Silane-modified polyether waterproof coating, preparation method and waterproof product

Abstract

The present application provides a silane-modified polyether waterproof coating, a preparation method and a waterproof product. The coating comprises 100 parts of Wacker alkoxy-terminated polyether; and based on 100 parts of Wacker alkoxy-terminated polyether: 65-96 parts of Zhonghua alkoxy-terminated polyether; 45-80 parts of epoxy-modified silicone resin; 8-17 parts of modified epoxy resin, the modified epoxy resin comprising an alkoxysilyl group, an epoxy group and an acrylic link; 250-380 parts of epoxy plasticizer; 5-24 parts of latent curing agent; 430-780 parts of pigment and filler; and 8-20 parts of additive. The modified epoxy resin in the coating of the present application contains an alkoxysilyl group, an epoxy group and an acrylic link, which can improve the adhesion performance and peel performance to waterproof coiled materials and the base surface.

Description

Technical Field

[0001] This 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 prepared based on a modified polyether resin, with functional auxiliaries, fillers, pigments, and catalysts added. It has advantages such as 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 organosilicon-modified polyether resin, initially mainly appeared in the form of terminal silane group polyether sealants. Silane group polyether sealants are also known as MS sealants, organosilicon-modified polyether sealants, and modified silicone sealants. Silane polyether building waterproof coatings are mainly used for waterproofing and moisture-proofing in areas such as kitchens, bathrooms, and balconies. When used, they are applied to the base layer and cured by reacting with moisture to form a continuous and seamless high-molecular elastic waterproof film. Silane-modified polyether waterproof coatings can be used in areas such as roofs and exterior walls with an appropriate protective layer applied. This coating can be applied by scraping, rolling, brushing, or spraying, and can be constructed to the designed thickness in one application, saving time and construction costs.

[0004] In the field of building waterproofing, silane-modified polyether waterproof coatings can be used to form a secondary waterproof layer in the cold operation construction of some waterproof membranes. Silane-modified polyether waterproof coatings and waterproof membranes can form a good bonding interface on the surface, showing excellent bonding performance. The formed coating-membrane adhesive layer has excellent bonding and adhesion performance, the bonding layer is tight and impermeable, with excellent performance, an overall excellent waterproof effect, and a long service life. As a new type of waterproof coating, it has been promoted.

[0005] However, the peel strength of the silane-modified polyether waterproof coating after being compounded with the membrane is low, and the bonding performance of the silane-modified polyether waterproof coating to the cement base surface is low, making it difficult to meet the construction progress requirements and waterproof requirements. Summary of the Invention

[0006] This 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 compounded with the membrane, as well as its bonding performance.

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

[0008] In a feasible embodiment of the first aspect of the present application, the epoxy equivalent range of the modified epoxy resin is 300 g / eq to 410 g / eq.

[0009] In a feasible embodiment of the first aspect of the present application, the modified epoxy resin includes the structure shown in the following formula 1:

[0010]

[0011] In formula 1, n is an integer from 1 to 25, X is an integer from 1 to 3; R1 is at least 2 methylene groups or phenyl groups, R2 is an alkyl group with 1 to 3 carbon atoms, R3 is a straight-chain or branched-chain alkyl group with 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 Kaneka alkoxy-terminated polyether includes one or more of SAX227, SAX327, SAX220 and SAX750.

[0014] In a feasible embodiment 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 embodiment 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 embodiment of the first aspect of the present application, the latent curing agent includes one or more of aldehyde imine curing agents, ketone imine curing agents and oxazolidine curing agents.

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

[0018] In a feasible embodiment of the first aspect of the present application, the additive includes one or several of water scavenger, accelerator, and catalyst.

[0019] Optionally, the water scavenger includes one or several of vinyltrimethoxysilane, vinyltriacetoxysilane, and vinyltriethoxysilane.

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

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

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

[0023] Mixing a predetermined weight portion of Wacker silane-modified polyether, Zhonghua silane-modified polyether, epoxy plasticizer, and pigment extender under the first condition to obtain a first reaction product;

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

[0025] Mixing the second reaction product with the additive under catalytic conditions to obtain the silane-modified polyether waterproof coating.

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

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

[0028] In the coating of the present application, the modified epoxy resin contains multiple epoxy groups and alkoxysilyl groups. The epoxy groups can react with the epoxy groups in the epoxy plasticizer and epoxy-modified silicone resin to crosslink with the hydrolyzed latent curing agent. The combined use of the three components containing epoxy groups can increase the speed and crosslinking density of the epoxy ring-opening crosslinking reaction, improve the adhesion and peel properties to waterproof coiled materials and cement base surfaces, and make the cured system free of free plasticizer, avoiding the migration of plasticizer and improving the compatibility, peel strength and adhesion with waterproof coiled materials.

[0029] Meanwhile, the modified epoxy resin also contains alkoxysilyl groups. After hydrolysis, the alkoxysilyl groups can undergo a condensation crosslinking reaction with alkoxy-terminated polyethers, and improve the adhesion by crosslinking with active groups such as hydroxyl groups on the cement base surface, hydroxyl groups and carboxyl groups in the coiled material matrix; it can also improve the problem that the silane-modified polyether waterproof coating has high requirements for the dryness of the base surface and poor adhesion effect on the wet concrete base surface; moreover, 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] Furthermore, the modified epoxy resin also contains acrylic acid linkages. A large number of polar groups contained in acrylic acid, such as hydroxyl groups and carboxyl groups, have good hydrophilicity and good affinity for the base surface, and can interact with polar groups on the base surface to form intermolecular forces, enhancing the adhesion; the epoxy resin modified by acrylic acid can also increase the molecular weight of the polymer, making the cured polymer molecular chains longer, denser and the intermolecular cohesion stronger, thereby enhancing the strength and toughness of the adhesive layer between the waterproof coating and the substrate. Detailed implementation mode

[0031] In order to make the invention purpose, technical solution and beneficial technical effects of the present application clearer, the present application will be further described in detail below with reference to embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application and 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 a range not explicitly recorded; and any lower limit can be combined with other lower limits to form a range not explicitly recorded, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recorded. In addition, although not explicitly recorded, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower or upper limit and combined with any other point or single value or combined with other lower or upper limits to form a range not explicitly recorded.

[0033] In the description herein, when a composition is described as containing, comprising, or including a particular component, or when a process is described as containing, comprising, or including a particular process step, it is contemplated that the compositions of the present application also consist essentially of or consist of the components, and the processes of the present application also consist essentially of or consist of the process steps.

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

[0035] In the description herein, it should be noted that, unless otherwise specified, "above" and "below" include the recited number, and the meaning of "plural" in "one or more" is more than two.

[0036] The above summary of the invention of the present application is not intended to describe every disclosed embodiment or every implementation of the present application. The following description more specifically illustrates exemplary embodiments. Throughout the application, guidance is provided through a series of examples that can be used in various combinations. In each instance, the listings are only representative groups and should not be construed as exhaustive.

[0037] Due to the migration of plasticizers, traditional silane-modified polyether waterproof coatings can cause compatibility problems with waterproof membranes. The migration of plasticizers causes a swelling effect on waterproof membranes, especially those composed of components such as bitumen and butyl rubber, reducing the cohesion and adhesion and peel strength of the membrane components to varying degrees. In addition, traditional silane-modified polyether waterproof coatings have less than ideal adhesion to cement substrates, with low adhesion performance and certain requirements for the dryness of the substrate. They cannot be applied on wet concrete substrates, have poor wettability, poor adhesion effect, and a significant decrease in adhesion strength, failing to meet the construction progress and waterproof requirements. Therefore, how to prepare a silane-modified polyether waterproof coating with excellent adhesion, no compatibility problems such as plasticizer migration to waterproof membranes, and the ability to be directly applied on wet substrates 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 and adhesion performance after the silane-modified polyether waterproof coating is compounded with the membrane.

[0039] In an embodiment of the first aspect of the present application, a silane-modified polyether waterproof coating is provided. The silane-modified polyether waterproof coating comprises components in the following parts by weight: Wacker alkoxy-terminated polyether, 100 parts; and based on 100 parts of Wacker alkoxy-terminated polyether: Kaneka alkoxy-terminated polyether, 65 - 96 parts; epoxy-modified silicone resin, 45 - 80 parts; modified epoxy resin, 8 - 17 parts, and the modified epoxy resin includes alkoxysilyl groups, epoxy groups and acrylic linkages; epoxy plasticizer, 250 - 380 parts; latent curing agent, 5 - 24 parts; pigment and filler, 430 - 780 parts; additive, 8 - 20 parts.

[0040] In the coating of the present application, the modified epoxy resin contains multiple epoxy groups and alkoxysilyl groups. Its epoxy groups can react with the epoxy groups in the epoxy plasticizer and the epoxy-modified silicone resin to crosslink with the hydrolyzed latent curing agent. The combined use of the three components containing epoxy groups can improve the speed and crosslinking density of the epoxy ring-opening crosslinking reaction, enhance the adhesion and peel properties to the waterproof coiled material and the base surface, and can make the cured system free of free plasticizer, avoiding the migration of the plasticizer, and improving the compatibility, peel strength and adhesion performance with the waterproof coiled material.

[0041] Meanwhile, the modified epoxy resin also contains alkoxysilyl groups. After hydrolysis, the alkoxysilyl groups can undergo a condensation crosslinking reaction with the alkoxy-terminated polyether, and improve the adhesion by crosslinking with active groups such as hydroxyl groups on the base surface, hydroxyl groups and carboxyl groups in the coiled material matrix; it can also improve the problem that the silane-modified polyether waterproof coating has high requirements for the dryness of the base surface and poor adhesion effect on the wet concrete base surface; in addition, 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 linkages. A large number of polar groups contained in acrylic acid, such as hydroxyl groups and carboxyl groups, have good hydrophilicity and good affinity for the base surface, and can interact with polar groups on the surface of the base surface to form intermolecular forces, enhancing the adhesion; the epoxy resin modified by acrylic acid can also increase the molecular weight of the polymer, making the cured polymer molecular chains longer, denser, and the intermolecular cohesion stronger, thereby enhancing the strength and toughness of the adhesive layer between the waterproof coating and the substrate.

[0043] In some embodiments, the epoxy equivalent range of the modified epoxy resin is 300 g / eq - 410 g / eq.

[0044] The modified epoxy resin of the present application also has a suitable epoxy equivalent range. In particular, the modified epoxy resin within the above range not only has high activity, fast crosslinking speed, and high crosslinking density, which can improve the peel strength and adhesion performance of the waterproof coil, 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 alkoxysilyl groups. The relatively higher proportion of epoxy groups can increase the speed and crosslinking density of the ring-opening crosslinking reaction of epoxy groups, and further improve the adhesion performance and peel strength to the waterproof coil and the base surface.

[0046] Bisphenol-type epoxy resin contains multiple epoxy groups, a bisphenyl ring rigid structure, and has good activity. Using bisphenyl-type epoxy resin as the backbone structure and introducing acrylic linkages with epoxy groups and alkoxysilyl groups can further improve the strength of the coating, such as adhesion strength, tensile strength, and tear strength. In some embodiments, the modified epoxy resin may include the structure shown in Formula 1 below:

[0047]

[0048] In Formula 1, n is an integer from 1 to 25, X is an integer from 1 to 3; R1 is no less than 2 methylene groups or phenyl groups, R2 is an alkyl group with 1 to 3 carbon atoms, R3 is a straight-chain or branched-chain alkyl group with 1 to 3 carbon atoms, and m1 + m2 = 3.

[0049] The plasticizer selected in the present application is a plasticizer with epoxy groups. Exactly because it contains epoxy groups, it can undergo ring-opening crosslinking reactions with the multiple epoxy 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, so that the plasticizer can be fixed in the coating film, preventing its migration and penetration into the coil, and increasing the speed and crosslinking density of the ring-opening crosslinking reaction of epoxy groups. 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 release amino groups by hydrolysis, so that it can undergo crosslinking reactions with the epoxy-group-containing components in the coating, reduce the swelling effect of free components in the system on the waterproof coil, and increase the curing speed of the coating. In some embodiments, the latent curing agent may include one or more of aldehyde imine curing agents, ketone imine curing agents, and oxazolidine curing agents. Optionally, it may include one or more of aldehyde imines, ketone imines, and oxazolidines.

[0051] In the present application, the polyether selected has alkoxy end groups. The alkoxy end groups in the polyether can undergo a dehydration reaction with the silanol groups formed after hydrolysis of the alkoxysilyl groups to form new silicon-oxygen bonds (Si-O-Si), enhancing the heat resistance and bonding 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 Kaneka 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 properties by selecting an epoxy organosilicon resin with better water resistance, weather resistance, and heat resistance. In some embodiments, the epoxy-modified organosilicon resin may include one or a combination of SH-023 and SH-9614.

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

[0054] The additives may include one or several of water scavengers, accelerators, and catalysts. Optionally, the water scavenger may include one or several of vinyltrimethoxysilane, vinyltriacetoxysilane, and vinyltriethoxysilane. Optionally, the accelerator may include one or several of triacetoxyethylsilane, vinyltriacetoxysilane, and diethyldiacetoxysilane. Optionally, the catalyst may include one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and chelated tin catalyst.

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

[0056] Mixing a predetermined weight portion of Wacker silane-modified polyether, Kaneka silane-modified polyether, epoxy plasticizer, and pigment and filler under a first condition to obtain a first reactant; mixing the first reactant with an epoxy-modified organosilicon resin, a modified epoxy resin, and a latent curing agent under a second condition to obtain a second reactant; mixing the second reactant with additives under a catalytic condition to obtain the silane-modified polyether waterproof coating.

[0057] Specifically, in the step of mixing a predetermined weight portion of Wacker silane-modified polyether, potassium silane-modified polyether, epoxy plasticizer, and pigment and filler under the first conditions to obtain a first reactant, the preparation of the first reactant may include adding Wacker silane-modified polyether, potassium silane-modified polyether, and epoxy plasticizer into a reaction kettle, mixing and stirring, heating to 90°C - 100°C, and adding pigment and filler while stirring; after the powder is completely stirred evenly, heating to 100°C - 110°C, evacuating the air, and performing a dehydration reaction for 3h - 4h to obtain the first reactant.

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

[0059] Specifically, in the step of mixing the second reactant and additives under catalytic conditions to obtain a silane-modified polyether waterproof coating, it may include cooling the second reactant to 50°C - 60°C, adding a water remover and a promoter, evacuating the air and stirring for 0.5h - 1h, then maintaining the temperature at 50°C - 60°C, adding a catalyst, evacuating the air and continuing to stir for 0.5h - 1h, cooling to below 50°C, protecting with nitrogen, and discharging the material.

[0060] Among them, the modified epoxy resin can be formed by the polymerization reaction of epoxy resin, acrylic monomer with an epoxy group, and amino silane coupling agent. Specifically, the modified epoxy resin can be prepared by the following method:

[0061] S01: Put the 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 1:1), and the amount of the mixed solvent of n-butanol and N,N-dimethylformamide is 10% - 15% of the total mass of the reaction. Start stirring until the epoxy resin is completely dissolved, control the material temperature at 90°C - 110°C, and then gradually drop the calculated amount of amino silane coupling agent into the reactor at a certain dropping rate, and react at a constant temperature for 2h - 3h under nitrogen protection to obtain reactant A.

[0062] Among them, bisphenol A epoxy resin E44 may include the structure shown in formula 2 below. The amino silane coupling agent may include the structure shown in formula 3 below. Reactant A may include the structure shown in formula 4 below.

[0063]

[0064]

[0065] In Formulas 2, 3, and 4, n can be an integer from 1 to 25 respectively; R1 can be an alkyl group or a phenyl group with no less than 2 methylene groups respectively, R2 can be an alkyl group with 1 to 3 carbon atoms respectively, R3 can be a straight-chain or branched-chain alkyl group with 1 to 3 carbon atoms respectively, and m1 + m2 = 3.

[0066] S02: Continue stirring under nitrogen protection, controlling the material temperature at 80°C to 85°C; then dropwise add a calculated amount of glycidyl methacrylate or 3,4-epoxyhexyl methacrylate and benzoyl peroxide into the reactor, controlling a certain dropping reaction rate, continue heating and stirring the reaction, controlling the temperature at 90°C to 95°C, and carrying out the constant-temperature reaction for 6h to 7h, then evacuate and carry out vacuum distillation for 0.5h to 1h to obtain a modified epoxy resin (which can have the structure shown in Formula 1 above). Among them, benzoyl peroxide is 0.3% to 0.5% of the total mass of this reaction.

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

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

[0069] Embodiment

[0070] The following examples more specifically describe the content disclosed in the present application. These examples are only for illustrative purposes, because various modifications and changes within the scope of the content disclosed in the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all 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 mentioned are ordinary commercially available products.

[0072] Preparation Example 1

[0073] The modified epoxy resin 1 in 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 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 at 100 °C, and then gradually drop the calculated amount of γ-aminopropyltrimethoxysilane, purchased from Hubei New Blue Sky New Materials Co., Ltd., into the reactor at a certain dropping rate. React at a constant temperature for 3 h under nitrogen protection to obtain reactant A.

[0075] S02: Continue stirring under nitrogen protection, control the material temperature at 80 °C; then drop the calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, control a certain dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 95 °C, react at a constant temperature for 7 h, and then evacuate and distill under reduced pressure for 1 h to obtain modified epoxy resin 1 (the structure shown in formula 1 above, epoxy equivalent is 340 g / eq).

[0076] Among them, benzoyl peroxide is 0.4% of the total mass of the reaction, and the molar ratio of epoxy resin E44, amino silane coupling agent to 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 Preparation Example 1, except that the molar ratio of epoxy resin E44, amino silane coupling agent to 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 of Preparation Example 1, except that the molar ratio of epoxy resin E44, amino silane coupling agent to 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 of Preparation Example 1, except that only step S01 is carried out.

[0083] Among them, the molar ratio of epoxy resin E44 to amino silane coupling agent is 2:2.02.

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

[0085]

[0086] Comparative Preparation Example 2

[0087] This preparation example of the modified epoxy resin D2 is prepared by the following method:

[0088] 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 1:1), and 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;

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

[0090] Among them, benzoyl peroxide is 0.4% of the total mass of the reaction; the molar ratio of epoxy resin E44 to glycidyl methacrylate is 1:2.

[0091] Example 1

[0092] This example of the silane-modified polyether waterproof coating comprises 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; epoxy soybean oil, 350 parts by weight; heavy calcium carbonate, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1 (Preparation Example 1, epoxy equivalent is 340 g / eq), 15 parts by weight; aldehyde imine 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 this example of the silane-modified polyether waterproof coating comprises the following steps:

[0095] (1) Add a predetermined weight portion of Wacker silane-modified polyether STP-E35, Kaneka silane-modified polyether SAX750, and epoxy soybean oil into a reaction kettle. Start stirring and heat up to 95°C. While stirring, add the pigment and filler heavy calcium carbonate and nano calcium carbonate. After the powder materials are completely stirred evenly, heat up to 105°C, evacuate the air, and carry out a dehydration reaction for 3.5 h to obtain a first reactant;

[0096] (2) Cool the first reactant to 65°C, add SH-023, modified epoxy resin, and aldehyde imine latent curing agent, evacuate the air and stir for 0.5 h to obtain a second reactant;

[0097] (3) Cool the second reactant to 55°C, add the water remover vinyltrimethoxysilane and the accelerator triacetoxyethylsilane, evacuate the air and stir for 0.5 h. Keep the temperature at 55°C, add the catalyst U303, evacuate the air and continue stirring for 0.5 h. Then cool down to below 50°C, fill with nitrogen for protection, and discharge to obtain a silane-modified polyether waterproof coating.

[0098] Example 2

[0099] The silane-modified polyether waterproof coating of this example comprises 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; epoxy soybean oil, 350 parts by weight; heavy calcium carbonate, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1, 8 parts by weight; aldehyde imine 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 of this example is basically the same as that of Example 1 and will not be elaborated here.

[0102] Example 3

[0103] The silane-modified polyether waterproof coating of this example comprises 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; epoxy soybean oil, 350 parts by weight; heavy calcium carbonate, 400 parts by weight; nano calcium carbonate, 260 parts by weight; modified epoxy resin 1, 17 parts by weight; aldehyde imine 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 of this example is basically the same as that of Example 1 and will not be elaborated here.

[0106] Example 4

[0107] The silane-modified polyether waterproof coating of this example comprises 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 carbonate, 400 parts by weight; nano calcium carbonate, 160 parts by weight; modified epoxy resin 1, 17 parts by weight; aldehyde imine 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 of this example is basically the same as that of Example 1 and will not be elaborated here.

[0110] Example 5

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

[0112] Example 6

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

[0114] Comparative Example 1

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

[0116] Comparative Example 2

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

[0118] Comparative Example 3

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

[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: Mount the surface of the cement mortar block in the above test piece on the fixture at one end of the electronic tensile testing machine, and bend the unbonded surface of the coil in the above test piece opposite to the bonding surface by 180° and clamp it in the fixture at the other end of the testing machine. Note to accurately position the test piece between the chucks to ensure that the applied tensile force is evenly distributed across the width of the test piece. Start the testing equipment and set the tensile speed to 100 mm / min.

[0133] (3) The test method for the bonding strength on a wet base surface shall be carried out in accordance with the provisions of GB / T 16777-2008.

[0134]

[0135] From the data in the table, it can also be seen from the comparison between Examples 1-6 and Comparative Examples 1-6 that in terms of various properties such as the bonding strength of the coating, the bonding strength on a wet base surface, the peel strength of the composite with the coil, and the peel failure form, the properties of the coatings in Examples 1-5 are more excellent. After reducing the usage amount of nano-calcium carbonate in Example 4, the bonding and peeling properties decreased to a certain extent; the bonding properties of the coatings and the peel strength of the composite with the coil in Comparative Examples 1-6 are significantly lower than those in Examples 1-6. From the data of the peel strength of the composite with the coil (N / mm) and the failure form, it can be clearly seen that in Comparative Example 2 where the common plasticizer dibutyl phthalate is substituted, especially the peel strength of the composite with the coil decreased significantly, and the cohesive strength of the coil also decreased to a large extent. The lower peel strength value caused the cohesive failure of the coil, indicating that the common plasticizer caused 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 formulation can play a certain synergistic role. The combination of epoxy-modified silicone resin SH-023 and modified epoxy resin improves the peel performance of the coil, and at the same time also improves 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, rather than limitations on the implementation manners of the present invention. For those of ordinary skill 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 implementation manners here. Any modifications, equivalent substitutions, and improvements made within the spirit and principle of the present invention shall 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 based on 100 parts of Wacker alkoxy-terminated polyether: Zhonghua alkoxy-terminated polyether, 65 - 96 parts; Epoxy-modified silicone resin, 45 - 80 parts; Modified epoxy resin, 8 - 17 parts; the modified epoxy resin includes alkoxysilyl groups, epoxy groups and acrylic linkages; the epoxy equivalent range of the modified epoxy resin is 300 g / eq - 410 g / eq; Epoxy plasticizer, 250 - 380 parts; Latent curing agent, 5 - 24 parts; Pigment extender, 430 - 780 parts; Additive, 8 - 20 parts; The modified epoxy resin includes the structure shown in Formula 1 below: In Formula 1, n is an integer from 1 to 25, and X is an integer from 1 to 3; R1 is an alkyl group or phenyl group with no less than 2 methylene groups, R2 is an alkyl group with 1 - 3 carbon atoms, R3 is a straight-chain or branched-chain alkyl group with 1 - 3 carbon atoms, and m1 + m2 = 3.

2. The silane-modified polyether waterproof coating according to claim 1, wherein The Wacker alkoxy-terminated polyether includes one or more of STP-E35, STP-E30, STP-E15 and STP-E10; and / or, The Zhonghua alkoxy-terminated polyether includes one or more of SAX227, SAX327, SAX220 and SAX750.

3. The silane-modified polyether waterproof coating according to claim 1, wherein The epoxy-modified silicone resin includes one or a combination of SH-023 and SH-9614.

4. The silane-modified polyether waterproof coating according to claim 1, wherein, 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; and / or, The latent curing agent includes one or more of aldehyde imine curing agents, ketone imine curing agents and oxazolidine curing agents.

5. The silane-modified polyether waterproof coating according to claim 1, wherein The pigment extender includes one or more of fumed silica, nano calcium carbonate, heavy calcium carbonate, carbon black and modified clay; and / or; The additive includes one or more of water removers, accelerators and catalysts.

6. The silane-modified polyether waterproof coating according to claim 5, wherein The water remover includes one or more of vinyltrimethoxysilane, vinyltriacetoxysilane and vinyltriethoxysilane.

7. The silane-modified polyether waterproof coating according to claim 5, characterized in that, The accelerator includes one or more of triacetoxyethylsilane, vinyltriacetoxysilane and diethyldiacetoxysilane.

8. The silane-modified polyether waterproof coating according to claim 5, characterized in that The catalyst includes one or more of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate and chelated tin catalyst.

9. The preparation method of the silane-modified polyether waterproof coating according to any one of claims 1 to 8, characterized in that, Comprising: Mixing a predetermined weight part of Wacker silane-modified polyether, Zhonghua silane-modified polyether, epoxy plasticizer and pigment extender under a first condition to obtain a first reactant; Mixing the first reactant with epoxy-modified silicone resin, modified epoxy resin and latent curing agent under a second condition to obtain a second reactant; Mixing the second reactant with an additive to obtain the silane-modified polyether waterproof coating.

10. The preparation method of the silane-modified polyether waterproof coating according to claim 9, characterized in that, In the step of mixing the first reactant with 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 the polymerization reaction of an epoxy resin, an acrylic monomer with an epoxy group and an amino silane coupling agent.

11. A waterproof article, comprising: A waterproof coating and an asphalt waterproof base material 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 8.

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