High-water-resistance high-toughness light-transmitting acrylic acid powder resin as well as preparation method and application thereof

Abstract

The invention provides high-water-resistance high-toughness light-transmitting acrylic acid powder resin as well as a preparation method and application thereof, and belongs to the technical field of powder resin. The high-water-resistance high-toughness light-transmitting acrylic acid powder resin is prepared from the following preparation raw materials in parts by mass: 100 parts of an organic solvent; 20 to 50 parts of methyl (meth) acrylate; 5 to 20 parts of (methyl) butyl acrylate; 1 to 15 parts of tert-butyl (meth) acrylate; 10 to 50 parts of an epoxy group raw material; 1-20 parts of vinyl versatate; 0 to 30 parts of styrene; 1-10 parts of an acrylate monomer containing two double bonds; 0-5 parts of reactive silicon dioxide powder; 0-5 parts of a single-ended reactive silicon monomer; 0-5 parts of a double-end reactive silicon monomer; 0.1 to 2 parts of a silane coupling agent; 0.1 to 8 parts of an initiator; and 0.1-5 parts of a chain transfer agent. The light-transmitting acrylic powder resin with high water resistance and high toughness has excellent water resistance and toughness and good light transmittance.

Description

Technical Field

[0001] The invention relates to the technical field of powdered resins, and in particular to a highly water-resistant, highly tough and light-transmitting acrylic powdered resin and a preparation method and application thereof. Background Art

[0002] At present, the demand for transparent resins in the fields of automotive wheels, photovoltaics, etc. is increasing, and the requirements for resin performance are also getting higher and higher. Especially in the field of photovoltaic applications, due to the harsh external application environment, the requirements for resin water resistance and toughness are becoming more and more stringent.

[0003] Powder resin is a material widely used in coatings, plastics and other industrial fields. It usually exists in powder form and can be cured by heating to form a solid coating or product. Among them, the most commonly used powder resins are polyester resin and epoxy resin. However, epoxy resin has the disadvantages of poor weather resistance and easy discoloration, while polyester resin is easy to hydrolyze and has average weather resistance. Polyacrylic acid powder resin has outstanding weather resistance, and its structure is designable, making it easy to modify the molecular chain.

[0004] However, there are relatively few polyacrylic acid powder resin products on the market, and the basic performance of the products is not much different. Due to the amorphous and cross-linked structural characteristics of acrylic resin, its film-forming density is not enough; and the molecular segments of some hydrophilic monomers have a certain hydrophilicity, resulting in the general water resistance of polyacrylic acid powder resin. In addition, in photovoltaic applications, products made of transparent powder resin are required to have a certain toughness and need to be able to be bent to ensure the safety of the battery cells during transportation or installation. Therefore, for resins used in the photovoltaic field, strong performance requirements need to be met to ensure the performance reliability of the final product. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a highly water-resistant, high-toughness, light-transmitting acrylic powder resin and its preparation method and application. The highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention has excellent water resistance and toughness, as well as good light transmittance.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a highly water-resistant, highly tough and light-transmitting acrylic powder resin, which is prepared from the following raw materials in parts by weight:

[0008]

[0009]

[0010] The epoxy raw material includes glycidyl methacrylate and / or allyl glycidyl ether;

[0011] The usage amounts of the single-end reactive silicon monomer and the double-end reactive silicon monomer are not both 0.

[0012] Preferably, the reactive group of the reactive silica powder is a double bond; and the particle size of the reactive silica powder is ≤1 μm.

[0013] Preferably, the silane coupling agent containing a double bond includes 3-(trimethoxysilyl)propyl methacrylate.

[0014] Preferably, the acrylic acid ester monomer containing two double bonds includes allyl (meth)acrylate.

[0015] Preferably, the organic solvent includes one or more of xylene, ethylene glycol butyl ether, ethyl acetate, solvent oil, toluene, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate;

[0016] The initiator includes one or more of tert-butyl perbenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxy-3,5,5-trimethylhexanoate;

[0017] The chain transfer agent includes dodecyl mercaptan and / or 2,4-diphenyl-4-methyl-1-pentene.

[0018] The present invention provides a method for preparing the above-mentioned highly water-resistant, highly tough and light-transmissive acrylic powder resin, comprising the following steps:

[0019] Mixing methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, epoxy raw material, tert-butyl carbonate, styrene, acrylate monomer containing two double bonds, reactive silica powder, double-end reactive silicon monomer, silane coupling agent containing double bonds, the first initiator and chain transfer agent to obtain a monomer mixture;

[0020] Mixing the single-end reactive silicon monomer with the first portion of the organic solvent to obtain a single-end reactive silicon monomer solution;

[0021] The monomer mixture is added dropwise to the preheated second organic solvent to start a free radical polymerization reaction. When 1 / 3 to 1 / 4 of the monomer mixture remains, the remaining monomer mixture and the single-end reactive silicon monomer solution are added dropwise to the second organic solvent simultaneously. After the addition is completed, a first heat preservation is performed;

[0022] After the first heat preservation, a second portion of initiator is added, and a second heat preservation is performed to obtain a free radical polymerization reaction liquid;

[0023] The organic solvent in the free radical polymerization reaction liquid is removed to obtain a highly water-resistant, highly tough and light-transmitting acrylic powder resin.

[0024] Preferably, the mass of the first initiator is 90-99% of the mass of the total initiator;

[0025] The mass of the first organic solvent is 0-20% of the mass of the whole organic solvent.

[0026] Preferably, the preheating temperature of the second organic solvent is 130-140°C.

[0027] Preferably, the first insulation time is 1 to 2 hours; the second insulation time is 2 to 3 hours.

[0028] The present invention provides application of the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin in the photovoltaic field or the automotive field.

[0029] The invention provides a highly water-resistant, high-toughness, light-transmitting acrylic powder resin, which is prepared from the following raw materials in parts by mass: 100 parts of an organic solvent; 20 to 50 parts of methyl (meth)acrylate; 5 to 20 parts of butyl (meth)acrylate; 1 to 15 parts of tert-butyl (meth)acrylate; 10 to 50 parts of an epoxy raw material; 1 to 20 parts of tert-butyl carbonate; 10 to 30 parts of styrene; 1 to 10 parts of an acrylate monomer containing two double bonds; 0 to 5 parts of reactive silicon dioxide powder; 0 to 5 parts of a single-end reactive silicon monomer; 0 to 5 parts of a double-end reactive silicon monomer; 0.1 to 2 parts of a silane coupling agent containing a double bond; 0.1 to 8 parts of an initiator; and 0.1 to 5 parts of a chain transfer agent. The epoxy raw material comprises glycidyl methacrylate and / or allyl glycidyl ether, and the amounts of the single-end reactive silicon monomer and the double-end reactive silicon monomer are not both 0.

[0030] The beneficial effects of the present invention are as follows:

[0031] ① The present invention uses styrene and acrylate monomers as main raw materials, and introduces reactive silica and reactive silicon monomers into the system, which can improve the flexibility and / or water resistance of the powdered resin. Specifically, the double-ended reactive silicon monomer can directly form a main molecular chain structure with the hydrocarbon chain, greatly improving the flexibility of the molecular chain; the single-ended reactive silicon monomer is distributed in the side chain of the molecular chain, which can provide a shielding effect and improve the water resistance of the resin itself.

[0032] ② The present invention adds a silane coupling agent containing a double bond to the raw material system, which can enhance the compatibility of the resin molecular chain with silicon dioxide or silicon monomer to ensure that the light transmittance is not affected; on the other hand, the silane coupling agent can form a silicon-oxygen cross-linked structure after cross-linking in water, which not only improves the density of the material, but also the cross-linked structure of the silicon-oxygen bond has higher toughness than the carbon-hydrogen bond, thereby improving the toughness of the resin.

[0033] ③ The present invention appropriately introduces an acrylate monomer containing two double bonds into the raw material system. This is a double hydrogen bond monomer, which will form a short-chain internal cross-linking structure during the polymerization process; and the powder resin will form an external cross-linking structure under the action of the curing agent during the subsequent molding process. The multi-dimensional and multiple cross-linking structure ensures the strength of the powder resin product and meets the actual application requirements.

[0034] ④ The present invention introduces tert-butyl vinyl carbonate into the raw material system, which can increase the hydrophobicity and flexibility of the polymer, and increase the adhesion and weather resistance; in addition, the monomer used in the present invention contains a tertiary carbon or long carbon chain side group structure, which will also improve the water resistance of the resin to a certain extent.

[0035] The present invention provides a method for preparing the above-mentioned highly water-resistant, highly tough and light-transmissive acrylic powder resin. In the process of synthesizing the powder resin, the present invention introduces reactive silica or reactive silicon monomer into the acrylic acid molecular chain to achieve uniform distribution of reactive silica or reactive silicon monomer on the side chain and the main chain, thereby improving the water resistance and toughness of the final product and meeting the application requirements of later products. In addition, the preparation method provided by the present invention is simple to operate, low in cost, and easy to realize industrial mass production.

[0036] The results of the embodiments show that the light transmittance of the highly water-resistant and highly tough transparent acrylic powder resin provided by the present invention is 92-93%, which is higher than the 90-92% of ordinary acrylic powder resins; the water absorption of the powder resin of the present invention is 0.5-1.35%, which is lower than the 2-4% of ordinary acrylic powder resins; the sample made of the powder resin of the present invention does not show cracks after a falling ball impact test, indicating that it has excellent toughness. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a physical picture of the highly water-resistant, high-toughness, light-transmitting acrylic powder resin obtained in Example 3;

[0038] Figure 2 This is a physical picture of the test sample obtained after the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin obtained in Example 1 was cured. DETAILED DESCRIPTION

[0039] The present invention provides a highly water-resistant, highly tough and light-transmitting acrylic powder resin, which is prepared from the following raw materials in parts by weight:

[0040]

[0041]

[0042] The epoxy raw material includes glycidyl methacrylate and / or allyl glycidyl ether;

[0043] The usage amounts of the single-end reactive silicon monomer and the double-end reactive silicon monomer are not both 0.

[0044] Unless otherwise specified, the raw materials used in the present invention are commercially available.

[0045] The raw materials for preparing the highly water-resistant, highly tough and light-transmitting acrylic powder resin provided by the present invention include 100 parts of an organic solvent by mass. In the present invention, the organic solvent is preferably one or more of xylene, ethylene glycol butyl ether, ethyl acetate, solvent oil, toluene, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate. In the present invention, the selection of the above solvents can dissolve the monomers and provide a uniform polymerization environment.

[0046] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness and light-transmitting acrylic powder resin provided by the present invention include 20 to 50 parts of methyl (meth)acrylate, preferably 30 to 40 parts; as a specific embodiment of the present invention, the amount of methyl (meth)acrylate is 20, 25, 30, 35, 40, 45 or 50 parts.

[0047] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness and light-transmitting acrylic powder resin provided by the present invention include 5 to 20 parts of butyl (meth)acrylate, preferably 10 to 15 parts; as a specific embodiment of the present invention, the amount of butyl (meth)acrylate is 5, 8, 10, 15 or 20 parts.

[0048] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness and light-transmitting acrylic powder resin provided by the present invention include 1 to 15 parts of tert-butyl (meth)acrylate, preferably 5 to 10 parts; as a specific embodiment of the present invention, the amount of tert-butyl (meth)acrylate is 1, 3, 5, 8, 10, 12 or 15 parts.

[0049] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention include 10 to 50 parts of epoxy raw materials, preferably 20 to 40 parts; as a specific embodiment of the present invention, the amount of the epoxy raw materials is 10, 15, 20, 25, 30, 35, 40, 45 or 50 parts. In the present invention, the epoxy raw materials include glycidyl methacrylate and / or allyl glycidyl ether. In the present invention, the epoxy raw materials are used to provide epoxy crosslinking groups for the purpose of crosslinking reaction with a curing agent later.

[0050] Based on the mass fraction of the organic solvent, the raw material for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention includes 1 to 20 parts of versatate, preferably 5 to 15 parts; as a specific embodiment of the present invention, the amount of versatate is 1, 3, 5, 8, 10, 15 or 20 parts. In the present invention, the versatate can increase the hydrophobicity and flexibility of the polymer, and increase the bonding force and weather resistance.

[0051] Based on the mass fraction of the organic solvent, the raw material for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention includes 10 to 30 parts of styrene, preferably 15 to 25 parts; as a specific embodiment of the present invention, the amount of styrene is 10, 15, 18, 20, 25 or 30 parts. In the present invention, the styrene can improve the mechanical properties, hardness, water resistance and solvent resistance of the polymer, and give the polymer high light transmittance.

[0052] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, highly tough and light-transmitting acrylic powder resin provided by the present invention include 1 to 10 parts of an acrylate monomer containing two double bonds, preferably 3 to 8 parts; as a specific embodiment of the present invention, the amount of the acrylate monomer containing two double bonds is 1, 3, 5, 8 or 10 parts. In the present invention, the acrylate monomer containing two double bonds preferably includes allyl (meth)acrylate. In the present invention, the acrylate monomer containing two double bonds is a double bond monomer, which will form a short-chain internal cross-linking structure during the polymerization process to ensure the strength and toughness of the polymer.

[0053] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 0 to 5 parts of reactive silica powder. As a specific embodiment of the present invention, the amount of the reactive silica powder is 0, 1, 2, 3, 4, or 5 parts. In the present invention, the particle size of the reactive silica powder is preferably ≤1 μm. In the present invention, the reactive group of the reactive silica powder is a double bond. As a specific embodiment of the present invention, the model of the reactive silica powder is Evonik SR711.

[0054] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention include 0 to 5 parts of a single-end reactive silicon monomer, preferably 1 to 4 parts; as a specific embodiment of the present invention, the amount of the single-end reactive silicon monomer is 0, 1, 2, 3, 4 or 5 parts. In the present invention, the single-end reactive silicon monomer is a reactive silane containing a double bond at one end, and is preferably a methacrylate siloxane oligomer. As a specific embodiment of the present invention, the single-end reactive silicon monomer is 3821M3, 3811F5, 3811F46 or 3823F5 produced by Siloke. In the present invention, the single-end reactive silicon monomer is distributed in the side chain of the molecular chain, which can provide a shielding effect and improve the water resistance of the resin itself.

[0055] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 0 to 5 parts of a double-ended reactive silicon monomer, preferably 1 to 4 parts; as a specific embodiment of the present invention, the amount of the double-ended reactive silicon monomer is 0, 1, 2, 3, 4 or 5 parts. In the present invention, the double-ended reactive silicon monomer is a reactive silane containing double bonds at both ends, and is preferably a dimethacrylate-terminated polysiloxane. As a specific embodiment of the present invention, the double-ended reactive silicon monomer is 3824F2, 3824M3 or 3572F5 produced by Siloke. In the present invention, the structural formula of 3824F2 is shown in Formula 1, and the molecular weight is 1300:

[0056]

[0057] In the present invention, the double-ended reactive silicon monomer can directly form a main molecular chain structure with the hydrocarbon chain, which greatly improves the flexibility of the molecular chain.

[0058] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 0.1 to 2 parts of a silane coupling agent containing a double bond, preferably 0.5 to 1.5 parts; as a specific embodiment of the present invention, the amount of the silane coupling agent containing a double bond is 0.1, 0.5, 0.8, 1, 1.2, 1.5, 1.8 or 2 parts. In the present invention, the silane coupling agent containing a double bond preferably includes 3-(trimethoxysilyl) propyl methacrylate. In the present invention, the silane coupling agent containing a double bond can enhance the compatibility of the resin molecular chain with silicon dioxide or silicon monomer on the one hand, ensuring that the light transmittance is not affected; on the other hand, the silane coupling agent can form a silicon-oxygen cross-linked structure after cross-linking in water, which not only improves the density of the material, but also the cross-linked structure of the silicon-oxygen bond is relatively tougher than the carbon-hydrogen bond, thereby improving the toughness of the resin.

[0059] Based on the mass fraction of the organic solvent, the raw materials for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention include 0.1 to 8 parts of an initiator, preferably 1 to 5 parts; as a specific embodiment of the present invention, the amount of the initiator is 0.1, 0.5, 1, 3, 5 or 8 parts. In the present invention, the initiator is preferably one or more of tert-butyl peroxybenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxy-3,5,5-trimethylhexanoate.

[0060] Based on the mass fraction of the organic solvent, the raw material for preparing the highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention includes 0.1 to 5 parts of a chain transfer agent, preferably 0.5 to 3 parts; as a specific embodiment of the present invention, the amount of the chain transfer agent is 0.1, 0.5, 1, 2, 3, 4 or 5 parts. In the present invention, the chain transfer agent is preferably dodecyl mercaptan and / or 2,4-diphenyl-4-methyl-1-pentene.

[0061] In the present invention, the particle size of the highly water-resistant, high-toughness, and light-transmissive acrylic powder resin is preferably 50 to 120 μm.

[0062] The present invention provides a method for preparing the above-mentioned highly water-resistant, highly tough and light-transmissive acrylic powder resin, comprising the following steps:

[0063] Mixing methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, epoxy raw material, tert-butyl carbonate, styrene, acrylate monomer containing two double bonds, reactive silica powder, double-end reactive silicon monomer, silane coupling agent containing double bonds, the first initiator and chain transfer agent to obtain a monomer mixture;

[0064] Mixing the single-end reactive silicon monomer with the first portion of the organic solvent to obtain a single-end reactive silicon monomer solution;

[0065] The monomer mixture is added dropwise to the preheated second organic solvent to start a free radical polymerization reaction. When 1 / 3 to 1 / 4 of the monomer mixture remains, the remaining monomer mixture and the single-end reactive silicon monomer solution are added dropwise to the second organic solvent simultaneously. After the addition is completed, a first heat preservation is performed;

[0066] After the first heat preservation, a second portion of initiator is added, and a second heat preservation is performed to obtain a free radical polymerization reaction liquid;

[0067] The organic solvent in the free radical polymerization reaction liquid is removed to obtain a highly water-resistant, highly tough and light-transmitting acrylic powder resin.

[0068] The present invention mixes methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, epoxy raw material, tert-butyl carbonate, styrene, acrylate monomer containing two double bonds, reactive silica powder, double-end reactive silicon monomer, silane coupling agent containing double bonds, the first initiator and chain transfer agent to obtain a monomer mixture. In the present invention, the mass of the first initiator is preferably 90-99% of the mass of the total initiator, more preferably 95%. The present invention has no special requirements for the mixing method, and the mixing method well known to those skilled in the art can be applied, such as stirring and mixing.

[0069] The present invention mixes a single-end reactive silicon monomer with a first portion of an organic solvent to obtain a single-end reactive silicon monomer solution. In the present invention, the mass of the first portion of the organic solvent is preferably 0 to 20% of the mass of the total organic solvent, more preferably 5 to 15%, specifically 1%, 5%, 10%, 15% or 20%. The present invention has no special requirements for the mixing method, and a mixing method well known in the art can be used, specifically, stirring and mixing. In the present invention, when the amount of the single-end reactive silicon monomer used is 0 part, this step is omitted.

[0070] The present invention drips the monomer mixture into the preheated second organic solvent to start a free radical polymerization reaction. When 1 / 3 to 1 / 4 of the monomer mixture remains, the remaining monomer mixture and the single-end reactive silicon monomer solution are simultaneously dripped into the second organic solvent. After the dripping is completed, the first insulation is performed. In the present invention, the preheating temperature of the second organic solvent is preferably 130 to 140°C, more preferably 135°C, and the preheating time is preferably 20 to 30 minutes. In the present invention, the role of preheating the second organic solvent is to provide a temperature environment suitable for the polymerization reaction, and at the same time, during the preheating process, the reaction system is filled with solvent vapor.

[0071] In the present invention, the total dripping time from the start of dripping the monomer mixture to the completion of dripping the remaining monomer mixture and the single-end reactive silicon monomer solution is preferably 4 to 6 hours, more preferably 5 hours. In the present invention, based on 100g of the monomer mixture, the dripping rate of the monomer mixture is preferably 15 to 25g / h. In the present invention, the temperature of the free radical polymerization reaction is preferably 134 to 138°C. In the present invention, the dripping speed of the remaining monomer mixture and the single-end reactive silicon monomer solution is independently preferably 5 to 18g / h. By controlling the order of adding materials, the present invention can distribute the double-end reactive silicon monomer in the main chain structure of the molecular chain and the single-end reactive silicon monomer in the side chain.

[0072] In the present invention, the temperature of the first heat preservation is preferably 134-138° C., and the time is preferably 1-2 hours. The present invention can ensure a more complete polymerization reaction through the first heat preservation.

[0073] After the first heat preservation, the present invention adds a second portion of initiator and performs a second heat preservation to obtain a free radical polymerization reaction liquid. In the present invention, the temperature of the second heat preservation is preferably 134 to 138° C., and the time is preferably 2 to 3 hours. The present invention can make the polymerization reaction more complete and reduce the presence of residual monomers through the second heat preservation.

[0074] After obtaining the free radical polymerization reaction liquid, the present invention removes the organic solvent in the free radical polymerization reaction liquid to obtain a highly water-resistant, highly tough, and light-transmissive acrylic powder resin. In the present invention, the method of removing the organic solvent is preferably vacuum distillation. The present invention has no special requirements for the specific operation of the vacuum distillation, as long as the organic solvent can be fully removed.

[0075] After removing the organic solvent from the free radical polymerization reaction liquid, the present invention preferably crushes and / or grinds the obtained solid to obtain a highly water-resistant, high-toughness, light-transmitting acrylic powder resin. The present invention has no special requirements for the specific method of crushing and grinding, and can be designed accordingly according to the particle size requirements of the highly water-resistant, high-toughness, light-transmitting acrylic powder resin.

[0076] The present invention provides application of the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin in the photovoltaic field or the automotive field.

[0077] In the present invention, the highly water-resistant, high-toughness, light-transmitting acrylic powder resin is preferably cured by a curing agent with a carboxyl group in practical applications, and the curing agent with a carboxylic acid is preferably dodecane diacid.

[0078] The highly water-resistant, high-toughness, light-transmitting acrylic powder resin provided by the present invention and its preparation method and application are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0079] In the following examples, MMA is methyl methacrylate;

[0080] BA is butyl acrylate;

[0081] TBA is tert-butyl acrylate;

[0082] GMA is glycidyl methacrylate;

[0083] vv-10 is tert-butylene carbonate;

[0084] AMA is allyl methacrylate.

[0085] Examples 1 to 5 and Comparative Examples 1 to 5

[0086] The raw material formula of the highly water-resistant, highly tough and light-transmitting acrylic powder resin in Examples 1 to 5 and Comparative Examples 1 to 5 is shown in Table 1:

[0087] Table 1 Raw material formula of highly water-resistant, highly tough and light-transmitting acrylic powder resin in Examples 1 to 5 and Comparative Examples 1 to 5 (parts by mass)

[0088]

[0089]

[0090] In Table 1, the silane coupling agent containing a double bond is 3-(trimethoxysilyl)propyl methacrylate, the initiator is di-tert-amyl peroxide, and the chain transfer agent is dodecyl mercaptan.

[0091] The preparation method of the highly water-resistant, high-toughness, light-transmitting acrylic powder resin in the embodiment is as follows:

[0092] (1) MMA, BA, TBA, epoxy raw materials, versatate, styrene, allyl methacrylate, reactive silica, dual-end reactive silicon monomer, silane coupling agent, the first initiator and chain transfer agent are mixed to obtain a monomer mixture, wherein the first initiator accounts for 95% of the mass of the total initiator;

[0093] (2) mixing the first portion of xylene with the single-end reactive silicon monomer to obtain a single-end reactive silicon monomer solution; wherein the first portion of xylene accounts for 10% of the mass of the total xylene;

[0094] (3) adding the monomer mixture dropwise to the remaining xylene preheated to 138° C. to start a free radical polymerization reaction at a reaction temperature of 138° C.; when the monomer mixture is added to the remaining 1 / 3, start adding the single-end reactive silicon monomer solution dropwise, and end the addition dropwise at the same time as the monomer mixture, and add dropwise for a total of 5 hours;

[0095] (4) Keep the temperature at 138°C for 1 hour; add the remaining initiator and keep the temperature at 138°C for another 2 hours;

[0096] (5) recovering xylene by distillation under reduced pressure until the solvent is completely extracted;

[0097] (6) Heating and discharging.

[0098] The preparation method of the powdered resin of the comparative example refers to the preparation method of the example, except that the corresponding raw materials are omitted or changed.

[0099] The actual picture of the highly water-resistant, high-toughness, light-transmitting acrylic powder resin obtained in Example 3 is as follows Figure 1 shown.

[0100] Performance Testing

[0101] The powdered resins obtained in the examples and comparative examples were prepared into test samples in the following manner:

[0102] Add 30wt% of curing agent (dodecyl diacid) and 2.5wt% of accelerator (tetrabutylammonium bromide) to the powder resin, mix well, and then melt extrude at 80-110°C, send it to a tablet press for tableting, a coarse grinder for crushing, a fine grinder for grinding, and sieve to obtain a powder coating with a particle size of 50-120μm, and then press it in a press at 130-150°C and a pressure of 1MPa to obtain a test sample with a thickness of 200μm.

[0103] The obtained test samples were subjected to transmittance, water absorption and falling ball impact tests, wherein the transmittance test instrument was Shimadzu UV-2600i UV-visible spectrophotometer; the water absorption was tested in accordance with GBT-1462-2005 fiber reinforced plastic water absorption test method; a falling ball impact test was carried out using a falling ball impact testing machine, using a steel ball with a weight of 227 g and a diameter of 38.1 mm, and free falling at a height of 1 m with an initial velocity of 0.

[0104] The actual picture of the test sample obtained after curing the high water-resistant, high-toughness and light-transmitting acrylic powder resin obtained in Example 1 is as follows Figure 2 shown.

[0105] The performance test results of the powdered resins obtained in the examples and comparative examples are shown in Table 2.

[0106] Table 2 Performance test results of powdered resin obtained in Examples and Comparative Examples

[0107]

[0108] It can be seen from Table 2 that the light transmittance of the highly water-resistant and highly tough light-transmitting acrylic powder resin of the present invention is 92-93%, while the light transmittance of ordinary commercially available acrylic powder resins is generally 90-92%; the water absorption of the highly water-resistant and highly tough light-transmitting acrylic powder resin of the present invention is 0.5-1.35%, while the water absorption of ordinary commercially available acrylic powder resins is generally 2-4%; the sample made of the powder resin of the present invention has no cracks after the falling ball impact test, indicating that it has excellent toughness.

[0109] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly water-resistant, high-toughness, light-transmitting acrylic powder resin, characterized in that: The preparation is obtained by including the following raw materials in parts by weight: The epoxy raw material includes glycidyl methacrylate and / or allyl glycidyl ether; The usage amounts of the single-end reactive silicon monomer and the double-end reactive silicon monomer are not both 0.

2. The highly water-resistant, high-toughness, light-transmitting acrylic powder resin according to claim 1, characterized in that: The reactive groups of the reactive silicon dioxide powder are double bonds; and the particle size of the reactive silicon dioxide powder is ≤1 μm.

3. The highly water-resistant, high-toughness, light-transmitting acrylic powder resin according to claim 1, characterized in that: The silane coupling agent containing a double bond includes 3-(trimethoxysilyl)propyl methacrylate.

4. The highly water-resistant, highly tough, light-transmitting acrylic powder resin according to claim 1, characterized in that: The acrylic acid ester monomer containing two double bonds includes allyl (meth)acrylate.

5. The highly water-resistant, highly tough and light-transmitting acrylic powder resin according to claim 1, characterized in that: The organic solvent includes one or more of xylene, ethylene glycol butyl ether, ethyl acetate, solvent oil, toluene, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate; The initiator includes one or more of tert-butyl perbenzoate, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxy-3,5,5-trimethylhexanoate; The chain transfer agent includes dodecyl mercaptan and / or 2,4-diphenyl-4-methyl-1-pentene.

6. The method for preparing the highly water-resistant, high-toughness, and light-transmitting acrylic powder resin according to any one of claims 1 to 5, characterized in that: The following steps are involved: Mixing methyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, epoxy raw material, tert-butyl carbonate, styrene, acrylate monomer containing two double bonds, reactive silica powder, double-end reactive silicon monomer, silane coupling agent containing double bonds, the first initiator and chain transfer agent to obtain a monomer mixture; Mixing the single-end reactive silicon monomer with the first portion of the organic solvent to obtain a single-end reactive silicon monomer solution; The monomer mixture is added dropwise to the preheated second organic solvent to start a free radical polymerization reaction. When 1 / 3 to 1 / 4 of the monomer mixture remains, the remaining monomer mixture and the single-end reactive silicon monomer solution are added dropwise to the second organic solvent simultaneously. After the addition is completed, a first heat preservation is performed; After the first heat preservation, a second portion of initiator is added, and a second heat preservation is performed to obtain a free radical polymerization reaction liquid; The organic solvent in the free radical polymerization reaction liquid is removed to obtain a highly water-resistant, highly tough and light-transmitting acrylic powder resin.

7. The preparation method according to claim 6, characterized in that: The mass of the first initiator is 90-99% of the mass of the total initiator; The mass of the first organic solvent is 0-20% of the mass of the whole organic solvent.

8. The preparation method according to claim 6, characterized in that: The preheating temperature of the second organic solvent is 130-140°C.

9. The preparation method according to claim 6, characterized in that: The first heat preservation time is 1 to 2 hours; the second heat preservation time is 2 to 3 hours.

10. Use of the highly water-resistant, highly tough, and light-transmitting acrylic powder resin according to any one of claims 1 to 5 or the highly water-resistant, highly tough, and light-transmitting acrylic powder resin prepared by the preparation method according to any one of claims 6 to 9 in the photovoltaic field or the automotive field.

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