High water-resistant high-toughness light-transmitting acrylic powder resin, and preparation method and application thereof

Abstract

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

Description

Technical Field

[0001] This invention relates to the field of powder resin technology, specifically to a high water-resistant, high-toughness, and light-transmitting acrylic powder resin, its preparation method, and its applications. Background Technology

[0002] Currently, the demand for transparent resins is increasing in fields such as automotive wheels and photovoltaics, and the requirements for resin performance are also becoming more stringent. Especially in photovoltaic applications, due to the harsh external environment, the requirements for the resin's water resistance and toughness are becoming increasingly stringent.

[0003] Powdered resins are widely used materials in coatings, plastics, and other industrial fields. They typically exist in powder form and can be cured by heat to form a robust coating or product. Polyester and epoxy resins are among the most commonly used powdered resins. However, epoxy resins suffer from poor weather resistance and are prone to discoloration, while polyester resins are easily hydrolyzed and have only moderate weather resistance. Polyacrylic acid powdered resins exhibit superior weather resistance and a designable structure, making molecular chain modification easier.

[0004] However, the market currently offers relatively few polyacrylic acid powder resin products, and their basic properties are largely similar. Due to the amorphous and cross-linked structural characteristics of acrylic resins, their film density is insufficient; furthermore, some hydrophilic monomers have hydrophilic molecular segments, resulting in generally poor water resistance for polyacrylic acid powder resins. In addition, photovoltaic applications require products made from transparent powder resins to possess a certain degree of toughness and bendability to ensure the safety of the solar cells during transportation and installation. Therefore, resins used in photovoltaics must meet strong and tough performance requirements to guarantee the reliability of the final product. Summary of the Invention

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

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a high water-resistant, high-toughness, and light-transmitting acrylic powder resin, prepared from raw materials comprising the following parts by weight:

[0008]

[0009]

[0010] The epoxy-based raw materials include glycidyl methacrylate and / or allyl glycidyl ether;

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

[0012] Preferably, the reactive groups of the reactive silica powder are double bonds; the particle size of the reactive silica powder is ≤1μm.

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

[0014] Preferably, the acrylate 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 peroxide, di-tert-butyl peroxide, di-tert-pentyl peroxide, tert-butyl hydroperoxide, and tert-butyl peroxide-3,5,5-trimethylhexanoate.

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

[0018] This invention provides a method for preparing the above-mentioned high water resistance, high toughness, and light-transmitting acrylic powder resin, comprising the following steps:

[0019] Methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, epoxy raw material, ethylene tert-carbonate, styrene, acrylate monomers containing two double bonds, reactive silica powder, double-terminated reactive silicon monomers, silane coupling agents containing double bonds, a first initiator and a chain transfer agent are mixed to obtain a monomer mixture.

[0020] The single-ended reactive silicon monomer is mixed with the first organic solvent to obtain a single-ended reactive silicon monomer solution.

[0021] The monomer mixture is added dropwise to the preheated second part of organic solvent to start the 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 added dropwise to the second part of organic solvent. After the addition is completed, the first heat preservation is performed.

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

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

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

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

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

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

[0028] This invention provides the application of the above-mentioned high water resistance, high toughness, and light-transmitting acrylic powder resin in the photovoltaic or automotive fields.

[0029] This invention provides a high water-resistant, high-toughness, and light-transmitting acrylic powder resin, prepared from the following raw materials in parts by weight: 100 parts organic solvent; 20-50 parts methyl methacrylate; 5-20 parts butyl methacrylate; 1-15 parts tert-butyl methacrylate; 10-50 parts epoxy group raw material; 1-20 parts ethylene tert-carbonate; 10-30 parts styrene; 1-10 parts acrylate monomer containing two double bonds; 0-5 parts reactive silica powder; 0-5 parts single-terminated reactive silica monomer; 0-5 parts double-terminated reactive silica monomer; 0.1-2 parts silane coupling agent containing double bonds; 0.1-8 parts initiator; 0.1-5 parts chain transfer agent; wherein the epoxy group raw material includes glycidyl methacrylate and / or allyl glycidyl ether, and the amounts of the single-terminated and double-terminated reactive silica monomers are not both 0.

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

[0031] ① This invention uses styrene and acrylate monomers as the 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 powder resin. Specifically, the double-ended reactive silicon monomers can directly form the main molecular chain structure with hydrocarbon chains, which greatly improves the flexibility of the molecular chain; the single-ended reactive silicon monomers are distributed on the side chains of the molecular chain, which can provide a shielding effect and improve the water resistance of the resin itself.

[0032] ② In this invention, a silane coupling agent containing double bonds is added to the raw material system. On the one hand, this can enhance the compatibility between the resin molecular chain and silicon dioxide or silicon monomers, ensuring that the light transmittance is not affected. On the other hand, after the silane coupling agent crosslinks with water, it can form a silicon-oxygen crosslinked structure, which not only improves the density of the material, but also makes the crosslinked structure of silicon-oxygen bonds more tough than carbon-hydrogen bonds, thereby improving the toughness of the resin.

[0033] ③ This invention appropriately introduces acrylate monomers containing two double bonds into the raw material system. These are double-hydrogen-bonded monomers, which will form a short-chain internal cross-linked structure during polymerization. Meanwhile, during the subsequent molding process, the powder resin, under the action of the curing agent, will form an external cross-linked structure. This multidimensional and multi-layered cross-linked structure ensures the strength of the powder resin product, meeting practical application requirements.

[0034] ④ The present invention introduces tertiary ethylene carbonate into the raw material system, which can increase the hydrophobicity and flexibility of the polymer, as well as increase the adhesion and weather resistance. In addition, the monomers used in the present invention contain side group structures with tertiary carbon or long carbon chains, which will also improve the water resistance of the resin to a certain extent.

[0035] This invention provides a method for preparing the aforementioned high water-resistant, high-toughness, and light-transmitting acrylic powder resin. In the powder resin synthesis process, reactive silica or reactive silicon monomers are introduced into the acrylic acid molecular chain, achieving a uniform distribution of reactive silica or reactive silicon monomers on the side chains and main chain. This improves the water resistance and toughness of the final product, meeting the requirements of subsequent product applications. Furthermore, the preparation method provided by this invention is simple to operate, low in cost, and easily scalable for industrial-scale mass production.

[0036] The results of the examples show that the light transmittance of the high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention is 92-93%, which is higher than that of ordinary acrylic powder resin (90-92%). The water absorption rate of the powder resin of the present invention is 0.5-1.35%, which is lower than that of ordinary acrylic powder resin (2-4%). ​​The samples prepared by the powder resin of the present invention did not show cracks after the falling ball impact test, indicating that it has excellent toughness. Attached Figure Description

[0037] Figure 1 This is a photograph of the high water resistance, high toughness, and light-transmitting acrylic powder resin obtained in Example 3.

[0038] Figure 2 This is a photograph of the test sample obtained after curing the high water resistance, high toughness, and light transmittance acrylic powder resin obtained in Example 1. Detailed Implementation

[0039] This invention provides a high water-resistant, high-toughness, and light-transmitting acrylic powder resin, prepared from raw materials comprising the following parts by weight:

[0040]

[0041]

[0042] The epoxy-based raw materials include glycidyl methacrylate and / or allyl glycidyl ether;

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

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

[0045] The raw materials for preparing the high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by this invention include 100 parts by weight. In this 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 this invention, the selection of the above solvents enables the dissolution of monomers and provides a uniform polymerization environment.

[0046] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 20 to 50 parts of methyl methacrylate, preferably 30 to 40 parts; as a specific embodiment of the present invention, the amount of methyl methacrylate used 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 high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 5 to 20 parts of butyl methacrylate, preferably 10 to 15 parts; as a specific embodiment of the present invention, the amount of butyl methacrylate used is 5, 8, 10, 15, or 20 parts.

[0048] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 1 to 15 parts of tert-butyl methacrylate, preferably 5 to 10 parts; as a specific embodiment of the present invention, the amount of tert-butyl methacrylate used 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 high water-resistant, high-toughness, and translucent acrylic powder resin provided by this invention include 10 to 50 parts of epoxy-based raw materials, preferably 20 to 40 parts. As a specific embodiment of this invention, the amount of the epoxy-based raw material is 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts. In this invention, the epoxy-based raw material includes glycidyl methacrylate and / or allyl glycidyl ether. In this invention, the epoxy-based raw material is used to provide epoxy crosslinking groups for subsequent crosslinking reactions with the curing agent.

[0050] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and translucent acrylic powder resin provided by this invention include 1 to 20 parts of ethylene tert-carbonate, preferably 5 to 15 parts; as a specific embodiment of this invention, the amount of ethylene tert-carbonate used is 1, 3, 5, 8, 10, 15, or 20 parts. In this invention, the ethylene tert-carbonate can increase the hydrophobicity and flexibility of the polymer, and increase its adhesion and weather resistance.

[0051] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and light-transmitting acrylic powder resin provided by the present invention include 10 to 30 parts of styrene, preferably 15 to 25 parts; as a specific embodiment of the present invention, the amount of styrene used 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 endow the polymer with high light transmittance.

[0052] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and translucent acrylic powder resin provided by this invention include 1 to 10 parts of an acrylate monomer containing two double bonds, preferably 3 to 8 parts. As a specific embodiment of this invention, the amount of the acrylate monomer containing two double bonds is 1, 3, 5, 8, or 10 parts. In this invention, the acrylate monomer containing two double bonds preferably includes allyl (meth)acrylate. In this invention, the acrylate monomer containing two double bonds is a double-bonded monomer, which forms a short-chain intra-linked structure during polymerization, ensuring the strength and toughness of the polymer.

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

[0054] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and translucent acrylic powder resin provided by this invention include 0 to 5 parts of a single-ended reactive silicon monomer, preferably 1 to 4 parts. In a specific embodiment of this invention, the amount of the single-ended reactive silicon monomer is 0, 1, 2, 3, 4, or 5 parts. In this invention, the single-ended reactive silicon monomer is a reactive silane containing a double bond at one end, specifically preferably a methacrylate siloxane oligomer. In a specific embodiment of this invention, the single-ended reactive silicon monomer is 3821M3, 3811F5, 3811F46, or 3823F5 produced by Sloco. In this invention, the single-ended reactive silicon monomer is distributed on 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 high 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, specifically 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 Sloco. In the present invention, the structural formula of 3824F2 is shown in Formula 1, and the molecular weight is 1300.

[0056]

[0057] In this invention, the double-ended reactive silicon monomer can directly form the main molecular chain structure with hydrocarbon chains, 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 high 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 double bonds, preferably 0.5 to 1.5 parts. As a specific embodiment of the present invention, the amount of the silane coupling agent containing double bonds 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 double bonds preferably includes propyl 3-(trimethoxysilyl)methacrylate. In the present invention, the silane coupling agent containing double bonds can, on the one hand, enhance the compatibility of the resin molecular chain with silica or silicon monomers, ensuring that the light transmittance is not affected; on the other hand, after the silane coupling agent crosslinks with water, it can form a silicon-oxygen crosslinked structure, which not only improves the material density, but also the crosslinked structure of silicon-oxygen bonds has higher toughness than carbon-hydrogen bonds, thereby improving the toughness of the resin.

[0059] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and translucent 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 peroxide, di-tert-butyl peroxide, di-tert-pentyl peroxide, tert-butyl hydroperoxide, and tert-butyl peroxide-3,5,5-trimethylhexanoate.

[0060] Based on the mass fraction of the organic solvent, the raw materials for preparing the high water-resistant, high-toughness, and translucent acrylic powder resin provided by the present invention include 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 this invention, the particle size of the high water-resistant, high-toughness, and light-transmitting acrylic powder resin is preferably 50–120 μm.

[0062] This invention provides a method for preparing the above-mentioned high water resistance, high toughness, and light-transmitting acrylic powder resin, comprising the following steps:

[0063] Methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, epoxy raw material, ethylene tert-carbonate, styrene, acrylate monomers containing two double bonds, reactive silica powder, double-terminated reactive silicon monomers, silane coupling agents containing double bonds, a first initiator and a chain transfer agent are mixed to obtain a monomer mixture.

[0064] The single-ended reactive silicon monomer is mixed with the first organic solvent to obtain a single-ended reactive silicon monomer solution.

[0065] The monomer mixture is added dropwise to the preheated second part of organic solvent to start the 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 added dropwise to the second part of organic solvent. After the addition is completed, the first heat preservation is performed.

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

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

[0068] This invention involves mixing methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, an epoxy-based raw material, ethylene tert-carbonate, styrene, an acrylate monomer containing two double bonds, reactive silica powder, a double-terminated reactive silicon monomer, a silane coupling agent containing double bonds, a first initiator, and a chain transfer agent to obtain a monomer mixture. In this invention, the mass of the first initiator is preferably 90-99% of the total initiator mass, more preferably 95%. This invention does not impose special requirements on the mixing method; any mixing method well known to those skilled in the art can be used, such as stirring.

[0069] This invention involves mixing a single-ended reactive silicon monomer with a first portion of organic solvent to obtain a single-ended reactive silicon monomer solution. In this invention, the mass of the first portion of organic solvent is preferably 0-20% of the total mass of the organic solvent, more preferably 5-15%, specifically 1%, 5%, 10%, 15%, or 20%. This invention does not have special requirements for the mixing method; any mixing method well-known in the art can be used, such as stirring. In this invention, this step is omitted when the amount of single-ended reactive silicon monomer is 0 parts.

[0070] In this invention, the monomer mixture is added dropwise to a preheated second portion of organic solvent to initiate a free radical polymerization reaction. When 1 / 3 to 1 / 4 of the monomer mixture remains, the remaining monomer mixture and a single-end reactive silicon monomer solution are simultaneously added dropwise to the second portion of organic solvent. After the addition is complete, a first heat preservation process is performed. In this invention, the preheating temperature of the second portion of organic solvent is preferably 130–140°C, more preferably 135°C, and the preheating time is preferably 20–30 minutes. In this invention, the preheating of the second portion of organic solvent provides a suitable temperature environment for the polymerization reaction, and simultaneously, during the preheating process, the reaction system is filled with solvent vapor.

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

[0072] In this invention, the preferred temperature for the first heat preservation is 134–138°C, and the preferred time is 1–2 hours. This invention, through the first heat preservation, ensures a more complete polymerization reaction.

[0073] After the first heat treatment, a second initiator is added, followed by a second heat treatment to obtain a free radical polymerization reaction solution. In this invention, the preferred temperature for the second heat treatment is 134–138°C, and the preferred time is 2–3 hours. Through this second heat treatment, the polymerization reaction can be made more complete, reducing the presence of residual monomers.

[0074] After obtaining the free radical polymerization reaction solution, the present invention removes the organic solvent from the free radical polymerization reaction solution to obtain a highly water-resistant, highly tough, and transparent acrylic powder resin. In the present invention, the method for removing the organic solvent is preferably vacuum distillation. The present invention does not have special requirements for the specific operation of the vacuum distillation, as long as the organic solvent is sufficiently removed.

[0075] After removing the organic solvent from the free radical polymerization reaction solution, the present invention preferably crushes and / or grinds the resulting solid to obtain a high water-resistant, high-toughness, and translucent acrylic powder resin. The present invention does not have special requirements for the specific crushing and grinding methods; they can be designed according to the particle size requirements of the high water-resistant, high-toughness, and translucent acrylic powder resin.

[0076] This invention provides the application of the above-mentioned high water resistance, high toughness, and light-transmitting acrylic powder resin in the photovoltaic or automotive fields.

[0077] In this invention, the high water-resistant, high-toughness, and light-transmitting acrylic powder resin is preferably cured using a curing agent containing carboxyl groups, and the curing agent containing carboxylic acid is preferably dodecyl diacid.

[0078] The following detailed description, in conjunction with embodiments, illustrates the high water resistance, high toughness, and light transmittance acrylic powder resin, its preparation method, and its applications provided by the present invention. However, these descriptions 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 stands for butyl acrylate;

[0081] TBA is tert-butyl acrylate;

[0082] GMA stands for glycidyl methacrylate.

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

[0084] AMA stands for allyl methacrylate.

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

[0086] The raw material formulations of the high water-resistant, high-toughness, and light-transmitting acrylic powder resins in Examples 1-5 and Comparative Examples 1-5 are shown in Table 1:

[0087] Table 1. Raw material formulations (parts by weight) of the high water-resistant, high-toughness, and light-transmitting acrylic powder resins in Examples 1-5 and Comparative Examples 1-5.

[0088]

[0089]

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

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

[0092] (1) Mix MMA, BA, TBA, epoxy raw materials, ethylene tert-carbonate, styrene, allyl methacrylate, reactive silica, double-terminated reactive silicon monomer, silane coupling agent, first initiator and chain transfer agent to obtain monomer mixture; wherein the first initiator accounts for 95% of the total initiator mass;

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

[0094] (3) The monomer mixture is added dropwise to the remaining xylene preheated at 138°C to start the free radical polymerization reaction at 138°C; when the monomer mixture is added to 1 / 3 of the remaining volume, the single-end reactive silicon monomer solution is added dropwise simultaneously with the monomer mixture, and the addition lasts for 5 hours.

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

[0096] (5) Recover xylene by vacuum distillation until all solvent is removed;

[0097] (6) Heat up and discharge the material.

[0098] The preparation method of the comparative powder resin is the same as that of the example, except that the corresponding raw materials are omitted or changed.

[0099] The physical image of the high water-resistant, high-toughness, and light-transmitting acrylic powder resin obtained in Example 3 is shown below. Figure 1 As shown.

[0100] Performance testing

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

[0102] Add 30 wt% curing agent (dodecyl diacid) and 2.5 wt% accelerator (tetrabutylammonium bromide) to the powder resin, mix evenly, melt extrude at 80-110℃, feed into a tablet press for tableting, crush in a coarse pulverizer, grind in a fine grinding mill, and sieve to obtain a powder coating with a particle size of 50-120 μm. Then press it into a film at 130-150℃ and a pressure of 1 MPa to obtain a test sample with a thickness of 200 μm.

[0103] The obtained test samples were subjected to transmittance, water absorption, and falling ball impact tests. The transmittance test instrument was a Shimadzu UV-2600i UV-Vis spectrophotometer. The water absorption rate was tested according to GBT-1462-2005 Test Method for Water Absorption of Fiber Reinforced Plastics. The falling ball impact test was carried out using a falling ball impact tester, with a steel ball weighing 227g and with a diameter of 38.1mm, which was allowed to fall freely from a height of 1m with an initial velocity of 0.

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

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

[0106] Table 2. Performance test results of the powder resins obtained in the examples and comparative examples.

[0107]

[0108] As shown in Table 2, the light transmittance of the high water-resistant, high-toughness, and transparent acrylic powder resin of this invention is 92-93%, while the light transmittance of ordinary commercially available acrylic powder resin is generally 90-92%. The water absorption rate of the high water-resistant, high-toughness, and transparent acrylic powder resin of this invention is 0.5-1.35%, while the water absorption rate of ordinary commercially available acrylic powder resin is generally 2-4%. The samples made from the powder resin of this invention did not show cracks after the falling ball impact test, indicating that it has excellent toughness.

[0109] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high water-resistant, high-toughness, light-transmitting acrylic powder resin, characterized in that, It is prepared from the following raw materials in parts by weight: 100 parts organic solvent; 20-50 parts of methyl methacrylate; 5-20 parts of butyl methacrylate; 1-15 parts of tert-butyl methacrylate; 10-50 parts of epoxy-based raw materials; 1-20 parts of ethylene tert-carbonate; 10-30 parts of styrene; 1 to 10 parts of acrylate monomers containing two double bonds; 1-4 parts of single-ended reactive silicon monomer; 1-4 parts of double-ended reactive silicon monomer; 0.1 to 2 parts of a silane coupling agent containing double bonds; Initiator 0.1-8 parts; Chain transfer agent 0.1-5 parts; The epoxy-based raw materials include glycidyl methacrylate and / or allyl glycidyl ether; The silane coupling agent containing double bonds includes propyl 3-(trimethoxysilyl)methacrylate; The acrylate monomer containing two double bonds is (meth)acrylate allyl acrylate; The single-ended reactive silicon monomer is a methacrylate siloxane oligomer; The double-ended reactive silicon monomer is a reactive silane containing double bonds at both ends; The preparation method of the high water-resistant, high-toughness, and light-transmitting acrylic powder resin includes the following steps: Methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, epoxy raw material, ethylene tert-carbonate, styrene, acrylate monomers containing two double bonds, double-terminated reactive silicon monomers, silane coupling agents containing double bonds, a first initiator and a chain transfer agent are mixed to obtain a monomer mixture. The single-ended reactive silicon monomer is mixed with the first organic solvent to obtain a single-ended reactive silicon monomer solution. The monomer mixture is added dropwise to the preheated second part of organic solvent to start the 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 added dropwise to the second part of organic solvent. After the addition is completed, the first heat preservation is performed. After the first heat preservation, a second part of initiator is added, and a second heat preservation is performed to obtain a free radical polymerization reaction solution; The organic solvent in the free radical polymerization reaction solution is removed to obtain a highly water-resistant, highly tough, and transparent acrylic powder resin.

2. The high water-resistant, high-toughness, translucent acrylic powder resin according to claim 1, characterized in that, The organic solvent includes one or more of xylene, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate; The initiator includes one or more of tert-butyl peroxide, di-tert-butyl peroxide, di-tert-pentyl peroxide, tert-butyl hydroperoxide, and tert-butyl peroxide-3,5,5-trimethylhexanoate. The chain transfer agent includes dodecyl mercaptan and / or 2,4-diphenyl-4-methyl-1-pentene.

3. The method for preparing the high water-resistant, high-toughness, and light-transmitting acrylic powder resin according to claim 1 or 2, characterized in that, Includes the following steps: Methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, epoxy raw material, ethylene tert-carbonate, styrene, acrylate monomers containing two double bonds, double-terminated reactive silicon monomers, silane coupling agents containing double bonds, a first initiator and a chain transfer agent are mixed to obtain a monomer mixture. The single-ended reactive silicon monomer is mixed with the first organic solvent to obtain a single-ended reactive silicon monomer solution. The monomer mixture is added dropwise to the preheated second part of organic solvent to start the 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 added dropwise to the second part of organic solvent. After the addition is completed, the first heat preservation is performed. After the first heat preservation, a second part of initiator is added, and a second heat preservation is performed to obtain a free radical polymerization reaction solution; The organic solvent in the free radical polymerization reaction solution is removed to obtain a highly water-resistant, highly tough, and transparent acrylic powder resin.

4. The preparation method according to claim 3, characterized in that, The first portion of the initiator accounts for 90-99% of the total initiator mass. The mass of the first organic solvent is 5 to 15% of the total mass of the organic solvent.

5. The preparation method according to claim 3, characterized in that, The preheating temperature of the second organic solvent is 130~140℃.

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

7. The application of the high water-resistant, high toughness, and light-transmitting acrylic powder resin according to claim 1 or 2, or the high water-resistant, high toughness, and light-transmitting acrylic powder resin prepared by the preparation method according to any one of claims 3 to 6, in the photovoltaic or automotive fields.

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