in Examples 1 to 6, and the composite peeling strength (N / mm) data and the failure form of the coils can clearly show that the comparative example 2 replaced by the ordinary plasticizer dibutyl phthalate, especially the composite peeling strength with the coils, is significantly reduced, and the cohesive strength of the coils is also reduced to a large extent, but the lower peeling strength value causes the cohesive failure of the coils, which indicates that the ordinary plasticizer causes compatibility problems such as softening of the coil matrix material. In addition, it can be seen that the use of epoxy-modified silicone resin SH-023 and modified epoxy resin in the formula can play a certain synergistic role. The epoxy-modified silicone resin SH-023 and modified epoxy resin together improve the peeling performance of the coiled material, and also improve the bonding performance to the base surface, especially the wet base surface.

[0136] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A silane-modified polyether waterproof coating, characterized in that: The silane-modified polyether waterproof coating comprises the following components in parts by weight: Wacker alkoxy-terminated polyether, 100 parts; and each based on 100 parts of Wacker alkoxy-terminated polyether: 65-96 parts of potassium alkoxy terminated polyether; Epoxy modified silicone resin, 45-80 parts; 8-17 parts of modified epoxy resin; the modified epoxy resin comprises alkoxysilane groups, epoxy groups and acrylic acid segments; Epoxy plasticizer, 250-380 parts; Latent curing agent, 5 to 24 parts; Pigments and fillers: 430-780 parts; Additives, 8 to 20 parts.

2. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The epoxy equivalent of the modified epoxy resin ranges from 300 g / eq to 410 g / eq.

3. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The modified epoxy resin comprises a structure as shown in Formula 1 below: In formula 1, n is an integer of 1 to 25, X is an integer of 1 to 3; R1 is not less than 2 methylene groups or phenyl groups, R2 is an alkyl group of 1 to 3 carbon atoms, R3 is a straight chain or branched alkyl group of 1 to 3 carbon atoms, and m1+m2=3.

4. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The Wacker alkoxy-terminated polyether includes one or more of STP-E35, STP-E30, STP-E15 and STP-E10; and or, The potassium alkoxy terminated polyether includes one or more of SAX227, SAX327, SAX220 and SAX750.

5. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The epoxy-modified silicone resin includes one of SH-023 and SH-9614 or a combination thereof.

6. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The epoxy plasticizer comprises one or more of epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil and epoxidized sunflower oil; and / or, The latent curing agent includes one or more of an aldimine curing agent, a ketimine curing agent and an oxazolidine curing agent.

7. The silane-modified polyether waterproof coating according to claim 1, characterized in that: The pigment filler includes one or more of fumed silica, nano calcium carbonate, heavy calcium carbonate, modified heavy calcium carbonate, nano clay, carbon black and modified clay; and / or; The additive includes one or more of a dewatering agent, a promoter and a catalyst; optionally, the dewatering agent includes one or more of vinyl trimethoxy silane, vinyl triacetoxy silane and vinyl triethoxy silane; Optionally, the accelerator includes one or more of triacetoxyethylsilane, vinyltriacetoxysilane and diethyldiacetoxysilane; Optionally, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and chelated tin catalyst.

8. The method for preparing the silane-modified polyether waterproof coating according to any one of claims 1 to 7, characterized in that: include: Mixing predetermined weight portions of Wacker silane-modified polyether, Kalium-modified silane-modified polyether, epoxy plasticizer, and pigment and filler under a first condition to obtain a first reactant; Mixing the first reactant, epoxy-modified silicone resin, modified epoxy resin and latent curing agent under a second condition to obtain a second reactant; The second reactant and the additive are mixed to obtain the silane-modified polyether waterproof coating.

9. The method for preparing the silane-modified polyether waterproof coating according to claim 8, characterized in that: In the step of mixing the first reactant and epoxy-modified silicone resin, modified epoxy resin and latent curing agent under a second condition to obtain a second reactant, the modified epoxy resin is formed by polymerization reaction of epoxy resin, acrylic monomer with epoxy group and aminosilane coupling agent.

10. A waterproof product comprising: A waterproof coating and an asphalt waterproof substrate covering the waterproof coating, wherein the waterproof coating is formed by the silane-modified polyether waterproof coating according to any one of claims 1 to 7.

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