Multi-cured PMMA elastic waterproof coating composition and preparation method thereof

Abstract

The present application discloses a multi-cured PMMA elastic waterproof coating composition and a preparation method thereof. It includes component A and component B; wherein component A includes optional additives and: PUA resin, the PUA resin prepolymer is obtained by reacting polyisocyanate and oligomer polyol according to a molar ratio of 1.1:1 to 1.5:1, and the end group of the molecular chain skeleton of the PUA resin includes a double bond; PU resin, the PU resin prepolymer is obtained by reacting polyisocyanate and oligomer polyol according to a molar ratio of 1.18:1 to 2.3:1, and the end group of the molecular chain skeleton of the PU resin includes ‑NCO; mercaptosilane coupling agent; active diluent; reducing agent; component B includes an oxidant. According to the embodiment of the present application, it can effectively solve the curing problems in various application scenarios through multiple curing reactions including free radical curing reaction and moisture curing reaction, and can also effectively deal with various base surfaces.

Description

Technical Field

[0001] The present application relates to waterproof coatings, and more particularly to a multi-cured PMMA elastic waterproof coating composition and a preparation method thereof. Background Art

[0002] Polymethyl Methacrylate (PMMA) is a high molecular polymer. The name of PMMA waterproof material comes from the fact that it uses MMA monomer as an active diluent. In the system, the initiator and the reducing agent contact each other and react to generate active free radicals. The active free radicals induce the polymerization reaction of the MMA monomer to form a polymerized polymer.

[0003] Existing PMMA waterproof coatings are high glass transition temperature coatings, which are used in scenes with low base mobility such as floors and railway tracks, and their use is very limited. When applied to concrete structures, cracking and freezing cracking problems will occur. In addition, existing PMMA waterproof coatings are very susceptible to oxygen attack and may cause incomplete curing. Summary of the invention

[0004] The embodiment of the present application provides a multi-cured PMMA elastic waterproof coating composition and a preparation method thereof, which can effectively solve the curing problems in various application scenarios through multiple curing reactions including free radical curing reactions and moisture curing reactions, and can also effectively cope with various substrates.

[0005] In the first aspect, an embodiment of the present application provides a multi-cured PMMA elastic waterproof coating composition, comprising component A and component B; wherein component A comprises optional additives and: 20 to 50 parts by weight of PUA resin, the PUA resin prepolymer is obtained by reacting polyisocyanate and oligomer polyol at a molar ratio of 1.1:1 to 1.5:1, and the end group of the molecular chain skeleton of the PUA resin comprises a double bond; 10 to 30 parts by weight of PU resin, the PU resin prepolymer is obtained by reacting polyisocyanate and oligomer polyol at a molar ratio of 1.18:1 to 2.3:1, and the end group of the molecular chain skeleton of the PU resin comprises -NCO; 10 to 15 parts by weight of mercaptosilane coupling agent; 20 to 50 parts by weight of active diluent; 4 to 10 parts by weight of reducing agent; component B comprises an oxidant; wherein the active diluent comprises MMA monomer, and the additive comprises an air drying agent.

[0006] It is not intended to be limited by any theory or explanation. The multiple-cured PMMA elastic waterproof coating composition of the embodiment of the present application includes the above-mentioned PUA resin, which has a specific R value (-NCO to -OH molar ratio), which can bring elasticity and flexibility to the waterproof coating, and the double bond at the end group provides a reaction point for the subsequent MMA monomer to form a chain growth and a three-dimensional network cross-linking structure on the molecular structure of the polyurethane, thereby obtaining an elastic PMMA coating with both strength and ductility, so as to be better suitable for various scenes, such as ground structures and roof structures with larger grass-roots activities. The multiple-cured PMMA elastic waterproof coating composition of the embodiment of the present application also includes the above-mentioned PU resin, which has a specific R value, can bring high tear strength to the waterproof coating, and the appropriately retained-NCO end group can react with moisture in the air to form a urea group, combining two PU resin molecules together to achieve moisture curing. At the same time, part of the PU resin has a double bond structure in the structure. When the oxidant and the reducing agent contact to generate free radicals, the free acrylic monomer and the double bond on the PU will be simultaneously triggered to achieve mixed curing of PU and PMMA to form an interpenetrating network structure. The multi-cured PMMA elastic waterproof coating composition of the embodiment of the present application also includes the above-mentioned mercaptosilane coupling agent, and utilizes the Michael addition click chemistry reaction between the mercapto group and the double bond under the action of free radicals to introduce an organic siloxane structure on the side chain of the PMMA polymer to achieve moisture curing; and the mercapto group acts as a chain transfer agent, which can effectively control the molecular weight of the PMMA polymer generated in the free radical reaction, reduce the formation of large-molecule PMMA polymers, and promote the improvement of the PMMA polymer conversion rate; in addition, the mercapto compound can also improve the air-drying property of the PMMA coating, resist oxygen inhibition, and achieve a smooth effect on the coating surface.

[0007] Therefore, the multi-cured PMMA elastic waterproof coating composition of the embodiment of the present application can achieve multiple curing effects including free radical curing reaction and moisture curing reaction through PUA resin, PU resin and mercaptosilane coupling agent with specific R value and end group, which can effectively solve the curing problems in various application scenarios. At the same time, it can also bring elasticity and high tear strength to the PMMA coating, and effectively deal with stress cracking and freeze cracking problems caused by large base activity.

[0008] In any embodiment of the present application, the PUA resin is obtained by reacting oligomer polyol, polyisocyanate, hydroxy acrylate, end-capped small molecule, catalyst and inhibitor.

[0009] In any embodiment of the present application, the molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

[0010] In any embodiment of the present application, the polyisocyanate includes at least one of HDI, TDI, MDI, IPDI and HMDI.

[0011] In any embodiment of the present application, the hydroxy acrylate includes at least one of hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxybutyl methacrylate.

[0012] In any embodiment of the present application, the end-capped small molecule includes at least one of benzyl alcohol, n-octanol, hydroxybutyric acid and isobornyl alcohol.

[0013] In any embodiment of the present application, the catalyst includes an organic tin catalyst, and the organic tin catalyst includes at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

[0014] In any embodiment of the present application, the polymerization inhibitor includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone and methylhydroquinone.

[0015] In any embodiment of the present application, the PU resin is obtained by reacting an oligomer polyol, a polyisocyanate and a catalyst.

[0016] In any embodiment of the present application, the molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

[0017] In any embodiment of the present application, the polyisocyanate includes at least one of HDI, TDI, MDI, IPDI and HMDI.

[0018] In any embodiment of the present application, the air-drying agent includes at least one of refined paraffin wax and semi-refined paraffin wax.

[0019] Preferably, the number of the refined paraffin or the semi-refined paraffin includes at least one of 52#, 54#, 56#, 58#, 60#, 62# and 68#.

[0020] In any embodiment of the present application, the filler is 400-2000 mesh and includes at least one of heavy calcium carbonate, light calcium carbonate, talcum powder, barium sulfate, aluminum hydroxide, titanium dioxide, fumed silica and nano calcium carbonate.

[0021] In any embodiment of the present application, the color paste includes at least one of emerald green, iron red and orange.

[0022] In any embodiment of the present application, the catalyst includes an organic tin catalyst, and the organic tin catalyst includes at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

[0023] In any embodiment of the present application, the plasticizer includes at least one of DOTP, DOP, and acetyl tributyl citrate.

[0024] In any embodiment of the present application, the mercaptosilane coupling agent includes γ-mercaptopropyltrimethoxysilane or (HS-(R1) n --Si(R2)3; where R1 is -CH2 and R2 is -O(CH2) m CH3, n≥1, m≥0.

[0025] In any embodiment of the present application, the reactive diluent includes at least one of methacrylic acid, methyl methacrylate, styrene, butyl acrylate, isooctyl acrylate, glycidyl acrylate, hydroxyethyl methacrylate, ethyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate.

[0026] In any embodiment of the present application, the reducing agent includes at least one of diethanolamine, dimethylethanolamine, N,N-diethylhydroxylamine, N,N-dimethyl-p-toluidine and N,N-diethylaniline.

[0027] In any embodiment of the present application, the oxidant includes at least one of benzoyl peroxide, dicumyl peroxide, and cumene hydroperoxide.

[0028] In any embodiment of the present application, the additive further includes at least one of the following:

[0029]

[0030] In any embodiment of the present application, the pH buffer includes at least one of tartaric acid, potassium dihydrogen phosphate, and sodium bicarbonate.

[0031] In any embodiment of the present application, the anti-ultraviolet aging agent includes UV-326 and At least one of UV-329.

[0032] In any embodiment of the present application, the antioxidant comprises 1010 and At least one of 686.

[0033] In any embodiment of the present application, the anti-settling agent includes A-200 fumed silica.

[0034] In any embodiment of the present application, the reinforcing agent includes at least one of 3102 Mitsubishi resin and 950 Mitsubishi resin.

[0035] In any embodiment of the present application, the latent curing agent includes at least one of the one-component moisture-curing polyurethane auxiliary drier WCAT-WQ01 and the polyurethane latent curing agent YRLH-1106.

[0036] In a second aspect, the present application provides a method for preparing a PMMA elastic waterproof coating composition, comprising: preparing a PUA resin, reacting an oligomer polyol with a polyisocyanate, and then adding a catalyst, an inhibitor, a capped small molecule, and a hydroxy acrylate in order, and reacting again to obtain a PUA resin; preparing a PU resin, reacting an oligomer polyol with a polyisocyanate, and then adding a catalyst, and reacting again to obtain a PU resin; preparing a component A, mixing materials containing a PUA resin, a PU resin, a mercaptosilane coupling agent, an active diluent, and a reducing agent to obtain a to component A; prepare component B, mix the materials containing the oxidant to obtain component B; prepare a PMMA elastic waterproof coating composition, store component A and component B independently, and obtain a PMMA elastic waterproof coating composition; wherein, in the preparation of PUA resin, the amount of the substance of the oligomer polyol is x1, and the amount of the substance of the polyisocyanate is y1, and y1:x1=1.1:1~1.5:1; in the preparation of PU resin, the amount of the substance of the oligomer polyol is x2, and the amount of the substance of the polyisocyanate is y2, and y2:x2=1.18:1~2.3:1.

[0037] In any embodiment of the present application, in the preparation of the PUA resin, the amount of the hydroxy acrylate substance is z, wherein z:(y1-x1)=1.1:1~1.2:1.

[0038] In any embodiment of the present application, in the preparation of component A, the material further includes an additive.

[0039] The multi-cured PMMA elastic waterproof coating composition and preparation method thereof of the embodiments of the present application can realize multiple curing effects including free radical curing reaction and moisture curing reaction through PUA resin, PU resin and mercaptosilane coupling agent with specific R value and end group, and can effectively solve the curing problems in various application scenarios. At the same time, it can also bring elasticity and high tear strength to PMMA coating, and effectively deal with stress cracking and frost cracking problems caused by large activity of the base layer. DETAILED DESCRIPTION

[0040] In order to more clearly understand the above-mentioned purposes, features and advantages of the present application, the scheme of the present application will be further described below. It should be noted that the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

[0041] In the following description, many specific details are set forth to facilitate a full understanding of the present disclosure, but the present application may also be implemented in other ways different from those described herein; it is obvious that the embodiments in the specification are only part of the embodiments of the present application, rather than all of the embodiments.

[0042] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0043] If not otherwise specified, all embodiments and optional embodiments of the present application may be combined with each other to form new technical solutions, and such technical solutions should be deemed to be included in the disclosure of the present application.

[0044] Unless otherwise specified, all technical features and optional technical features of the present application may be combined with each other to form new technical solutions, and such technical solutions should be deemed to be included in the disclosure of the present application.

[0045] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0046] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0047] Unless otherwise specified, this application adopts conventional test methods or test methods recommended by the instrument.

[0048] PMMA refers to polymethyl methacrylate, a high molecular polymer also known as acrylic or organic glass. It has the advantages of high transparency, low price, and easy machining. It is a commonly used glass substitute material.

[0049] PMMA coating: The main body of PMMA coating is composed of acrylate monomers including MMA monomers, oxidants, reducing agents, powders, etc. When using, several components are mixed and then applied to the base layer to form a waterproof structure.

[0050] MMA refers to methyl methacrylate, also known as methyl methacrylate, which is an organic compound.

[0051] PUA resin refers to polyurethane acrylate. The molecules of PUA resin contain acrylic functional groups and urethane bonds. After curing, it has the high wear resistance, adhesion, flexibility, high peel strength and excellent low temperature resistance of polyurethane and the excellent optical properties and weather resistance of polyacrylate.

[0052] PU resin refers to polyurethane, the full name of which is polyurethane, which is a polymer material with excellent mechanical properties formed by polyols and polyisocyanates through condensation reaction. Several main classifications of polyurethane include polyether type, polyester type, polyimide type and polyurea type, etc. They can be made into polyurethane plastics (mainly foam plastics), polyurethane fibers (called spandex in China), polyurethane rubbers and elastomers and other materials. The PU resin described in this application refers to a polyurethane resin that does not contain an acrylate group.

[0053] TDI refers to toluene diisocyanate, which has six isomers, namely toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,4-diisocyanate and toluene-3,5-diisocyanate. Among them, toluene-2,4-diisocyanate and toluene-2,6-diisocyanate are the most common isomers. Toluene diisocyanate in industry is usually a mixture of toluene-2,4-diisocyanate and toluene-2,6-diisocyanate.

[0054] MDI refers to diphenylmethane diisocyanate.

[0055] IPDI refers to isophorone diisocyanate, with the chemical formula C 12 H 18 N2O2 is an alicyclic diisocyanate. IPDI is one of the least active varieties among the commonly used diisocyanate products. It has a stable reaction. Its two isocyanate groups have different reactivity of about ten times, which is conducive to the preparation of various prepolymers. In addition, its vapor pressure is low, which makes it safer to use and operate.

[0056] HMDI refers to dicyclohexylmethane diisocyanate.

[0057] DOTP refers to dioctyl terephthalate, an organic compound with a molecular formula of C 24 H 38 O4.

[0058] DOP refers to dioctyl phthalate, an organic ester compound and a commonly used plasticizer.

[0059] R value: refers to the molar ratio (R value) of isocyanate group (-NCO) to hydroxyl group (-OH) in the polyurethane prepolymer, also known as the isocyanate index.

[0060] Oligomeric polyols are divided into polyether and polyester polyols, which constitute the soft segments of polyurethane molecules. Polyether polyols mainly include polytetrahydrofuran diol, polyethylene glycol and polypropylene glycol; polyester polyols mainly include polyhexane adipate diol, polycarbonate diol, polybutylene adipate diol and polycaprolactone diol.

[0061] Free radical curing: The contact between the oxidant (RR) and the reductant can rapidly generate active free radicals R* and release a large amount of heat; the active free radical R* will attack the acrylate monomer with a double bond to obtain an active monomer free radical RA*; the active monomer free radical RA* continues to attack the acrylate monomer with a double bond to obtain an active monomer free radical RAA* (RA......A*), and so on, until it encounters R* for disproportionation termination, and the molecular weight no longer increases, and finally a polymer of RAAR is obtained. At this time, the molecular weight of the polymer is very large (about tens of thousands), and the activity level of the polymer is very low at the microscopic level. Macroscopically, it behaves as a hard material. This process is called free radical curing or free radical addition.

[0062] Oxygen inhibition: During the free radical curing process, the active monomer free radical RAA* encounters R* for disproportionation termination, and finally obtains the polymer of RAAR; and oxygen O2 itself is also an active free radical, so it will react with the active monomer free radical RAA* to obtain RAAO2. At this time, the molecular weight of the polymer cannot increase, the microscopic activity of the polymer is relatively large, and the macroscopic performance is sticky. The film surface is sticky and the bottom is hard. This situation is called oxygen inhibition. Increasing the number of active monomer free radicals RAA*, reducing the oxygen density, or preventing oxygen from contacting the active monomer free radicals RAA* are effective means to prevent oxygen inhibition.

[0063] Moisture curing: Moisture curing refers to the behavior of water as a cross-linking agent to chemically combine two or more polymer chains. Common moisture curing includes moisture curing of polyurethane and moisture curing of MS glue. The former is achieved by grafting -NCO groups on the ends of polyurethane. When applied on the base surface, polyurethane will slowly absorb moisture from the air, and water and -NCO will react to form urea groups, which will bind two polyurethane molecules together, and the coating will show enhanced cohesion. The latter is achieved by grafting -Si(OEt)3 on the ends of polyether molecular chains (MS glue). When applied on the base surface, MS glue will slowly absorb moisture from the air, and water and -Si(OEt)3 will react to form -Si-O-Si-base, which will bind two MS glue molecules together, and the coating will show enhanced cohesion.

[0064] The existing PMMA waterproof coating realizes the self-polymerization reaction of MMA monomer through the redox reaction of oxidant and reductant. Since the oxidant and reductant are mixed in equal proportions in molar equivalent ratio, a large number of free radicals will be generated at the moment of contact. Therefore, PMMA waterproof coating can achieve coagulation in 20 minutes and surface drying in 60 minutes, which can shorten the construction period to a certain extent. However, the following problems will inevitably occur:

[0065] 1. PMMA waterproof coatings are used in places with less active bases, such as floors and railway tracks, and the scenarios are very limited. Most buildings are made of concrete structures, which will shrink and settle during long-term service, that is, the base is active, which will cause stress cracking and frost cracking.

[0066] 2. The reaction process is too rapid and generates a huge amount of heat. The huge heat generated will cause the monomer to volatilize and cause the environment to overheat (possibly resulting in the risk of explosion), causing harm to the health and personal safety of workers.

[0067] 3. The saturated vapor pressure of MMA monomer is very low, and the operators on site will inhale a large amount of MMA gas. In addition, the initiator and the reducing agent act very quickly, and the free radical quenching speed is also very fast, which can easily cause the MMA monomer to react incompletely and remain in the final coating, which will have an immeasurable impact on the health of users and the water environment.

[0068] 4. PMMA waterproof coatings are easily attacked by oxygen and may not be fully cured, commonly known as oxygen inhibition. Oxygen inhibition is more prominent in scenes with high wind speed, low air pressure and high humidity. The solution to this problem is to isolate or eliminate oxygen. The methods include covering the coating with a film, introducing a sealant (such as wax) or an oxygen scavenger (thiol, etc.) into the coating. However, these methods inevitably have the problem of poor environmental adaptability. The humidity, temperature and cleanliness of the environment will have a great impact on the implementation of these methods.

[0069] This application prepares a PUA resin with a specific R value, double bond termination, and polar and large steric hindrance functional groups grafted at the end of the molecular chain skeleton, so that PUA and MMA monomers form a polyurethane molecular structure with a three-dimensional network cross-linking structure under the action of free radicals. The polyurethane molecular structure has high tear strength, ductility and elasticity, so that it can be better applied to various scenarios. The introduced polar and large steric hindrance functional groups can reduce the viscosity of the resin, promote the floating of the air drying agent (wax), form an oxygen barrier layer, and improve the surface drying property.

[0070] The present application prepares a PU resin with a specific R value and -NCO retained at the end group, and utilizes the -NCO end group to react with moisture in the air to form a urea group, thereby combining two PU resin molecules together to achieve moisture curing. At the same time, the double bonds on some PU resins will achieve free radical-induced copolymerization with acrylate monomers, thereby further forming a cross-linking system.

[0071] The present application optimizes the monomer ratio of the active diluent, thereby improving the adhesion of the coating to the cement foundation, while further reducing the odor and residue of acrylic acid, thereby reducing the impact on construction workers and the environment.

[0072] The present application optimizes the types and ratios of redox reactions and creatively introduces a pH buffer to ensure the pH stability of the system, thereby reducing reaction heat and achieving a high conversion rate.

[0073] Through the joint action of various components in the PMMA elastic waterproof coating composition, the present application can effectively solve the problems of being difficult to dry or not drying in various application scenarios, shorten the construction period, and achieve the purpose of reducing costs and increasing efficiency; it can improve the coating's ability to absorb shock waves, and achieve organic coupling of multiple functions such as waterproofing, noise reduction, and impact resistance, which can further reduce users' construction costs and save three-dimensional space.

[0074]

Multiple cured PMMA elastic waterproof coating composition

[0075] A multi-cured PMMA elastic waterproof coating composition comprises a component A and a component B; wherein the component A comprises optional additives and: 20 to 50 parts by weight of a PUA resin, wherein the PUA resin prepolymer is obtained by reacting a polyisocyanate and an oligomer polyol at a molar ratio of 1.1:1 to 1.5:1, and the end groups of the molecular chain skeleton of the PUA resin comprise double bonds; 10 to 30 parts by weight of a PU resin, wherein the PU resin prepolymer is obtained by reacting a polyisocyanate and an oligomer polyol at a molar ratio of 1.18:1 to 2.3:1, and the end groups of the molecular chain skeleton of the PU resin comprise -NCO; 10 to 15 parts by weight of a mercaptosilane coupling agent; 20 to 50 parts by weight of an active diluent; and 4 to 10 parts by weight of a reducing agent; the component B comprises an oxidant; the active diluent comprises an MMA monomer, and the additive comprises an air drying agent.

[0076] Without intending to be limited by any theory or explanation, the multiple-cured PMMA elastic waterproof coating composition of the embodiment of the present application includes the above-mentioned PUA resin, which has a specific R value, can bring elasticity and flexibility to the waterproof coating, and through the double bonds at the end groups, the MMA monomers behind form chain growth and three-dimensional network cross-linking structures on the molecular structure of the polyurethane to provide reaction points, thereby obtaining an elastic PMMA coating with both strength and ductility, so as to be better suitable for various scenes, such as ground structures and roof structures with larger grass-roots activities. The multiple-cured PMMA elastic waterproof coating composition of the embodiment of the present application also includes the above-mentioned PU resin, which has a specific R value, can bring high tear strength to the waterproof coating, and the appropriately retained -NCO end group can react with moisture in the air to form a urea group, combining two PU resin molecules together to achieve moisture curing. At the same time, the double bonds on some PU resins will realize free radical-induced copolymerization with acrylate monomers, thereby further forming a cross-linking system. The multi-cured PMMA elastic waterproof coating composition of the embodiment of the present application also includes the above-mentioned mercaptosilane coupling agent, and utilizes the Michael addition click chemistry reaction between the mercapto group and the double bond under the action of free radicals to introduce an organic siloxane structure on the side chain of the PMMA polymer to achieve moisture curing; and the mercapto group acts as a chain transfer agent, which can effectively control the molecular weight of the PMMA polymer generated in the free radical reaction, reduce the formation of large-molecule PMMA polymers, and promote the improvement of the PMMA polymer conversion rate; in addition, the mercapto compound can also improve the air-drying property of the PMMA coating, resist oxygen inhibition, and achieve a smooth effect on the coating surface.

[0077] Therefore, the multi-cured PMMA elastic waterproof coating composition of the embodiment of the present application can achieve multiple curing effects including free radical curing reaction and moisture curing reaction through PUA resin, PU resin and mercaptosilane coupling agent with specific R value and end group, which can effectively solve the curing problems in various application scenarios. At the same time, it can also bring elasticity and high tear strength to the PMMA coating, and effectively deal with stress cracking and freeze cracking problems caused by large base activity.

[0078] In some embodiments, the PUA resin is obtained by reacting oligomer polyols, polyisocyanates, hydroxy acrylates, end-capped small molecules, catalysts and inhibitors. Oligomer polyols and polyisocyanates can react to form polyurethanes of a certain molecular weight. Under the action of end-capped small molecules, catalysts and inhibitors, double bonds and end-capped small molecules can be introduced into the end groups of the polyurethane and the ends of the molecular chain skeleton, respectively. The end-capped small molecules can be segments containing polar and large steric hindrance functional groups, which play a role in reducing the viscosity of the resin and promoting the floating of the air-drying agent (wax). In one example, the segments containing polar and large steric hindrance functional groups can be at least one of a benzene ring, an n-octyl group, a butyric acid group, and an isobornyl group.

[0079] The PUA resin described in the embodiment of the present application can be obtained by reacting oligomer polyols and polyisocyanates to generate polyurethane of a certain molecular weight, and then introducing double bonds and end-capped small molecules into the end groups and ends of the molecular chain skeleton of the above-mentioned polyurethane under the joint action of end-capped small molecules, catalysts and inhibitors.

[0080] In one embodiment, the PUA resin can be prepared by the following steps:

[0081] Put the oligomer polyol into a reactor, heat it to 100-110°C, and vacuum dehydrate for 2.5-3.5 hours. After testing the moisture content to be less than 0.5%, reduce the temperature to 70-80°C, add polyisocyanate according to the preset specific R value, react for 2.5-3.5 hours, add 2-0.6 thousandths of the total amount of oligomer polyol and polyisocyanate as an organic tin catalyst, add inhibitor, small molecule end-capping agent, and hydroxy acrylate in order, react at 70-80°C for 1.5-2.5 hours, then reduce the temperature to 40-50°C to obtain PUA resin.

[0082] As an example, after cooling to 40-50° C., MMA monomer can be added to obtain a mixture of PUA resin and MMA monomer. Mixing PUA resin and MMA monomer in advance can dilute PUA resin with MMA monomer, reduce the viscosity of PUA resin, and facilitate PUA resin out of the pot.

[0083] As an example, the amount of MMA monomer added may be 25-35% of the total amount of the PUA resin.

[0084] In one embodiment, the molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

[0085] In some embodiments, the oligomer polyol may be a polyether diol.

[0086] Optionally, the molecular weight of the oligomer polyol is independently selected from any value among 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000 or any range therebetween.

[0087] In one embodiment, the polyisocyanate includes at least one of HDI, TDI, MDI, IPDI, and HMDI.

[0088] In one embodiment, the hydroxy acrylate includes at least one of hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxybutyl methacrylate.

[0089] In one embodiment, the capped small molecule includes at least one of benzyl alcohol, n-octanol, hydroxybutyric acid, and isobornyl alcohol.

[0090] In one embodiment, the catalyst comprises an organic tin catalyst, and the organic tin catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

[0091] In one embodiment, the polymerization inhibitor includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone, and methylhydroquinone.

[0092] In one embodiment, the PU resin is obtained by reacting an oligomer polyol, a polyisocyanate and a catalyst. In the reaction, additives required in component A, such as an air drying agent, a filler, a color paste and a plasticizer, can also be added together. At this time, the PU resin obtained by reacting the oligomer polyol and the polyisocyanate exists in the form of a mixture with the additives. Those skilled in the art can adjust the ratio of the oligomer polyol and the polyisocyanate and the reaction conditions as needed.

[0093] In one embodiment, the PU resin can be prepared by the following steps:

[0094] Put oligomer polyol, air drying agent, filler, color paste, and plasticizer into a reaction kettle, heat to 100-110°C, vacuum dehydrate for 2.5-3.5 hours, test the moisture content to be less than 5 / 1000, then reduce the temperature to 70-80°C, add polyisocyanate according to the preset specific R value, react for 2.5-3.5 hours, add 2 / 1000 to 6 / 1000 organic tin catalyst of the total amount of oligomer polyol and polyisocyanate, react at 70-80°C for 1.5-2.5 hours, then reduce the temperature to 40-50°C to obtain PU resin. Among them, the order of adding air drying agent, filler, and color paste can also be adding after the polymerization reaction is completed.

[0095] In one embodiment, the molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

[0096] Optionally, the molecular weight of the oligomer polyol is independently selected from any value among 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000 or any range therebetween.

[0097] In one embodiment, the polyisocyanate includes at least one of HDI, TDI, MDI, IPDI, and HMDI.

[0098] In one embodiment, the air-drying agent includes at least one of refined paraffin wax and semi-refined paraffin wax. The addition of the air-drying agent can accelerate the reaction, improve the performance, and promote the solidification.

[0099] Preferably, the number of the refined paraffin or the semi-refined paraffin includes at least one of 52#, 54#, 56#, 58#, 60#, 62# and 68#.

[0100] In one embodiment, the filler is 400-2000 mesh, including at least one of heavy calcium carbonate, light calcium carbonate, talcum powder, barium sulfate, aluminum hydroxide, titanium dioxide, fumed silica and nano calcium carbonate. The filler within this range can increase or decrease the viscosity of the material.

[0101] In one embodiment, the color paste includes at least one of emerald green, iron red and orange. The color of the coating can be adjusted to meet the needs of different customers. The appropriate coating color paste ratio can make the coating color accurate, bright and durable, and improve the aesthetics of the fields of construction, decoration, etc.

[0102] In one embodiment, the catalyst comprises an organic tin catalyst, and the organic tin catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

[0103] In one embodiment, the plasticizer includes at least one of DOTP, DOP, and acetyl tributyl citrate.

[0104] In one embodiment, the active diluent further comprises at least one of methacrylic acid, styrene, butyl acrylate, isooctyl acrylate, glycidyl acrylate, hydroxyethyl methacrylate, ethyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate. The active diluent can dissolve or disperse the components in the PMMA elastic waterproof coating composition, and can participate in free radical curing during the film-forming process of the coating.

[0105] In one embodiment, the mercaptosilane coupling agent includes γ-mercaptopropyltrimethoxysilane or (HS-(R1) n -Si(R2)3; wherein R1 is -CH2- and R2 is -O(CH2) mCH3, n≥1, m≥0. The addition of mercaptosilane coupling agent can make the mercapto group and double bond react with Michael addition click chemistry under the action of free radicals, introduce organic siloxane structure on the side chain of PMMA polymer, and realize moisture curing; and mercapto group as chain transfer agent can effectively control the molecular weight of PMMA polymer generated in free radical reaction, reduce the formation of macromolecular PMMA polymer, and promote the improvement of PMMA polymer conversion rate; in addition, mercapto compounds can also improve the air drying property of PMMA coating, that is, anti-oxygen inhibition, and realize the smooth feeling of coating surface.

[0106] In one embodiment, the reducing agent includes at least one of diethanolamine, dimethylethanolamine, N,N-diethylhydroxylamine, N,N-dimethyl-p-toluidine, and N,N-diethylaniline.

[0107] In one embodiment, the oxidizing agent includes at least one of benzoyl peroxide, dicumyl peroxide, and cumene hydroperoxide.

[0108] In one embodiment, the additive further comprises at least one of the following:

[0109]

[0110]

[0111] In one embodiment, the pH buffer includes at least one of tartaric acid, potassium dihydrogen phosphate and sodium bicarbonate. The present application creatively introduces a pH buffer to ensure the pH stability of the system, achieve a high conversion rate while reducing the reaction heat, thereby improving construction safety and ensuring the health of construction workers.

[0112] In one embodiment, the anti-ultraviolet aging agent includes UV-326 and At least one of UV-329.

[0113] In one embodiment, the antioxidant comprises 1010 and At least one of 686.

[0114] In one embodiment, the anti-settling agent includes A-200 fumed silica.

[0115] In one embodiment, the reinforcing agent includes at least one of 3102 Mitsubishi resin and 950 Mitsubishi resin.

[0116] In one embodiment, the latent curing agent includes at least one of a one-component moisture-curing polyurethane auxiliary drier WCAT-WQ01 and a polyurethane latent curing agent YRLH-1106.

[0117] The latent curing agent can be added during the synthesis of the PU resin to form a mixture of the PU resin and the latent curing agent, so as to facilitate the moisture curing of the -NCO terminal group of the PU resin in the later formation of PMMA-based coatings.

[0118]

Preparation method

[0119] A method for preparing a PMMA elastic waterproof coating composition comprises the following steps S10-S50:

[0120] S10: preparing PUA resin, reacting oligomer polyol and polyisocyanate, adding catalyst, polymerization inhibitor, end-capping small molecule and hydroxy acrylate in order, reacting again to obtain PUA resin, wherein the amount of oligomer polyol is x1, the amount of polyisocyanate is y1, and y1:x1=1.1:1-1.5:1;

[0121] In step S10, the types and amounts of oligomer polyol, polyisocyanate, catalyst, polymerization inhibitor, end-capped small molecule, and hydroxy acrylate can be as described in the first aspect, and will not be repeated here. The reaction conditions of step S10 are not specifically limited, and those skilled in the art can adjust them as needed.

[0122] S20: preparing PU resin, reacting oligomer polyol and polyisocyanate, adding a catalyst, and reacting again to obtain PU resin, wherein the amount of the oligomer polyol is x2, the amount of the polyisocyanate is y2, and y2:x2=1.18:1-2.3:1;

[0123] In step S20, the types and amounts of oligomer polyol, polyisocyanate and catalyst can be as described in the first aspect, and will not be repeated here. The reaction conditions of step S20 are not specifically limited, and those skilled in the art can adjust them as needed.

[0124] S30: preparing component A by mixing materials containing PUA resin, PU resin, mercaptosilane coupling agent, active diluent and reducing agent to obtain component A;

[0125] In step S30, the material may further contain additives. The additives may include at least one of a pH buffer, an anti-ultraviolet aging agent, an antioxidant, an anti-settling agent, a reinforcing agent, an air drying agent, a filler, a color paste, and a plasticizer. The types and amounts of the pH buffer, the anti-ultraviolet aging agent, the antioxidant, the anti-settling agent, the reinforcing agent, the air drying agent, the filler, the color paste, and the plasticizer may be as described in the first aspect, and will not be repeated here.

[0126] In one embodiment, the additives can be at least partially added during the preparation process of the PUA resin or PU resin. For example, in step S20, the PU resin is prepared by dehydrating the material containing the oligomer polyol, air drying agent, filler, color paste, and plasticizer to obtain a material with a moisture content of less than 0.5 parts per thousand, and then adding polyisocyanate. After the reaction, a catalyst is added and the reaction is performed again to obtain the PU resin.

[0127] The types and amounts of mercaptosilane coupling agent, active diluent, and reducing agent can be as described in the first aspect, and will not be repeated here. The reaction conditions of step S30 are not specifically limited, and those skilled in the art can adjust as needed. As an example, according to parts by weight, 20 to 50 parts of PUA resin and 10 to 30 parts of PU resin are added to a high-speed disperser, sheared and dispersed for 20 to 40 minutes, 20 to 50 parts of active diluent are added in 2 to 3 times, sheared for 0.5 to 1.5 hours and dispersed evenly, 0.5 to 3 parts of pH buffer, 1 to 2 parts of anti-ultraviolet aging agent, 1 to 2 parts of antioxidant, 4 to 10 parts of reducing agent, 2 to 5 parts of anti-settling agent, 10 to 18 parts of reinforcing agent, 10 to 15 parts of mercaptosilane coupling agent are sequentially added, sheared for 0.5 to 1.5 hours and dispersed evenly, and discharged to obtain component A. As an example, the shear rate can be 4000 to 10000 rpm.

[0128] S40: preparing component B, mixing materials containing an oxidant to obtain component B;

[0129] S50: preparing a PMMA elastic waterproof coating composition, storing component A and component B independently, and obtaining a PMMA elastic waterproof coating composition.

[0130] When used in on-site construction, the separately packaged components A and B are mixed in a certain proportion, and the film-forming process begins under the action of the oxidant and the reductant, and finally a PMMA elastic waterproof structure is obtained.

[0131] In one embodiment, in the preparation of the PUA resin, the amount of the substance of the hydroxy acrylate is z, wherein z:(y1-x1)=1.1:1 to 1.2:1. Optionally, the value of z:(y1-x1) is independently selected from any value of 1.10:1, 1.11:1, 1.12:1, 1.13:1, 1.14:1, 1.15:1, 1.16:1, 1.17:1, 1.18:1, 1.19:1, 1.20:1 or any range value between the two.

[0132] In the present application, the amount of hydroxy acrylate added can be added according to the residual -NCO content so that the raw materials in step S10 react completely.

[0133] Example 1

[0134] S10: 50 kg (portions) of polyether (PPG2000) were put into a reactor, heated to 105°C, and vacuum-dehydrated for 3 hours. After the moisture content was tested to be less than 0.5%, the temperature was lowered to 75°C, and 8 kg (portions) of isophorone diisocyanate (IPDI) were added. After reacting for 3 hours, 1.5 kg (portions) of hydroxyethyl acrylate and 0.25 kg (portions) of dibutyltin dilaurate were added. 0.085 kg (portion) of hydroquinone and 0.419 kg (portion) of benzyl alcohol were added in sequence. After reacting at 75°C for 2 hours, the temperature was lowered to 45°C, 18.076 kg (portions) of methyl methacrylate (MMA) were added, and the material was discharged to obtain PUA resin.

[0135] S20: 1000kg (portion) of polyether (PPG2000), 20kg (portion) of refined paraffin (air drying agent), 1500kg (portion) of heavy calcium (filler), 25kg (portion) of composite emerald green (color paste), and 750kg (portion) of chlorinated paraffin (plasticizer) are put into a reactor, heated to 105°C, and vacuum-dehydrated for 3 hours. After testing the moisture content to be less than 0.5%, the temperature is lowered to 75°C, and 244.6kg (portion) of isophorone diisocyanate (IPDI) is added. After reacting for 3 hours, 2kg (portion) of dibutyltin dilaurate is added. After reacting at 75°C for 2 hours, the temperature is lowered to 45°C, and the material is discharged to obtain PU resin.

[0136] S30: 50 kg (portion) of PUA resin and 25 kg (portion) of PU resin were added to a high-speed disperser, and sheared and dispersed at 3000 rpm for 30 minutes. 30 kg (portion) of methyl methacrylate was added in three portions, and sheared at 3000 rpm for 1 hour to disperse evenly. 0.5 kg (portion) of pH buffer (tartaric acid), 1 kg (portion) of anti-ultraviolet aging agent ( UV-326), 1kg (portion) antioxidant ( 1010), 4kg (portions) reducing agent (dimethylethanolamine), 2kg (portions) anti-settling agent (A-200 thickening anti-settling agent), 10kg (portions) reinforcing agent (3102 resin (Mitsubishi)), 10kg (portions) mercaptosilane coupling agent (γ-mercaptopropyltrimethoxysilane), shear at 3500rpm for 1 hour to disperse evenly, discharge, and obtain component A.

[0137] S40: 8 g (parts) of benzoyl peroxide as component B;

[0138] S50: Component A and component B are stored independently to obtain a PMMA elastic waterproof coating composition.

[0139] Example 2

[0140] The experimental steps are the same as those in Example 1, except that 18.076 kg (parts) of methyl methacrylate in step S10 is omitted, that is, no methyl methacrylate is added in step S10, and only 30 kg (parts) of methyl methacrylate is added in step S30.

[0141] Example 3

[0142] The experimental steps are the same as those in Example 1, except that after the temperature is lowered to 45° C. in step S20 and before the material is discharged, an additional 28 kg (portions) of polyurethane latent curing agent YRLH-1106 is added.

[0143] Example 4

[0144] The experimental steps are the same as those in Example 1, except that the amount of methyl methacrylate added in step S30 is changed to 40 parts by weight.

[0145] Example 5

[0146] The experimental steps are the same as those in Example 1, except that the type of reducing agent in step S30 is changed to diethanolamine.

[0147] Example 6

[0148] The experimental steps are the same as those in Example 1, except that no pH buffer is added in step S30.

[0149] Example 7

[0150] The experimental steps are the same as those in Example 1, except that the amount of the active diluent added in step S30 is changed to 25 parts by weight.

[0151] Example 8

[0152] The experimental steps are the same as those in Example 1, except that the reactive diluent (30 kg (parts) of methyl methacrylate) added in step S30 is replaced by glycidyl acrylate, isooctyl acrylate and ethylene glycol dimethacrylate (mass ratio 1:1:1).

[0153] Comparative Example 1

[0154] The experimental steps are the same as those in Example 1, except that the amount of reducing agent added in step S30 is changed to 12 parts by weight.

[0155] Comparative Example 2

[0156] The experimental steps are the same as those in Example 1, except that the amount of the reducing agent added in step S30 is changed to 2 parts by weight.

[0157] Comparative Example 3

[0158] The experimental steps are the same as those in Example 1, except that the type of reducing agent in step S30 is changed to cobalt nitrate.

[0159] Comparative Example 4

[0160] The experimental steps are the same as those in Example 1, except that the amount of the active diluent added in step S30 is changed to 80 parts by weight.

[0161] Comparative Example 5

[0162] The experimental steps are the same as those in Example 1, except that the amount of the active diluent added in step S30 is changed to 2 parts by weight.

[0163] Data analysis

[0164] The components A and B in Examples 1-7 and Comparative Examples 1-5 were mixed in the same proportion to form a waterproof structure, and the performance of the waterproof structure was tested. The test method is as follows. The test results are shown in Table 1:

[0165] Tear strength: According to the requirements of GB / T 19250-2013 polyurethane waterproof coating

[0166] Elongation at break: According to the requirements of GB / T 19250-2013 polyurethane waterproof coating

[0167] Tensile strength: According to the requirements of GB / T 19250-2013 polyurethane waterproof coating

[0168] Table 1

[0169] Tear strength / (N / mm) Elongation at break / (%) Tensile strength / (MPa) Example 1 45 600 4.5 Example 2 46 420 4.3 Example 3 46 650 5.0 Example 4 40 500 5.5 Example 5 30 700 3.2 Example 6 41 680 3.8 Example 7 20 800 2.0 Example 8 50 200 5.5 Comparative Example 1 26 250 6.0 Comparative Example 2 10 780 1.3 Comparative Example 3 28 200 6.1 Comparative Example 4 30 150 7.5 Comparative Example 5 36 750 1.8

[0170] As can be seen from the above table, the addition of active diluent at S10 or S30 has a greater impact on the performance of the system. If added later, the viscosity of the system will be too high, which is not conducive to dispersion, resulting in uneven curing of the polymer coating and stress defects. Under the condition of a certain reducing agent, the amount of active diluent has an impact on the tensile strength and elongation at break of the system, because the active diluent provides a three-dimensional cross-linked network. The type and amount of reducing agent mainly affect the physical properties by affecting the curing speed and conversion rate of the active diluent. Insufficient amount will cause damage to the tensile strength and tear strength. Replacing other reducing agents will cause the viscosity to rise too fast due to uncontrollable speed, resulting in high strength and insufficient elongation at break. Adjusting the type of active diluent can obtain correspondingly improved strength. Not adding pH buffer will weaken the free radical speed, resulting in poor performance in all aspects. Adding latent curing agent can effectively reduce the reaction with water to produce polyurea during the curing process of polyurethane, further promote its chain growth, so the coating has the best performance in all aspects.

[0171] The above is only a specific implementation of the present application. Those skilled in the art can clearly understand that for the convenience and simplicity of description, the specific working processes of the systems, modules and units described above can refer to the corresponding processes in the aforementioned method embodiments, and will not be repeated here. It should be understood that the protection scope of the present application is not limited to this. Any technician familiar with the technical field can easily think of various equivalent modifications or replacements within the technical scope disclosed in this application, and these modifications or replacements should be included in the protection scope of this application.

Claims

1. A multi-cured PMMA elastic waterproof coating composition, characterized in that: It includes component A and component B; Wherein, component A includes optional additives and: 20 to 50 parts by weight of a PUA resin, wherein a prepolymer of the PUA resin is obtained by reacting a polyisocyanate and an oligomer polyol at a molar ratio of 1.1:1 to 1.5:1, and the end group of the molecular chain skeleton of the PUA resin includes a double bond; 10 to 30 parts by weight of a PU resin, wherein the prepolymer of the PU resin is obtained by reacting a polyisocyanate and an oligomer polyol in a molar ratio of 1.18:1 to 2.3:1, and the terminal groups of the molecular chain skeleton of the PU resin include -NCO; 10 to 15 parts by weight of a mercaptosilane coupling agent; 20 to 50 parts by weight of a reactive diluent; 4 to 10 parts by weight of a reducing agent; Component B includes an oxidant; Wherein, the active diluent includes MMA monomer, and the additive includes an air-drying agent; The reducing agent includes at least one of diethanolamine, dimethylethanolamine, N,N-diethylhydroxylamine, N,N-dimethyl-p-toluidine and N,N-diethylaniline.

2. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The PUA resin is obtained by reacting oligomer polyol, polyisocyanate, hydroxy acrylate, end-capped small molecules, a catalyst and an inhibitor.

3. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

4. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The polyisocyanate includes at least one of HDI, TDI, MDI, IPDI and HMDI.

5. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The hydroxy acrylate includes at least one of hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxybutyl methacrylate.

6. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The end-capped small molecule includes at least one of benzyl alcohol, n-octanol, hydroxybutyric acid and isobornyl alcohol.

7. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The catalyst comprises an organic tin catalyst, and the organic tin catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

8. The PMMA elastic waterproof coating composition according to claim 2, characterized in that: The polymerization inhibitor includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone and methylhydroquinone.

9. The PMMA elastic waterproof coating composition according to any one of claims 1 to 8, characterized in that: The PU resin is obtained by reacting oligomer polyol, polyisocyanate and a catalyst.

10. The PMMA elastic waterproof coating composition according to claim 9, characterized in that: The molecular weight of the oligomer polyol is 1000-6000 and the functionality is 2-3.

11. The PMMA elastic waterproof coating composition according to claim 9, characterized in that: The polyisocyanate includes at least one of HDI, TDI, MDI, IPDI and HMDI.

12. The PMMA elastic waterproof coating composition according to claim 9, characterized in that: The catalyst comprises an organic tin catalyst, and the organic tin catalyst comprises at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, methyltin trichloride, dibutyltin dichloride and dibutyltin diacetate.

13. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The gas drying agent includes at least one of refined paraffin and semi-refined paraffin, and the number of the refined paraffin or the semi-refined paraffin includes at least one of 52#, 54#, 56#, 58#, 60#, 62# and 68#.

14. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The reactive diluent further comprises at least one of methacrylic acid, styrene, butyl acrylate, isooctyl acrylate, glycidyl acrylate, hydroxyethyl methacrylate, ethyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate and trimethylolpropane triacrylate.

15. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The mercaptosilane coupling agent includes HS-(R1) n -Si(R2)3; Wherein, R1 is -CH2-, R2 is -O(CH2) m CH3, n≥1, m≥0.

16. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The oxidant includes at least one of benzoyl peroxide, dicumyl peroxide and cumene hydroperoxide.

17. The PMMA elastic waterproof coating composition according to claim 1, characterized in that: The additives also include at least one of the following:

18. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The pH buffer includes at least one of tartaric acid, potassium dihydrogen phosphate and sodium bicarbonate.

19. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The anti-ultraviolet aging agent includes UV-326 and At least one of UV-329.

20. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The antioxidant includes 1010 and At least one of 686.

21. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The anti-settling agent includes A-200 fumed silica.

22. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The reinforcing agent includes at least one of 3102 Mitsubishi resin and 950 Mitsubishi resin.

23. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The latent curing agent includes at least one of a single-component moisture-curing polyurethane auxiliary drier WCAT-WQ01 and a polyurethane latent curing agent YRLH-1106.

24. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The filler has a mesh size of 400 to 2000 and includes at least one of heavy calcium carbonate, light calcium carbonate, talcum powder, barium sulfate, aluminum hydroxide, titanium dioxide, fumed silica and nano calcium carbonate.

25. The PMMA elastic waterproof coating composition according to claim 17, characterized in that: The plasticizer includes at least one of DOTP, DOP and acetyl tributyl citrate.

26. A method for preparing the PMMA elastic waterproof coating composition according to any one of claims 9 to 25, characterized in that: include: To prepare the PUA resin, after reacting the oligomer polyol and the polyisocyanate, a catalyst, an inhibitor, a capped small molecule, and a hydroxy acrylate are added in order, and the PUA resin is obtained after reacting again; To prepare PU resin, oligomer polyol and polyisocyanate are reacted, a catalyst is added, and the reaction is repeated to obtain the PU resin; Prepare component A by mixing materials containing the PUA resin, the PU resin, a mercaptosilane coupling agent, an active diluent and a reducing agent to obtain component A; Prepare component B by mixing materials containing an oxidant to obtain the component B; preparing a PMMA elastic waterproof coating composition, storing the component A and the component B independently to obtain the PMMA elastic waterproof coating composition; Wherein, in the preparation of the PUA resin, the amount of the oligomer polyol is x1, the amount of the polyisocyanate is y1, y1:x1=1.1:1-1.5:1; In the preparation of PU resin, the amount of the oligomer polyol is x2, the amount of the polyisocyanate is y2, and y2:x2=1.18:1-2.3:

1.

27. The preparation method according to claim 26, characterized in that: In the preparation of PUA resin, The amount of the hydroxy acrylate is z, wherein z:(y1-x1)=1.1:1 to 1.2:

1.

28. The preparation method according to claim 26, characterized in that: In preparing the A component, the material also includes additives.

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