A new type of light water sports board HEM forming material and forming process

Abstract

A novel light weight water sports board HEM forming material is obtained by the following method: hydrophobic liquid or colloidal silicone modified epoxy polymer is prepared by using tetramethylcyclotetrasiloxane, allyl glycidyl ether and styrene; polyether modification is carried out by using 50-80 parts of epoxy resin, 5-10 parts of the aforementioned silicone modified epoxy polymer, 5-10 parts of epoxy active diluent and amino-terminated polyether; further emulsification; the emulsified product is added with water, dicyandiamide, accelerator and foaming agent to form a coating foaming material; after coating and drying, an epoxy expansion core material EEC is obtained, the foaming ratio of the epoxy expansion core material EEC is in the range of 50-150 times, and the density of the foaming core material obtained after heat expansion is in the range of 0.01-0.05 g / cm 3 . The heat expansion molding forming HEM process is applied to the carbon fiber molding of water sports board, low density and controllable density, can resist seawater adsorption and resist sun exposure. The forming efficiency is high, the quality is good, and the raw material loss is reduced.

Description

Technical Field

[0001] This invention relates to the field of lightweight water sports board manufacturing, and in particular to a novel lightweight water sports board HEM molding material and its molding process. Background Technology

[0002] Surfboards are generally made of an inner core and an outer fiber layer. The original surfboards used wood for the core, which was relatively heavy. Due to the demand for weight reduction, most modern surfboards use high-density expanded polystyrene (EPS) or polyurethane (PU). The core material density is typically required to be below 0.025 g / cm³. 3 However, while meeting these density requirements, these materials often struggle to withstand the temperature challenges of traditional carbon fiber compression molding. Traditional carbon fiber compression molding typically operates at temperatures between 100-160℃ for 30-120 minutes, requiring the core material to withstand these temperatures and timeframes without decomposition, expansion, or shrinkage; otherwise, the fiber product's appearance will lack fullness. Furthermore, regardless of whether water sports are conducted in seawater or freshwater, damage to the surfboard surface and water absorption by the core material can easily lead to weight gain and accelerated aging. Exposure to sunlight and increased temperatures can also cause bulging, deformation, or delamination and cracking.

[0003] High-density polystyrene (EPS) foam is lightweight and has good strength. EPS is also recyclable, making it an environmentally friendly material. However, because EPS shrinks at temperatures above 90°C, it is not suitable for medium- and low-temperature molding processes exceeding 100°C. Therefore, this material is only suitable for hand lay-up fiber cloth covering processes. This cannot overcome all the drawbacks of the hand lay-up process, such as the volatile odor from the hand lay-up resin causing environmental pollution, uncontrollable differences in product weight and size due to manual production by workers, and the long curing time required for the resin, resulting in low production efficiency.

[0004] Polyurethane (PU) foam is a synthetic polymer foam material with good flexibility and resistance to compressive deformation. However, its production is environmentally unfriendly. The core material for surfboards is obtained through CNC cutting and repeated sanding and finishing, generating a large amount of scrap that is difficult to recycle. Although PU material is very durable under normal conditions, if the outer fiber layer is damaged due to trauma or breakage, the PU core will absorb water and age rapidly, causing the foam to break and become brittle. Moreover, PU has relatively poor compressive properties; when subjected to small-area impacts, the core material is easily dented or crushed, leading to irreversible damage.

[0005] Polymethacrylimide (PMI) foam is a cross-linked rigid foam material with a 100% closed-cell structure. Its uniformly cross-linked pore structure endows it with outstanding structural stability and excellent mechanical properties. When used as a core material, it must be CNC machined, inevitably resulting in waste of scrap material during the cutting process, typically 30%-50%. The lower limit of the material's conventional density is 0.025 g / cm³. 3 However, bottlenecks arise in applications with lower densities. To ensure a strong bond between the core material and the outer carbon fiber prepreg, an adhesive coating process is required on the surface of the PMI core material, reducing efficiency, increasing weight, and raising costs. Furthermore, because this foam material is a rigid foam, its toughness and resilience are extremely poor. When subjected to small-area impacts, the core material can easily dent or crush, leading to irreversible damage.

[0006] Regarding molding processes, the aforementioned high-density polystyrene (EPS), polyurethane (PU), and polymethacrylimide (PMI) foam core materials are mostly processed using CNC machining, with compression molding rarely seen. Patent CN103146216A discloses a high-energy adhesive product, its preparation method, and its uses. This high-energy adhesive product, by weight per kilogram, comprises: thermoplastic rubber 15-25; ethyl acetate 10-25; foaming agent 6-20; methyl ethyl ketone (MEK) 30-60; plasticizer 0.5-3; antioxidant 0.5-2.5; stearic acid 0.5-2; crosslinking agent 2-3.5; and polyester fiber 3-10. It is a thermoplastic rubber-based chemical foaming material, making it difficult to achieve a density below 0.025 g / cm³. 3 The demand for foam and the organic solvents used in the preparation process are not conducive to environmental protection and ensuring the health of employees during the production process.

[0007] Patent CN107089017A discloses a thermal expansion process for high-energy adhesive molded fiber composite products. Specifically, the process involves cutting and preparing fiber composite fabric and high-energy adhesive according to structural design specifications; layering the fiber composite fabric according to mechanical structural design requirements, wrapping it around the high-energy adhesive to obtain a rolled product; preheating the rolled product on a heating table at room temperature to -80℃ for 3-60 minutes, squeezing out interlayer gas as much as possible, and flattening it; then placing the product in a pre-molding mold and pre-molding it according to the design of the mold to obtain a pre-molded product; preheating the pre-molded product in a preheated oven at 35-75℃ for 3-60 minutes, then removing it and placing it in a molding mold, closing the mold tightly; sending the mold to a hot press molding table, where the high-energy adhesive expands under heating and then does not shrink, or expands first and then shrinks, completing the product molding; sending the molded product to a cooling table for cooling, then to a demolding table to open the mold and remove the product. The high-energy adhesive and fiber composite fabric are expanded and cured together in one step. The implicit assumption of this process is that it is only suitable for products with relatively thin thickness. If the product is thicker than 1 cm, the curing of the prepreg and the expansion of the high-energy adhesive will be asynchronous. The high temperature of the mold will first act on the tightly attached fiber prepreg, causing the prepreg to be heated and cured quickly. Once the prepreg is cured first, it will limit the heat expansion of the internal high-energy adhesive, resulting in insufficient foam expansion and an insufficiently full appearance of the product. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a novel lightweight water sports board with a thermal expansion molding process (HEM) material and its molding process, which is adaptable to carbon fiber compression molding, has low density and controllable density, and is resistant to seawater adsorption and sun exposure.

[0009] To address the aforementioned technical problems, this invention provides a novel lightweight HEM molding material for water sports boards, characterized by being prepared through the following steps:

[0010] Step 1: Preparation of silicone-modified epoxy polymer: A hydrophobic silicone-modified epoxy polymer, abbreviated as SiEP, is prepared using tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene.

[0011] Step 2: Prepare the organosilicon polyether modified epoxy polymer, abbreviated as SiEEP, using the following components and proportions:

[0012] 1) Epoxy resin, abbreviated as EP, 50-80 parts by weight,

[0013] 2) 5-10 parts by weight of the organosilicon-modified epoxy polymer SiEP obtained in step 1.

[0014] 3) Epoxy reactive diluent, abbreviated as ED, 5-10 parts by weight.

[0015] 4) Amino-terminated polyether, abbreviated as PEA, the number of moles of NH bonds in the feed amount is 0.2-0.5 times the number of moles of epoxy groups in the system;

[0016] Step 3: Add the silicone polyether modified epoxy polymer SiEEP obtained in Step 2 to a solvent, emulsify and dilute to obtain silicone polyether modified epoxy emulsion, abbreviated as AQ-SiEEP; The formula used is: 100 parts by weight of silicone polyether modified epoxy polymer SiEEP obtained in Step 2, 10-20 parts by weight of co-solvent, and 60-100 parts by weight of main solvent.

[0017] Step 4: Preparation of coating foam material: It is prepared by mixing the following components and proportions:

[0018] 1) Organosilicon polyether modified epoxy emulsion AQ-SiEEP, 50-70 parts by weight,

[0019] 2) Water, 0-30 parts by weight

[0020] 3) The amount of dicyandiamide (DICY) used is 0.9-1.0 times the molar number of epoxy in the organosilicon polyether modified epoxy emulsion AQ-SiEEP, multiplied by the active hydrogen equivalent.

[0021] 4) Accelerator, the dosage is 0.5-1.5 times the weight of dicyandiamide (DICY) in the feed.

[0022] 5) Foaming agent, 50-100 parts by weight;

[0023] Step 5: Preparation of epoxy expandable core material (EEC): The foaming material obtained in Step 4 is coated onto release paper and dried to obtain epoxy expandable core material (EEC) that can be peeled off from the release paper. The expansion ratio of the epoxy expandable core material (EEC) ranges from 50 to 150 times, and the density of the foamed core material obtained after thermal expansion ranges from 0.01 to 0.05 g / cm³. 3 .

[0024] As a further preferred embodiment, in step 1, the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene is 1:2:2. The preparation process is as follows: In an inert gas-protected reactor, tetramethylcyclotetrasiloxane is added and the temperature is maintained at 80°C. A mixture of 25% allyl glycidyl ether and 25% styrene is added while stirring at 500 rpm. Then, 20-60 ppm of platinum catalyst (CAS number 68478-92-2) is added dropwise. The stirring is maintained at 500 rpm for 10 minutes. Then, the remaining 75% of the mixture of allyl glycidyl ether (AGE) and 75% styrene (ST) is added dropwise. The dropping rate is controlled to maintain the temperature of the system within the range of 80-90°C. After the addition is complete, the reaction is maintained with stirring for 4 hours. Then, the temperature is raised to 120°C, and the low-boiling-point solvent is removed under reduced pressure (absolute pressure 10-20 kPa). A transparent liquid is obtained by discharging the product, which is an organosilicon-modified epoxy polymer (SiEP).

[0025] The SiEP obtained in step 1 includes two isomers with the following structural formulas:

[0026] , , , .

[0027] In step 2, the epoxy resin is one or any combination of two or more of epoxy resin E-06, epoxy resin E-12, epoxy resin E-20, epoxy resin E-44, and epoxy resin E-51; the epoxy reactive diluent is one or any combination of two or more of benzyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polypropylene glycol diglycidyl ether; and the terminal amino polyether is one or any combination of two or more of polypropylene diamine D230, polypropylene diamine D400, polyethylene diamine ED600, and polyethylene diamine ED900.

[0028] The preparation process in step 2 is as follows: Epoxy resin EP, silicone-modified epoxy polymer SiEP obtained in step 1, and epoxy reactive diluent ED are weighed according to the proportion and added to the reactor. The temperature is maintained at 70°C, and the mixture is stirred and mixed at 300-900 rpm for 2-4 hours. Then, terminal amino polyether PEA is added according to the calculated amount of feed, and the mixture is stirred and mixed at 300-900 rpm for 1-2 hours. The mixture is then left to stand at room temperature for more than 12 hours for later use to obtain silicone polyether-modified epoxy polymer SiEEP.

[0029] The main solvent in step 3 is water; the co-solvent is one or any combination of two or more of isopropanol, ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, and dipropylene glycol butyl ether.

[0030] The specific procedure for step 3 is as follows: Weigh the organosilicon polyether modified epoxy polymer SiEEP and co-solvent obtained in step 2 according to the ratio, and add them to the emulsification device one after another. Raise the temperature to 80°C, stir at 900-1000 rpm for 0.5 hours until uniform, cool down to 60°C, and add the main solvent dropwise while stirring for 1.5 hours at 3000 rpm. Maintain high speed shear emulsification for 1 hour, and then cool down to 40°C and maintain high speed stirring at 3000 rpm for 1 hour to obtain organosilicon polyether modified epoxy emulsion AQ-SiEEP.

[0031] In step 4, the accelerator is preferably an organic urea accelerator, 1,1'-(4-methyl-m-phenylene)bis(3,3-dimethylurea) with CAS number 17526-94-2.

[0032] In step 4, the foaming agent is a thermally expanding microsphere; the foaming agent is selected from NOURYON's 551DU40, 461DU20, 051DU40, 920DU20, 920DU40; or MATSUMOTO's F-48D, F-50D, F-65D, MSH-340, MSH-550, F-100MD, F-78KD, F-82D; or SEKISUI's EHM204, EHM302, EM303, EM406, EML101.

[0033] The epoxy expanded core material EEC coating obtained in step 5 has a weight of 100-300 g / m². 2 .

[0034] Meanwhile, the present invention also provides a molding process for manufacturing a novel lightweight water sports board (HEM) from the above-mentioned materials, characterized by comprising the following steps:

[0035] 1) The dimensions of the foaming mold manufactured according to the design dimensions of the water sports board, with the volume of the foam cavity multiplied by the desired core material density of 0.01-0.05 g / cm³. 3 Calculate the weight of epoxy expanded core material (EEC) to be added; weigh the corresponding weight of epoxy expanded core material (EEC) and place it into the foaming mold, close the mold and lock the mold effectively;

[0036] 2) Transfer the foaming mold to the hot press platen for hot pressing foaming expansion, and then cold press to cool down to obtain the foamed core material of the water sports board;

[0037] 3) Wrap fiber prepreg around the foamed core material of the water sports board to obtain a prepreg enclosure;

[0038] 4) The prepreg package is placed into the molding mold of the sports board, hot-pressed on the hot press plate, and then cold-pressed to obtain the rough blank of the water sports board.

[0039] As an important performance characteristic obtained by the present invention, the water absorption capacity of the rough blank of the water sports board is 20g-80g.

[0040] The preferred specific method for step 2) is as follows: the foaming mold is transferred to the hot press platform, which is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at 120-160℃. The upper and lower hot presses are then closed, and the pressure range of the hot press is 10-100 kgf / cm². 2 Foaming time: 30-120 min; Open the hot press platform to release pressure; Transfer the mold to the cold press platform, which is pre-connected to a cooling device with sufficient cooling power, maintaining the platform temperature at 0-25℃; Close the upper and lower cold presses, with a press pressure range of 10-100 kgf / cm². 2 The mold is cooled; when the temperature of the mold drops below 60°C, the cold press platform is opened, the mold is removed, and the mold is opened to obtain the foamed core material of the water sports board.

[0041] In step 1), a rigid foam connecting plate is pre-embedded in the lower mold base of the foaming mold for subsequent connection of the flat rod; the rigid foam connecting plate has a strength of 0.04-0.05 g / cm³. 3 Polyimide foam, or 0.04-0.05 g / cm³ 3 Polyurethane foam, or 0.04-0.05 g / cm³ 3 Polyvinyl chloride foam.

[0042] The preferred method for step 4) of the water sports board rough molding is as follows: The prepreg package is placed into the molding mold of the sports board, the mold is closed and effectively locked; it is then transferred to a hot press platform, which is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at 100-160℃; the upper and lower hot presses are closed, and the press pressure range is 10-100 kgf / cm². 2 The molding time is 50-120 minutes. Open the hot press platform to release pressure; transfer the mold to the cold press platform, which is pre-connected to a cooling device with sufficient cooling power. Maintain the platform temperature at 0-25℃. Close the upper and lower cold presses. The press pressure range is 10-100 kgf / cm². 2 The mold is cooled down. When the temperature of the mold drops below 60°C, the cold press plate is opened, the mold is removed, the mold is unlocked and opened to obtain a lightweight water sports board blank.

[0043] In step 3), when preparing the prepreg enclosure, the fiber prepreg consists of two layers of glass fiber prepreg close to the foamed core material, and an outer layer of 3k carbon fiber prepreg.

[0044] The water sports board preform obtained by this invention exhibits excellent performance. During fatigue testing, after 30,000 reciprocating cycles at a set force of 50 kg at the center of the front foot sleeve hole, the interface between the surface fiber composite material and the internal EEC foam core material remained intact.

[0045] When the water sports board blank is subjected to the lateral bending test, the water sports board is fixed on a vertical test device, and an 850mm long flat rod (9) is fixed on the base (8). A 50kg weight (10) is hung on the top of the outer end of the flat rod. The weight of the weight is used to load the downward force. The water sports board base is subjected to bending test once in each of the two directions. The fiber layer and the internal foam core material at the base remain intact.

[0046] When performing tensile tests on the rough blank of the water sports board, the two ends of the water sports board are pressed down near the middle, and a universal tensile testing machine is used to stretch it upward from the groove of the base of the water sports board. The stretching speed is 25mm / min, and the stretching force is stopped when it reaches 500kg. The fiber layer of the base structure and the internal foam core material remain intact.

[0047] Compared with existing water sports board molding materials and processes, the novel lightweight water sports board HEM (Heat Expansion Molding) molding material and process of this invention can achieve the following beneficial effects on the water sports board:

[0048] 1. Excellent resistance to seawater adsorption. This invention utilizes tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene to modify the organosilicon functional groups, preparing a hydrophobic liquid or colloidal organosilicon-modified epoxy polymer (SiEP). This allows for the preparation of core materials and the final water sports board with excellent resistance to seawater adsorption.

[0049] 2. Excellent resilience. The polyether functional groups are modified with terminal amino polyethers in appropriate molar ratios, further enhancing the toughness of the core material and resulting in excellent resilience. This allows the surfboard to bounce back to its original shape well when subjected to minor impacts and deformations during use, extending the surfboard's lifespan.

[0050] 3. High expansion ratio and controllable foam density. The epoxy expandable core material (EEC) of this invention, through the synergistic effect of a foaming agent and a resin system, can achieve a foaming ratio range of 50-150 times and an expanded foam core material density of 0.01-0.05 g / cm³. 3 It can achieve a concentration of less than 0.025 g / cm³. 3The expanded expanded foam core material (EEC) with its high density is a feature not found in traditional foam materials currently on the market, which are also suitable for medium and low temperature molding. This further leads to an unexpected lightweight effect for surfboards. The required weight of EEC can be calculated according to the desired density and mold cavity volume. The EEC sheet is weighed and placed in the foaming mold, and finally, the expanded expanded foam core material with the designed density is obtained through foaming and molding. Therefore, the density is controllable.

[0051] 4. The epoxy thermosetting system introduced into the EEC formulation of the present invention enables the foamed core material to achieve ring-opening crosslinking reaction under medium and low temperature conditions, thereby increasing the crosslinking density of the resin system. This further prevents the surfboard from bulging and deforming when baked at 80°C, and overcomes the difficulty of heat absorption and deformation of carbon fiber surfboards under high ultraviolet radiation at the beach. In addition, since the epoxy resin component in EEC is of the same type as the epoxy resin in the prepreg, the interface between the two will have better bonding strength, effectively preventing the surfboard from peeling off during use.

[0052] 5. The product has a full appearance and good strength. This invention uses the synergistic effect of a foaming agent and a resin system to not only achieve thermal expansion molding of the core material and controllable expansion, but also, during the product thermoforming stage, the foaming agent inside the core material generates an expansion force from the inside out under medium and low temperature conditions. This expansion can give the fiber product a fuller appearance and better interlayer bonding of the prepreg, thereby improving the strength performance of the product.

[0053] 6. Reduced waste and lower costs. The EEC material of this invention can meet the requirements of HEM thermal expansion molding process, foaming within the mold. Unlike the traditional CNC additive process for foam, this avoids material processing waste and reduces costs.

[0054] 7. The HEM molding process of this invention differs from the traditional hand lay-up process, enabling compression molding in the field of water sports boards, resulting in improved controllability of product weight and quality, improved dimensional accuracy, greatly improved production efficiency, and a significantly improved production environment. Attached Figure Description

[0055] Figure 1 This invention relates to a foaming ratio testing device.

[0056] Figure 2 This is a schematic cross-sectional view of the surfboard blank of the present invention.

[0057] Figure 3 This invention relates to a lateral bending resistance testing device. Detailed Implementation

[0058] The technical solution of the present invention will be further described in detail below through embodiments. Each embodiment is only a preferred implementation to illustrate the technical solution of the present invention and does not constitute a limitation of the present invention.

[0059] In this invention, "parts" refers to parts by weight. Specific implementation steps are shown in Table 1.

[0060] Table 1

[0061] Detailed Implementation Steps Table

[0062] Step 2 Preparation of organosilicon polyether modified epoxy polymer SiEEP Step 3 Preparation of organosilicon polyether modified epoxy emulsion AQ-SiEEP Step 4 Preparation of coating foam material Step 5 Preparation of epoxy expanded core material EEC Step 6 HEM molding of sports board Step 7 Performance testing of sports board blanks

[0063] Example 1

[0064] The novel lightweight water sports board HEM (Heat Expansion Molding) molding material of the present invention is prepared by the following steps.

[0065] Step 1: First, prepare the organosilicon-modified epoxy polymer: Use tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene to prepare a hydrophobic organosilicon-modified epoxy polymer, abbreviated as SiEP.

[0066] Tetramethylcyclotetrasiloxane (CAS: 2370-88-9, abbreviated as D4H), allyl glycidyl ether (CAS: 106-92-3, abbreviated as AGE), and styrene (CAS: 100-42-5, abbreviated as ST) were prepared in a molar ratio of 1:2:2. The specific steps were as follows: The entire process was carried out in a reactor under inert gas protection. A certain amount of D4H was added, and the temperature was maintained at 80℃. Then, a mixture of 25% AGE and 25% ST was added while stirring at 500 rpm. Add 20-60 ppm of platinum catalyst (CAS: 68478-92-2) dropwise, stirring at 500 rpm for 10 min, then add the remaining 75% of AGE and 75% of ST mixture dropwise, controlling the dropwise addition rate to maintain the system temperature within the range of 80-90℃. After the addition is complete, maintain stirring for 4 hours, then raise the temperature to 120℃, remove the low-boiling-point solvent under reduced pressure (absolute pressure 10-20 kPa), and discharge to obtain a transparent liquid organosilicon-modified epoxy polymer SiEP.

[0067] The resulting SiEP includes two isomers with the following structural formulas:

[0068] , , , .

[0069] Step 2: Prepare organosilicon polyether modified epoxy polymer, abbreviated as SiEEP.

[0070] The components and formulations corresponding to Example 1 in Table 2 are as follows:

[0071] 1. Epoxy resin EP is selected in 80 parts of E-44. E-44 is a common product model in this field, and qualified products from various manufacturers are acceptable.

[0072] 2. 8 parts by weight of the organosilicon-modified epoxy polymer SiEP obtained in step 1;

[0073] 3. 10 parts of 1,6-hexanediol diglycidyl ether are selected as the epoxy reactive diluent ED. This is a common product model in this field, and qualified products from various manufacturers are acceptable.

[0074] 4. The molar number of NH bonds in the amount of amino-terminated polyether (PEA) fed should be 0.3 times the molar number of epoxy groups in the system. The commonly used product model D400 in this field should be selected, and qualified products from various manufacturers are acceptable.

[0075] The preparation process is as follows:

[0076] Weigh epoxy resin E-44, the silicone-modified epoxy polymer SiEP obtained in step 1, and 1,6-hexanediol diglycidyl ether according to the above proportions and add them to the reactor. Maintain the temperature at 70°C and stir at 300-900 rpm for 2-4 hours. Then add PEA according to the calculated amount of feed and stir at 300-900 rpm for 1-2 hours. Let it stand at room temperature in a sealed container for more than 12 hours for later use. The silicone polyether-modified epoxy polymer is obtained, abbreviated as SiEEP, and is denoted as SiEEP-1# in Table 2.

[0077] Table 2

[0078] SiEEP-1# Examples 1 and 9 E-44 80 8 1,6-Hexanediol diglycidyl ether 10 D400 The number of NH bonds is 0.3 times the number of epoxy groups in the system. SiEEP-2# Examples 2, 4, and 8 E-51 60 10 Polypropylene glycol diglycidyl ether 8 D400 The number of NH bonds is 0.5 times the number of epoxy groups in the system. SiEEP-3# Examples 3 and 5 E-51 50 5 Butyl glycidyl ether 9 D230 The number of NH bonds is 0.2 times the number of epoxy groups in the system. SiEEP-4# Examples 6 and 7 E-06 70 10 benzyl glycidyl ether 5 ED600 The number of NH bonds is 0.4 times the number of epoxy groups in the system. SiEEP-5# Example 10 E-20 65 5 Phenylated glycidyl ether 8 ED900 The number of NH bonds is 0.3 times the number of epoxy groups in the system. SiEEP-6# E-44 70 10 diglycidyl ether 7 D230 The number of NH bonds is 0.2 times the number of epoxy groups in the system.

[0079] In fact, in this invention, in addition to the components mentioned in Example 1, the epoxy resin EP can also be one or any combination of two or more of epoxy resins E-06, E-12, E-20, E-44, and E-51; the active epoxy diluent ED can also be one or any combination of two or more of benzyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polypropylene glycol diglycidyl ether; the terminal amino polyether can also be one or any combination of two or more of polypropylene diamine D230, polypropylene diamine D400, ethylene diamine ED600, and ethylene diamine ED900.

[0080] Step 3: Prepare organosilicon polyether modified epoxy emulsion, abbreviated as AQ-SiEEP.

[0081] Table 3

[0082] Step 3: Components and proportions for preparing the organosilicon polyether modified epoxy emulsion AQ-SiEEP

[0083] Examples 1 and 9 AQ-SiEEP-1# SiEEP-1# 100 Isopropanol 15 100 water Examples 2, 4, and 8 AQ-SiEEP-2# SiEEP-2# 100 Propylene glycol methyl ether 10 Water 60 Examples 3 and 5 AQ-SiEEP-3# SiEEP-3# 100 Ethylene glycol butyl ether 20 Water 80 Examples 6 and 7 AQ-SiEEP-4# SiEEP-4# 100 Dipropylene glycol butyl ether 20 100 water Example 10 AQ-SiEEP-5# SiEEP-5# 100 Ethylene glycol 20 100 water

[0084] The organosilicon polyether modified epoxy polymer SiEEP obtained in step 2 is added to a solvent for emulsification and dilution to obtain organosilicon polyether modified epoxy emulsion, abbreviated as AQ-SiEEP;

[0085] The emulsification formulation in this invention comprises: 100 parts by weight of the organosilicon polyether-modified epoxy polymer SiEEP obtained in step 2, 10-20 parts by weight of the co-solvent, and 60-100 parts by weight of the main solvent. In this invention, the co-solvent is one or any combination of two or more of isopropanol, ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, and dipropylene glycol butyl ether. The main solvent can be water or other solvents.

[0086] In this Example 1, the proportions shown in Table 3 of Example 1 are used.

[0087] Weigh the silicone polyether-modified epoxy polymer SiEEP-1# obtained in step 2 and the co-solvent isopropanol, and add them sequentially to the emulsification device. Raise the temperature to 80°C, stir at 900-1000 rpm for 0.5 hours until homogeneous, then cool to 60°C. While stirring at 3000 rpm, add the designed amount of main solvent H2O dropwise over 1.5 hours, maintaining high-speed shear emulsification for 1 hour. Then cool to 40°C and maintain high-speed stirring at 3000 rpm for 1 hour to obtain the silicone polyether-modified epoxy emulsion AQ-SiEEP. In this embodiment, the main solvent is preferably water, and the resulting emulsion is silicone polyether-modified epoxy emulsion AQ-SiEEP, denoted as AQ-SiEEP-1# in Table 3. In this embodiment, the preferred main solvent is water, but isopropanol, ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, dipropylene glycol butyl ether, or any combination of two or more of these can also be used as the main solvent.

[0088] Step 4: Prepare the coating foaming material

[0089] Using the components and proportions shown in Example 1 of Table 4, add the organosilicon polyether modified epoxy emulsion AQ-SiEEP, water, dicyandiamide DICY, accelerator, and foaming agent to the mixing tank in the correct proportions. Stir at 1000-1200 rpm for about 1 hour until uniform, and obtain the coating foaming material, which is recorded as EEC-1# in Table 4, for use in step 5.

[0090] The organosilicon polyether modified epoxy emulsion AQ-SiEEP in this embodiment is the waterborne organosilicon polyether modified epoxy emulsion AQ-SiEEP-1# obtained in step 3 of embodiment 1.

[0091] The accelerator mentioned in this step is an organic urea accelerator, 1,1'-(4-methyl-m-phenylene)bis(3,3-dimethylurea) with CAS number 17526-94-2.

[0092] The foaming agent is a thermally expanding microsphere foaming agent, which can be purchased from NOURYON (551DU40, 461DU20, 051DU40, 920DU20, 920DU40); or MATSUMOTO (F-48D, F-50D, F-65D, MSH-340, MSH-550, F-100MD, F-78KD, F-82D); or SEKISUI (EHM204, EHM302, EM303, EM406, EML101 type thermally expanding microsphere foaming agents).

[0093] Table 4

[0094] (Columns 2-9 of Table 4 are: Step 4, Components and proportions for preparing the coating foam; Columns 10-11 of Table 4 are: EEC obtained in Step 5)

[0095] Example 1 EEC-1# AQ-SiEEP-1# 70 10 The amount of epoxy in AQ-SiEEP multiplied by 0.9 times the active hydrogen equivalent. 1.5 times the weight of the DICY feed. 920DU20 100 120 135 Example 2 EEC-2# AQ-SiEEP-2# 70 10 The amount of epoxy in AQ-SiEEP multiplied by 0.9 times the active hydrogen equivalent. 0.5 times the weight of DICY feed. 920DU40 70 240 115 Example 3 EEC-3# AQ-SiEEP-3# 70 10 The AQ-SiEEP epoxy molar number multiplied by the active hydrogen equivalent is 1.0 times. 0.5 times the weight of DICY feed. 461DU20 95 289 50 Example 4 EEC-4# AQ-SiEEP-2# 60 2 The amount of epoxy in AQ-SiEEP multiplied by 0.9 times the active hydrogen equivalent. 1.5 times the weight of the DICY feed. EMH204 100 100 130 Example 5 EEC-5# AQ-SiEEP-3# 60 8 The AQ-SiEEP epoxy molar number multiplied by the active hydrogen equivalent is 1.0 times. 1.0 times the weight of DICY feed. EHM302 70 300 85 Example 6 EEC-6# AQ-SiEEP-4# 60 8 The amount of epoxy in AQ-SiEEP multiplied by 0.9 times the active hydrogen equivalent. 0.5 times the weight of DICY feed. EML101 75 240 62 Example 7 EEC-7# AQ-SiEEP-4# 50 0 The AQ-SiEEP epoxy molar number multiplied by the active hydrogen equivalent is 1.0 times. 1.0 times the weight of DICY feed. F-65D 70 120 60 Example 8 EEC-8# AQ-SiEEP-2# 70 8 The amount of active hydrogen equivalent is 0.95 times the number of molar epoxy atoms in AQ-SiEEP. 1.0 times the weight of DICY feed. F-78KD 70 100 120 Example 9 EEC-9# AQ-SiEEP-1# 70 10 The AQ-SiEEP epoxy molar number multiplied by the active hydrogen equivalent is 1.0 times. 1.5 times the weight of the DICY feed. F-82D 100 240 140 Example 10 EEC-10# AQ-SiEEP-5# 50 0 The AQ-SiEEP epoxy molar number multiplied by the active hydrogen equivalent is 1.0 times. 1.0 times the weight of DICY feed. MSH-550 50 225 65

[0096] Step 5: Prepare the epoxy expanded core (EEC).

[0097] The coating foam material EEC-1# obtained in step 4 is coated onto release paper using a coating device in the prior art, and then dried to obtain epoxy expanded core material EEC that can be peeled off from the release paper, denoted as EEC-1# in Table 4.

[0098] In this embodiment 1, the preferred coating method is comma coating, but it can also be either reverse roll coating or extrusion coating. The release paper is selected with a basis weight range of 100-150 g / m². 2 Both are acceptable, and the peel strength of the coated surface can be 0.4-0.6N / 25mm.

[0099] Weigh the dried EEC-1# and find its square gram weight to be 120 g / m². 2 .

[0100] To test the expansion ratio of the EEC-1#, the self-made expansion ratio testing device T002 of this invention, such as... Figure 1As shown, a cubic mold has a 6cm×6cm×6cm mold groove in the middle. The hollow part corresponds to a 5.8cm×5.8cm×3cm pressing block that can be pushed in and removed. The pressing block has a handle on top. The testing method is as follows:

[0101] 1. Place the T002 mold and the pressing block on a pneumatic hot press and preheat at 150°C for 25 minutes;

[0102] 2. Cut EEC-1#, take a 60mm×60mm square sample, calculate its volume (the volume before foaming), put it into the test mold, and cover it with the pressure block. The pressure block provides the test pressure of 1 atm by its own weight.

[0103] 3. Foaming temperature 150±5℃, time 20min, then remove the foamed body;

[0104] 4. Measure the dimensions of the foam using vernier calipers;

[0105] 5. Expansion ratio = Volume after foaming / Volume before foaming. The expansion ratio of Example 1 was 135 times, which is recorded in Table 4.

[0106] Step 6: Using the epoxy expanded core material EEC-1# obtained in Step 5, a lightweight water sports board is formed by heat expansion molding (HEM) process.

[0107] In this embodiment, a surfboard (or other sports boards) is selected as the molded product, and the molding is carried out according to the data corresponding to Embodiment 1 in Table 5.

[0108] Table 5

[0109] List of HEM molding examples for surfboards

[0110] Example 3 SURF-1# EEC-3# 0.02 Polyimide foam 140 90 10 100 120 10 Example 1 SURF-2# EEC-1# 0.015 Polyimide foam 140 120 50 140 90 50 Example 9 SURF-3# EEC-9# 0.01 polyurethane foam 120 30 50 100 120 50 Example 8 SURF-4# EEC-8# 0.03 Polyvinyl chloride foam 160 60 10 160 50 10 Example 2 SURF-5# EEC-2# 0.05 Polyvinyl chloride foam 120 90 100 120 100 100 Example 4 SURF-6# EEC-4# 0.025 polyurethane foam 140 120 10 140 90 10

[0111] The specific molding process is as follows:

[0112] STEP 1, Mold preparation and HEM molding of foamed core material:

[0113] Manufacture the foam mold according to the surfboard's design dimensions. Clean the inner cavities of the upper and lower molds, apply release agent, and pre-embed rigid foam connecting plates at the base of the bottom mold, such as... Figure 2 As shown, the rigid foam connecting plate 3 is used to connect the flat rod to the injection-molded hydrofoil channel 5. The material of the rigid foam connecting plate 3 is preferably 0.04-0.05 g / cm³. 3 Polyimide foam. Rigid foam connecting plate 3 has an adhesive coating layer 4 on its outer surface. Based on the foaming mold dimensions, the volume of the foam cavity × the designed core material density is 0.015 g / cm³. 3Calculate the weight of the epoxy expanded core material EEC to be added; weigh the corresponding weight of epoxy expanded core material EEC-1# and put it into the foaming mold, close the mold and lock the mold effectively;

[0114] The aforementioned foaming mold is transferred to the hot press platform. The hot press platform is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at approximately 140°C. The upper and lower hot presses are then closed, and the pressure range of the hot press is 50 kgf / cm². 2 The foaming time is approximately 120 minutes. Open the hot press platform to release pressure. Transfer the mold to the cold press platform, which is pre-connected to a cooling device with sufficient cooling power. Maintain the platform temperature between 0-25℃. Close the upper and lower cold presses. The press pressure range is 50 kgf / cm². 2 The mold is cooled; when the mold temperature drops below 60°C, the cold press platform is opened, the mold is removed, and the mold is opened to obtain the surfboard foam core material 6 of this embodiment 1. Figure 2 As shown in the diagram.

[0115] STEP 2, Preparation of prepreg inclusions:

[0116] The foamed core material 6 obtained in STEP1 was lightly sanded with 150# sandpaper to remove any trace amounts of release agent that might be adhering to the surface. Then, it was cleaned with an air gun. Based on the existing layup structure, several layers of fiber prepreg were wrapped around the surface of the foamed core material to obtain a prepreg enclosure. A structural diagram is shown below. Figure 2 As shown. The fiber prepreg consists of two layers of glass fiber prepreg 2 close to the foamed core material, and an outer layer of 3k carbon fiber prepreg 1. Other layup structures are also possible, depending on the actual product requirements.

[0117] STEP 3: Press molding of surfboard blank:

[0118] The prepreg package is placed into the surfboard molding mold, the mold is closed and locked effectively; it is then transferred to the hot press platform, which is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at approximately 140°C. The upper and lower hot presses are closed, and the press pressure is 50 kgf / cm². 2 Approximately 10-10050 kgf / cm² 2 Either is acceptable. Molding time is 90 minutes. Open the hot press platform to release pressure; transfer the mold to the cold press platform. The cold press platform is pre-connected to a cooling device with sufficient cooling power, maintaining the platform temperature at 0-25℃. Close the upper and lower cold presses. The press pressure range is 50 kgf / cm². 2The mold is cooled down. When the temperature of the mold drops below 60°C, the cold press platen is opened, the mold is removed, the mold is unlocked and opened to obtain a lightweight surfboard blank, denoted as SURF-2#.

[0119] Step 7: Perform fatigue tests, lateral bending tests, and tensile tests on the obtained surfboard blank, as shown in Table 6.

[0120] 1. Fatigue test.

[0121] The surfboard is locked and fixed onto the fatigue testing machine, which has two parallel cylinders. One cylinder holds the surfboard in place, while the other cylinder, located in the middle of the front foot sleeve hole, performs 30,000 reciprocating motions with a set force of 50 kg.

[0122] The test results were satisfactory: after 30,000 fatigue tests, no cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC foam core material.

[0123] 2. Lateral bending resistance test.

[0124] like Figure 3 The diagram shows the lateral bending resistance testing device. A surfboard 7 is fixed to the vertical testing device, and an 850mm long integrated flat rod 9 is fixed to the surfboard's base 8, which is 90mm wide. A 50kg weight 10 is hung on the top of the flat rod. The weight's own weight generates a downward force to test the structural strength of the base. The surfboard base is subjected to bending loads in both directions once.

[0125] The test results were satisfactory: the structure of the base did not show any delamination or breakage between the fiber layer and the internal foam core material.

[0126] 3. Tensile strength test.

[0127] Tools involved: a universal tensile testing machine capable of loading 500kg, and fixing clamps.

[0128] Secure the surfboard to the testing machine by pressing down on both ends near the center with pressure bars, ensuring the front pressure bar is 25cm away from the hydrofoil groove; place the T-nut in the center of the surfboard's base groove and tighten it; use a universal tensile testing machine capable of loading 500kg to stretch the surfboard upwards at a speed of 25mm / min, stopping when the tensile force reaches 500kg, or stopping prematurely if the surfboard breaks down midway.

[0129] The test results were satisfactory: the base structure did not show any delamination or breakage between the fiber layer and the internal foam core material.

[0130] 4. Water absorption test.

[0131] The testing procedure involved manually cutting a 3cm long and 1cm deep incision in the fiber-reinforced outer layer of the surfboard at the very center of the bottom using a blade, penetrating the fiber-reinforced outer layer to the interior of the EEC foam core. The surfboard was then floated on the seawater surface, with the damaged area in complete contact with the seawater. The ambient temperature during the test was 25℃, and the relative humidity was 40%-50%.

[0132] Before the test, the surfboard's weight (g) was recorded as M0. After 12 hours of testing, the surfboard was removed, and the surface seawater was wiped clean until no visible water droplets remained. The surfboard was then weighed and recorded as M. a ; Calculate relative water absorption = M a -M0=30g, record in Table 6. Qualified test result: relative water absorption less than 100g.

[0133] Table 6

[0134] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank.

[0135] Example 3 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 55g Example 1 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 30g Example 9 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 20g Example 8 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 56g Example 2 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 80g Example 4 No cracking or delamination was observed at the interface between the surface fiber composite material and the internal EEC core material after 30,000 fatigue tests. The base structure underwent bending tests in both directions once, and no delamination or breakage was observed between the fiber layer and the internal foam material. No delamination or breakage was observed between the fiber layer and the internal foam material in the base structure. Qualified 25g

[0136] Example 2

[0137] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0138] The components, proportions, and preparation methods are the same as in Example 1.

[0139] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0140] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 2 in Table 2. The resulting organosilicon polyether modified epoxy polymer is denoted as SiEEP-2# in Table 2.

[0141] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0142] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 2 in Table 3. The resulting organosilicon polyether modified epoxy emulsion is denoted as AQ-SiEEP-2# in Table 3.

[0143] Step 4: Prepare the coating material.

[0144] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 2 in Table 4. The resulting coating material corresponds to EEC-2# in Table 4.

[0145] Step 5: Prepare epoxy expanded core material.

[0146] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-2# has a square weight of 240 g / m². 2 Record this in Table 4.

[0147] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-2# was measured to be 115 times, which is also recorded in Table 4.

[0148] Step 6: Using the epoxy expanded core material EEC-2# obtained in Step 5, the surfboard is molded using a thermal expansion molding (HEM) process. The specific process is the same as Step 6 of the embodiment, except that the parameters and components are as shown in Example 2 of Table 5. The obtained surfboard blank is designated SURF-5#.

[0149] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank SURF-5# according to the method and equipment in Step 7 of Example 1. The results are shown in Table 6, which corresponds to the description in Example 2.

[0150] Example 3

[0151] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0152] The components, proportions, and preparation methods are the same as in Example 1.

[0153] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0154] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 3 in Table 2. The resulting organosilicon polyether modified epoxy polymer is denoted as SiEEP-3# in Table 2.

[0155] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0156] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 3 in Table 3. The resulting organosilicon polyether modified epoxy emulsion is denoted as AQ-SiEEP-3# in Table 3.

[0157] Step 4: Prepare the coating material.

[0158] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 3 in Table 4. The resulting coating material corresponds to EEC-3# in Table 4.

[0159] Step 5: Prepare epoxy expanded core material.

[0160] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-3# has a square gram weight of 289 g / m². 2 Record this in Table 4.

[0161] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-3# was measured to be 50 times, and it was also recorded in Table 4.

[0162] Step 6: Using the epoxy expanded core material EEC-3# obtained in Step 5, the surfboard is molded using a thermal expansion molding (HEM) process. The specific process is the same as Step 6 of the embodiment, except that the parameters and components are as shown in Table 5, Example 3. The obtained surfboard blank is designated SURF-1#.

[0163] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank SURF-1# according to the method and equipment in Step 7 of Example 1. The results are shown in Table 6, corresponding to the description in Example 3.

[0164] Example 4

[0165] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0166] The components, proportions, and preparation methods are the same as in Example 1.

[0167] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0168] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 4 of Table 2 (i.e. Example 2). The resulting organosilicon polyether modified epoxy polymer is SiEEP-2# in Table 2.

[0169] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0170] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 4 in Table 3. The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-2# in Table 3.

[0171] Step 4: Prepare the coating material.

[0172] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 4 in Table 4. The resulting coating material corresponds to EEC-4# in Table 4.

[0173] Step 5: Prepare epoxy expanded core material.

[0174] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-4# has a square gram weight of 100 g / m². 2 Record this in Table 4.

[0175] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-4# was measured to be 130 times, and it was also recorded in Table 4.

[0176] Step 6: Using the epoxy expanded core material EEC-4# obtained in Step 5, the surfboard is formed using a thermal expansion molding (HEM) process. The specific process is the same as Step 6 in the example, except that the parameters and components are as shown in Example 4 of Table 5. The obtained surfboard blank is designated SURF-6#.

[0177] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank SURF-6# according to the method and equipment in Step 7 of Example 1. The results are shown in Table 6, corresponding to the description in Example 4.

[0178] Example 5

[0179] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0180] The components, proportions, and preparation methods are the same as in Example 1.

[0181] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0182] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 5 of Table 2 (i.e. Example 3). The resulting organosilicon polyether modified epoxy polymer is SiEEP-3# in Table 2.

[0183] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0184] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 5 of Table 3 (i.e. Example 3). The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-3# in Table 3.

[0185] Step 4: Prepare the coating material.

[0186] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 5 in Table 4. The resulting coating material corresponds to EEC-5# in Table 4.

[0187] Step 5: Prepare epoxy expanded core material.

[0188] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-5# has a square gram weight of 300 g / m². 2 Record this in Table 4.

[0189] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-5# was measured to be 85 times, and it was also recorded in Table 4.

[0190] In this embodiment 5, steps 6 and 7 were not performed. The preparation steps and effects are the same as in other embodiments, and will not be described in detail.

[0191] Example 6

[0192] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0193] The components, proportions, and preparation methods are the same as in Example 1.

[0194] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0195] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 6 in Table 2. The resulting organosilicon polyether modified epoxy polymer is SiEEP-4# in Table 2.

[0196] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0197] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 6 in Table 3 (i.e. Example 7). The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-4# in Table 3.

[0198] Step 4: Prepare the coating material.

[0199] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 6 in Table 4. The resulting coating material corresponds to EEC-6# in Table 4.

[0200] Step 5: Prepare epoxy expanded core material.

[0201] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-6# has a square gram weight of 240 g / m². 2 Record this in Table 4.

[0202] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-5# was measured to be 62 times, which is also recorded in Table 4.

[0203] In this embodiment 6, steps 6 and 7 were not performed. The preparation steps and effects are the same as in other embodiments, and will not be described in detail.

[0204] Example 7

[0205] Steps 1-3 are the same as steps 1-3 in Example 6.

[0206] Step 4: Prepare the coating material.

[0207] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 7 in Table 4. The resulting coating material corresponds to EEC-7# in Table 4.

[0208] Step 5: Prepare epoxy expanded core material.

[0209] The preparation method is the same as in Example 6. After coating and drying, the epoxy expanded core material EEC-7# has a square gram weight of 120 g / m². 2 Record this in Table 4.

[0210] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-5# was measured to be 60 times, and it was also recorded in Table 4.

[0211] In this embodiment 7, steps 6 and 7 were not performed. The preparation steps and effects are the same as in other embodiments, and will not be described in detail.

[0212] Example 8

[0213] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0214] The components, proportions, and preparation methods are the same as in Example 1.

[0215] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0216] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 8 of Table 2 (i.e. Example 2). The resulting organosilicon polyether modified epoxy polymer is SiEEP-2# in Table 2.

[0217] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0218] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 8 of Table 3 (i.e. Example 2). The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-2# in Table 3.

[0219] Step 4: Prepare the coating material.

[0220] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 8 in Table 4. The resulting coating material corresponds to EEC-8# in Table 4.

[0221] Step 5: Prepare epoxy expanded core material.

[0222] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-4# has a square gram weight of 100 g / m². 2 Record this in Table 4.

[0223] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-4# was measured to be 120 times, and it was also recorded in Table 4.

[0224] Step 6: Using the epoxy expanded core material EEC-8# obtained in Step 5, the surfboard is molded using a thermal expansion molding (HEM) process. The specific process is the same as Step 6 in the embodiment, except that the parameters and components are as shown in Table 5, Example 8. The obtained surfboard blank is designated SURF-4#.

[0225] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank SURF-6# according to the method and equipment in Step 7 of Example 1. The results are shown in Table 6, corresponding to the description in Example 8.

[0226] Example 9

[0227] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0228] The components, proportions, and preparation methods are the same as in Example 1.

[0229] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0230] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 9 of Table 2 (i.e. Example 1). The resulting organosilicon polyether modified epoxy polymer is SiEEP-1# in Table 2.

[0231] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0232] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 9 of Table 3 (i.e. Example 1). The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-1# in Table 3.

[0233] Step 4: Prepare the coating material.

[0234] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 9 in Table 4. The resulting coating material corresponds to EEC-9# in Table 4.

[0235] Step 5: Prepare epoxy expanded core material.

[0236] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-9# has a square gram weight of 240 g / m². 2 Record this in Table 4.

[0237] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-4# was measured to be 140 times, and it was also recorded in Table 4.

[0238] Step 6: Using the epoxy expanded core material EEC-9# obtained in Step 5, the surfboard is molded using a thermal expansion molding (HEM) process. The specific process is the same as Step 6 in the embodiment, except that the parameters and components are as shown in Example 9 of Table 5. The obtained surfboard blank is designated SURF-3#.

[0239] Step 7: Perform fatigue testing, lateral bending resistance testing, and tensile testing on the obtained surfboard blank SURF-3# according to the method and equipment in Step 7 of Example 1. The results are shown in Table 6, corresponding to Example 9.

[0240] Example 10

[0241] Step 1: First, prepare the organosilicon-modified epoxy polymer.

[0242] The components, proportions, and preparation methods are the same as in Example 1.

[0243] Step 2: Prepare organosilicon polyether modified epoxy polymer.

[0244] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 10 in Table 2. The resulting organosilicon polyether modified epoxy polymer is SiEEP-5# in Table 2.

[0245] Step 3: Prepare organosilicon polyether modified epoxy emulsion.

[0246] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 10 in Table 3. The resulting organosilicon polyether modified epoxy emulsion is AQ-SiEEP-5# in Table 3.

[0247] Step 4: Prepare the coating material.

[0248] The preparation method is the same as in Example 1, except that the selection and proportion of components are as shown in Example 10 in Table 4, and the resulting coating material corresponds to EEC-10# in Table 4.

[0249] Step 5: Prepare epoxy expanded core material.

[0250] The preparation method is the same as in Example 1. After coating and drying, the epoxy expanded core material EEC-10# has a square gram weight of 225 g / m². 2 Record this in Table 4.

[0251] According to the foaming ratio test method in Example 1, the foaming ratio of EEC-4# was measured to be 65 times, and it was also recorded in Table 4.

[0252] In this embodiment 10, steps 6 and 7 were not performed. The preparation steps and effects are the same as in other embodiments, and will not be described in detail.

Claims

1. A novel lightweight HEM molding material for water sports boards, characterized in that, It is prepared through the following steps: Step 1: Preparation of silicone-modified epoxy polymer: A hydrophobic silicone-modified epoxy polymer, abbreviated as SiEP, is prepared using tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene. Step 2: Prepare the organosilicon polyether modified epoxy polymer, abbreviated as SiEEP, using the following components and proportions: 1) Epoxy resin, abbreviated as EP, 50-80 parts by weight, 2) 5-10 parts by weight of the organosilicon-modified epoxy polymer SiEP obtained in step 1. 3) Epoxy reactive diluent, abbreviated as ED, 5-10 parts by weight. 4) Amino-terminated polyether, abbreviated as PEA, the number of moles of NH bonds in the feed amount is 0.2-0.5 times the number of moles of epoxy groups in the system; Step 3: Add the silicone polyether modified epoxy polymer SiEEP obtained in Step 2 to a solvent, emulsify and dilute to obtain silicone polyether modified epoxy emulsion, abbreviated as AQ-SiEEP; The formula used is: 100 parts by weight of silicone polyether modified epoxy polymer SiEEP obtained in Step 2, 10-20 parts by weight of co-solvent, and 60-100 parts by weight of main solvent. Step 4: Preparation of coating foam material: It is prepared by mixing the following components and proportions: 1) Organosilicon polyether modified epoxy emulsion AQ-SiEEP, 50-70 parts by weight, 2) Water, 0-30 parts by weight 3) The amount of dicyandiamide (DICY) used is 0.9-1.0 times the molar number of epoxy in the organosilicon polyether modified epoxy emulsion AQ-SiEEP, multiplied by the active hydrogen equivalent. 4) Accelerator, the dosage is 0.5-1.5 times the weight of dicyandiamide (DICY) in the feed. 5) Foaming agent, 50-100 parts by weight; Step 5: Preparation of epoxy expandable core material (EEC): The foaming material obtained in Step 4 is coated onto release paper and dried to obtain epoxy expandable core material (EEC) that can be peeled off from the release paper. The expansion ratio of the epoxy expandable core material (EEC) ranges from 50 to 150 times, and the density of the foamed core material obtained after thermal expansion ranges from 0.01 to 0.05 g / cm³. 3 ; In step 1, the molar ratio of tetramethylcyclotetrasiloxane, allyl glycidyl ether, and styrene is 1:2:

2. The preparation process is as follows: In an inert gas-protected reactor, tetramethylcyclotetrasiloxane is added and the temperature is maintained at 80°C. 25% of an allyl glycidyl ether and 25% of a styrene mixture are added while stirring at 500 rpm. Then, 20-60 ppm of platinum catalyst (CAS No. 68478-92-2) is added dropwise. Stirring is maintained at 500 rpm for 10 min. Then, the remaining 75% of an allyl glycidyl ether (AGE) and 75% of a styrene (ST) mixture are added dropwise. The dropwise addition rate is controlled to maintain the system temperature within the range of 80-90°C. After the addition is complete, the reaction is stirred for 4 hours. Then, the temperature is raised to 120°C, and the low-boiling-point solvent is removed under reduced pressure (absolute pressure 10-20 kPa). A transparent liquid is obtained by discharging the product, which is an organosilicon-modified epoxy polymer (SiEP).

2. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, The SiEP obtained in step 1 includes two isomers with the following structural formulas: ， ， ， 。 3. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, In step 2, the epoxy resin is one or any combination of two or more of epoxy resin E-06, epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 and epoxy resin E-51. The epoxy reactive diluent is one or any combination of two or more of the following: benzyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polypropylene glycol diglycidyl ether. The terminal amino polyether is one or any combination of two or more of polypropylene diamine D230, polypropylene diamine D400, ethylene diamine ED600, and ethylene diamine ED900.

4. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, The preparation process in step 2 is as follows: Epoxy resin EP, silicone-modified epoxy polymer SiEP obtained in step 1, and epoxy reactive diluent ED are weighed according to the proportion and added to the reactor. The temperature is maintained at 70°C, and the mixture is stirred and mixed at 300-900 rpm for 2-4 hours. Then, terminal amino polyether PEA is added according to the calculated amount of feed, and the mixture is stirred and mixed at 300-900 rpm for 1-2 hours. The mixture is then left to stand at room temperature for more than 12 hours for later use to obtain silicone polyether-modified epoxy polymer SiEEP.

5. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, The main solvent in step 3 is water; the co-solvent is one or any combination of two or more of isopropanol, ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, and dipropylene glycol butyl ether.

6. The novel lightweight water sports board HEM molding material according to claim 5, characterized in that, The specific procedure for step 3 is as follows: Weigh the organosilicon polyether modified epoxy polymer SiEEP and co-solvent obtained in step 2 according to the ratio, and add them to the emulsification device one after another. Raise the temperature to 80°C, stir at 900-1000 rpm for 0.5 hours until uniform, cool down to 60°C, and add the main solvent dropwise while stirring for 1.5 hours at 3000 rpm. Maintain high speed shear emulsification for 1 hour, and then cool down to 40°C and maintain high speed stirring at 3000 rpm for 1 hour to obtain organosilicon polyether modified epoxy emulsion AQ-SiEEP.

7. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, In step 4, the accelerator is an organic urea accelerator, 1,1'-(4-methyl-m-phenylene)bis(3,3-dimethylurea) with CAS number 17526-94-2.

8. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, In step 4, the foaming agent is a type of thermally expanding microspheres; The foaming agent is selected from NOURYON's 551DU40, 461DU20, 051DU40, 920DU20, and 920DU40; Or Mateuso's F-48D, F-50D, F-65D, MSH-340, MSH-550, F-100MD, F-78KD, and F-82D; Or SEKISUI's EHM204, EHM302, EM303, EM406, and EML101.

9. The novel lightweight water sports board HEM molding material according to claim 1, characterized in that, The epoxy expanded core material EEC coating obtained in step 5 has a weight of 100-300 g / m². 2 .

10. A molding process for manufacturing a novel lightweight water sports board HEM using the lightweight water sports board HEM molding material according to any one of claims 1-9, characterized in that, Includes the following steps: 1) The dimensions of the foaming mold manufactured according to the design dimensions of the water sports board, with the volume of the foam cavity multiplied by the desired core material density of 0.01-0.05 g / cm³. 3 Calculate the weight of epoxy expanded core material (EEC) to be added; weigh the corresponding weight of epoxy expanded core material (EEC) and place it into the foaming mold, close the mold and lock the mold effectively; 2) Transfer the foaming mold to the hot press platen for hot pressing foaming expansion, and then cold press to cool down to obtain the foamed core material of the water sports board; 3) Wrap fiber prepreg around the foamed core material of the water sports board to obtain a prepreg enclosure; 4) The prepreg package is placed into the molding mold of the sports board, hot-pressed on the hot press plate, and then cold-pressed to obtain the rough blank of the water sports board.

11. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, The water absorption capacity of the rough blank of the water sports board is 20g-80g.

12. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, In step 2), the foaming mold is transferred to the hot press platform. The hot press platform is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at 120-160℃. The upper and lower hot presses are then closed, and the pressure range of the hot press is 10-100 kgf / cm². 2 Foaming time: 30-120 min; Open the hot press platform to release pressure; Transfer the mold to the cold press platform, which is pre-connected to a cooling device with sufficient cooling power, maintaining the platform temperature at 0-25℃; Close the upper and lower cold presses, with a press pressure range of 10-100 kgf / cm². 2 The mold is cooled; when the temperature of the mold drops below 60°C, the cold press platform is opened, the mold is removed, and the mold is opened to obtain the foamed core material of the water sports board.

13. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, In step 1), the foaming mold has a rigid foam connecting plate pre-embedded in the base of the lower mold for subsequent connection of the flat rod; the rigid foam connecting plate has a strength of 0.04-0.05 g / cm³. 3 Polyimide foam, or 0.04-0.05 g / cm³ 3 Polyurethane foam, or 0.04-0.05 g / cm³ 3 Polyvinyl chloride foam.

14. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, The specific procedure for step 4) of the water sports board rough molding is as follows: The prepreg package is placed into the molding mold of the sports board, the mold is closed and effectively locked; it is then transferred to a hot press platform, which is pre-connected to a heating device with sufficient heating power to maintain the platform temperature at 100-160℃; the upper and lower hot presses are closed, and the press pressure range is 10-100 kgf / cm². 2 The molding time is 50-120 minutes. Open the hot press platform to release pressure; transfer the mold to the cold press platform, which is pre-connected to a cooling device with sufficient cooling power. Maintain the platform temperature at 0-25℃. Close the upper and lower cold presses. The press pressure range is 10-100 kgf / cm². 2 The mold is cooled down. When the temperature of the mold drops below 60°C, the cold press plate is opened, the mold is removed, the mold is unlocked and opened to obtain a lightweight water sports board blank.

15. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, In step 3), when preparing the prepreg enclosure, the fiber prepreg consists of two layers of glass fiber prepreg close to the foamed core material, and an outer layer of 3k carbon fiber prepreg.

16. The novel lightweight water sports board HEM molding process according to claim 10, characterized in that, When fatigue testing was performed on the rough blank of the water sports board, after 30,000 reciprocating motions at the middle position of the front foot sleeve hole with a set force of 50 kg, the interface between the surface fiber composite material and the internal EEC foam core material remained intact. When the water sports board blank is subjected to the lateral bending test, the water sports board is fixed on a vertical test device, and an 850mm long flat rod (9) is fixed on the base (8). A 50kg weight (10) is hung on the top of the outer end of the flat rod. The weight of the weight is used to load the downward force. The water sports board base is subjected to bending test once in each of the two directions. The fiber layer and the internal foam core material at the base remain intact. When performing tensile tests on the rough blank of the water sports board, the two ends of the water sports board are pressed down near the middle, and a universal tensile testing machine is used to stretch it upward from the groove of the base of the water sports board. The stretching speed is 25mm / min, and the stretching force is stopped when it reaches 500kg. The fiber layer of the base structure and the internal foam core material remain intact.

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