Metal ion coordination toughened liquid acrylate resin and its preparation method
Patent Information
- Application Number
- CN202411947726.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-26
- Publication Date
- 2026-09-22
- Estimated Expiration
- 2044-12-26
AI Technical Summary
[0004]本发明的主要目的在于针对现有丙烯酸酯类树脂韧性差等问题和不足，提供一种金属离子配位增韧的液态丙烯酸酯树脂，可显著提升丙烯酸酯类树脂的耐冲击性能，并兼顾良好的可回收性能，适用性广
[0038]1)本发明首先通过配位反应将金属离子与树脂促进剂进行键合制备金属离子配位促进剂，然后将其引入液态丙烯酸酯树脂的制备体系中，可显著提升所得树脂的综合力学性能；
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional materials technology, specifically relating to a liquid acrylate resin toughened by metal ion coordination and its preparation method. Background Technology
[0002] Liquid acrylic thermoplastic resins, with their excellent mechanical properties, weather resistance, light transmittance, recyclability, and weldability, are widely used in composite materials, 3D printing, optical components, and other fields. With the rapid development of these fields, the demand for liquid acrylic resins has increased significantly, demonstrating enormous market potential.
[0003] However, the toughness of current liquid acrylate resins is generally poor, making them unable to withstand large impact loads and prone to brittle fracture, which seriously hinders their further development and application. Improving the impact resistance of liquid acrylate resins through further design, and ultimately preparing liquid acrylate thermoplastic resins with excellent toughness, is a crucial problem that needs to be solved. Summary of the Invention
[0004] The main objective of this invention is to address the problems and shortcomings of existing acrylate resins, such as poor toughness, by providing a liquid acrylate resin with metal ion coordination toughening, which can significantly improve the impact resistance of acrylate resins while also ensuring good recyclability and wide applicability.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing a metal ion-coordination-toughened liquid acrylate resin includes the following steps:
[0007] 1) Synthesis of metal ion coordination promoters:
[0008] The accelerator was added to an alcohol solvent, followed by the addition of a metal coordination compound. The mixture was then refluxed and stirred until the metal coordination compound was completely dissolved. Peroxide was added and the mixture was heated and stirred to react. After post-treatment, a metal ion coordination accelerator was obtained.
[0009] 2) Preparation of metal ion-coordinated liquid acrylate resin:
[0010] Methyl methacrylate monomer and acrylic monomer are added to a reaction vessel, and the mixture is heated and stirred under a protective atmosphere, then cooled. A metal ion coordination promoter is then added, and the mixture is stirred. An oxygen inhibition agent is then added, and the mixture is stirred until homogeneous and then cooled to room temperature to obtain the metal ion-coordinated toughened liquid acrylate resin.
[0011] In the above scheme, the accelerator can be N,N-dimethylaniline, N,N-diethylaniline, or N,N-dimethyl-p-toluidine, etc.
[0012] In the above scheme, the alcohol solvent can be one or more of ethanol, methanol, ethylene glycol, isopropanol, etc.
[0013] In the above scheme, the solid-liquid ratio of the accelerator to the alcohol solvent is 1g:3-5mL.
[0014] In the above scheme, the metal ligand can be one or more of ferric chloride, ferrous chloride, zinc chloride, copper chloride, chromium chloride, ferric nitrate, zinc nitrate, copper nitrate, and silver nitrate; its addition amount is 0.5 to 5 wt% of the accelerator mass, preferably 1.5 to 2.5 wt%.
[0015] In the above scheme, the temperature for the condensation reflux stirring is 50-80℃, and the time is 15-30min.
[0016] Furthermore, the temperature used for the condensation reflux stirring is 65–75°C.
[0017] In the above scheme, the peroxide can be one or more of benzoyl peroxide, ammonium persulfate, potassium persulfate, etc.; its addition amount is 0.5 to 1.5 wt% of the accelerator mass; preferably 0.8 to 1.2 wt%.
[0018] In the above scheme, the heating and stirring reaction in step 1) is carried out at a temperature of 55-65°C for 2-6 hours.
[0019] In the above scheme, the post-processing includes: dilution with water, filtration to obtain precipitate, and vacuum drying.
[0020] In the above scheme, the solid-liquid ratio of the accelerator introduced in step 1) to water is 1g:15-25mL.
[0021] In the above scheme, the vacuum drying is carried out at a temperature of 55-65℃, a vacuum degree of -0.06--0.1MPa, and a time of 8-12h.
[0022] In the above scheme, the acrylic monomer can be one or more of acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, etc., and its amount is 10 to 25 wt% of the mass of methyl methacrylate monomer; preferably 14 to 16 wt%.
[0023] In the above scheme, the heating and stirring treatment in step 2) is carried out at a temperature of 70-90℃ for 2-4 hours, and then cooled to 35-45℃; preferably, it is stirred at 75-85℃ for 2.5-3.5 hours.
[0024] In the above scheme, the amount of the metal ion coordination promoter is 0.1 to 1 wt% of the mass of methyl methacrylate monomer, preferably 0.4 to 0.6 wt%.
[0025] In the above scheme, the 30-60 min mentioned in step 2) is preferably 35-45 min.
[0026] In the above scheme, the oxygen inhibition agent can be one or more of pentaerythritol tetrakis(3-mercaptopropionic acid), p-hydroxyanisole, methyl hydroquinone, etc.; its amount accounts for 0.1 to 0.4 wt% of the mass of methyl methacrylate monomer, preferably 0.25 to 0.35 wt%.
[0027] The present invention also provides a curing and molding method for the above-mentioned metal ion-coordinated toughened liquid acrylate resin and its composite material, comprising the following steps: adding an initiator to the obtained metal ion-coordinated liquid acrylate resin, stirring at room temperature, degassing under vacuum, then casting or combining it with fiber-reinforced materials, curing at room temperature to obtain the corresponding resin molded specimen or fiber-reinforced thermoplastic composite material.
[0028] In the above scheme, the initiator can be benzoyl peroxide or the like; its amount accounts for 0.2 to 0.4% of the mass of the metal ion coordinated liquid acrylate resin.
[0029] In the above scheme, the room temperature stirring time is 10 to 30 minutes.
[0030] In the above scheme, the vacuum degree used for vacuum degassing is -0.06 to -0.08 MPa, and the degassing time is 5 to 10 minutes.
[0031] In the above scheme, the room temperature curing time is 6 to 8 hours.
[0032] Furthermore, the fiber-reinforcing material is 1 to 2 times the mass of the metal ion-coordinated toughened liquid acrylate resin.
[0033] The present invention also provides a method for recycling the above-mentioned resin molded specimens or fiber-reinforced thermoplastic composite materials, comprising the following steps: dissolving the obtained resin molded specimens or fiber-reinforced thermoplastic composite materials in an organic solvent (acetone, etc.), separating the fibers from the matrix resin by filtration or centrifugation after complete dissolution, cleaning the fiber surface with pure solvent or water, recycling and surface treating it for use in the production of new composite materials; precipitating the thermoplastic resin components in the solution by means of evaporation, precipitation or heating and purifying them to obtain regenerated thermoplastic resin materials, which can be regranulated and processed.
[0034] The fibers recovered using the above method avoid thermal degradation or mechanical damage, ensuring the high strength properties of the reinforcing fibers. Furthermore, the matrix resin, selectively dissolved by solvents, has high purity, effectively guaranteeing its performance.
[0035] The principle of this invention is as follows:
[0036] This invention first bonds metal ions to a resin accelerator through a coordination reaction, and then introduces the resulting metal ion-accelerator coordination system into the polymerization reaction of liquid acrylate resin. This can effectively promote the establishment of coordination crosslinks between resin molecular chains, improve intermolecular forces, form crosslinking between polyacrylate macromolecules, significantly improve the toughness of the resulting resin products, and enhance their impact resistance; at the same time, it can ensure good recyclability.
[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0038] 1) This invention first prepares a metal ion coordination accelerator by bonding metal ions with a resin accelerator through a coordination reaction, and then introduces it into the preparation system of liquid acrylate resin, which can significantly improve the comprehensive mechanical properties of the obtained resin.
[0039] 2) The metal ion coordination promoter described in this invention can effectively increase the cross-linking effect between acrylate resin molecules, effectively inhibit the occurrence of side reactions, simultaneously improve the compression performance and impact resistance of the obtained resin products, and ensure good recyclability.
[0040] 3) The preparation method involved in this invention is relatively simple and the reaction conditions are relatively mild, making it suitable for widespread application and applicable to fields such as aerospace, automobiles, and marine vessels. Attached Figure Description
[0041] Figure 1 a) is a conventional liquid acrylate resin obtained in Comparative Example 1, and b) is a morphology diagram of the metal ion coordinated liquid acrylate resin obtained in Example 1.
[0042] Figure 2 The infrared spectra of the metal ion coordinated liquid acrylate resin obtained in Example 1 and the conventional liquid acrylate resin obtained in Comparative Example 1 are shown.
[0043] Figure 3 The compressive strength and impact toughness test results are for the metal ion coordinated liquid acrylate resin obtained in Example 1, the conventional liquid acrylate resin obtained in Comparative Example 1, and the iron coordinated liquid acrylate resin obtained in Comparative Example 2.
[0044] Figure 4 This is a photograph of the chemical recovery of the metal ion-coordinated liquid acrylate resin obtained in Example 1. Detailed Implementation
[0045] The applicant will now provide a more detailed description of the present invention with reference to specific embodiments, so that those skilled in the art can more clearly understand the present invention. However, the following content should not be construed as limiting the scope of protection claimed in the claims of the present invention.
[0046] All chemical reagents and solvents used in the examples were of analytical grade. The stirring was performed using a magnetic stirrer.
[0047] In the following embodiments, the preparation method of the metal ion-coordination-toughened liquid acrylate resin includes the following steps:
[0048] 1) Synthesis of metal ion coordination promoters;
[0049] 100g of accelerator (N,N-dimethylaniline) was added to a reagent bottle containing 500mL of ethanol, followed by the addition of a metal coordination compound with a accelerator content of 0.5-5wt%. The mixture was refluxed and stirred at 50-80℃. After the metal coordination compound was completely dissolved, a peroxide with a accelerator content of 0.5-1.5wt% was added, and the mixture was stirred and reacted at 60℃ for 2-6 hours. 1500-2500mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was then dried in a vacuum drying oven at 55-65℃ under a vacuum of -0.06 to -0.1MPa for 8-12 hours to obtain the metal ion coordination accelerator.
[0050] 2) Preparation of metal ion-coordinated liquid acrylate resin;
[0051] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 10-25wt% of acrylic monomer. Nitrogen atmosphere was introduced, and the mixture was stirred at 70-90℃ for 2-4 hours. The temperature was then lowered to 35-45℃, and 0.1-1wt% of metal ion coordination promoter was added. The mixture was stirred for 30-60 minutes, and 0.1-0.4wt% of oxygen inhibition agent was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain a metal ion coordinated liquid acrylate resin.
[0052] 3) Curing and molding of metal ion-coordinated liquid acrylate resins and their composites;
[0053] Add 0.2-0.4 wt% benzoyl peroxide to the liquid resin obtained in step two, stir at room temperature for 10-30 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.06 to -0.08 MPa, maintain for 5-10 min to remove air bubbles in the resin, then pour it into a mold or combine it with fiber-reinforced materials, place it at room temperature to cure for 6-8 h, and demold to obtain a resin casting or fiber-reinforced thermoplastic composite material.
[0054] Further, the metal ligand added in step 1) is one or a mixture of several of the following: ferric chloride, ferrous chloride, zinc chloride, copper chloride, chromium chloride, ferric nitrate, zinc nitrate, copper nitrate, and silver nitrate, and the amount added is 2 wt% of the accelerator.
[0055] Furthermore, in step 1), the mixture is refluxed and stirred at 70°C.
[0056] Further, the peroxide added in step 1) is one or a mixture of several of benzoyl peroxide, ammonium persulfate, and potassium persulfate; the amount added is 1 wt% of the accelerator content. Other aspects are the same as in any one of specific embodiments one to three.
[0057] Further, in step 1), the reaction is stirred at 60°C for 4 hours, and then 2000 mL of deionized water is added.
[0058] Furthermore, in step 1), a vacuum of -0.08 MPa is applied in a vacuum drying oven at 60°C.
[0059] Furthermore, the acrylic monomer added in step 2) is one or a mixture of several of acrylic acid, methacrylic acid, methyl acrylate, and butyl acrylate, and the amount added accounts for 15 wt% of the monomer content.
[0060] Furthermore, in step 2), the mixture is stirred at 80°C for 3 hours.
[0061] Further, in step 2), add 0.5 wt% of metal ion coordination promoter and continue stirring for 40 min.
[0062] Further, in step 2), an oxygen inhibitor with a monomer content of 0.3 wt% is added. The oxygen inhibitor is one or a mixture of several of pentaerythritol tetrakis(3-mercaptopropionic acid), p-hydroxyanisole, and methyl hydroquinone.
[0063] Further, in step 3), the amount of benzoyl peroxide added is 0.3 wt%, and the mixture is stirred at room temperature for 20 min.
[0064] Further, in step 3), the vacuum gauge pressure is evacuated to -0.07 MPa and maintained for 8 minutes to remove air bubbles from the resin.
[0065] Furthermore, in step 3), the mixture is placed at room temperature for curing for 7 hours.
[0066] Specific embodiments include the following:
[0067] Example 1
[0068] A liquid acrylate resin with metal ion coordination toughening is prepared by the following steps:
[0069] 1) Synthesis of metal ion coordination promoters;
[0070] 100g of accelerator (N,N-dimethylaniline) was added to a reagent bottle containing 500mL of ethanol, followed by 2wt% ferric chloride. The mixture was refluxed and stirred at 70°C. After the ferric chloride was completely dissolved, 1wt% benzoyl peroxide was added, and the mixture was stirred and reacted at 60°C for 4 hours. 2000mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was dried in a vacuum drying oven (-0.08MPa) at 60°C for 10 hours to obtain the ferric ion coordination accelerator.
[0071] 2) Preparation of metal ion-coordinated liquid acrylate resin;
[0072] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 15wt% acrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The temperature was lowered to 40°C, and 0.5wt% iron ion coordination accelerator monomer was added. The mixture was stirred for another 40 minutes, and then 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain iron ion coordinated liquid acrylate resin.
[0073] 3) Curing and molding of metal ion-coordinated liquid acrylate resin;
[0074] Add 0.3 wt% benzoyl peroxide to the obtained iron ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then pour it into a mold, place it at room temperature to cure for 7 h, and demold to obtain the resin casting.
[0075] Example 2
[0076] A liquid acrylate resin with metal ion coordination toughening is prepared by the following steps:
[0077] 1) Synthesis of metal ion coordination promoters;
[0078] 100g of accelerator (N,N-dimethylaniline) was added to a reagent bottle containing 500mL of ethanol, followed by 2wt% copper chloride. The mixture was refluxed and stirred at 70°C. After the copper chloride was completely dissolved, 1wt% benzoyl peroxide was added, and the mixture was stirred and reacted at 60°C for 4 hours. 2000mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was dried in a vacuum drying oven (-0.08MPa) at 60°C for 10 hours to obtain a copper ion coordination accelerator.
[0079] 2) Preparation of metal ion-coordinated liquid acrylate resin:
[0080] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 15wt% acrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The temperature was lowered to 40°C, and 0.5wt% copper ion coordination accelerator monomer was added. The mixture was stirred for another 40 minutes, and then 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain copper ion coordinated liquid acrylate resin.
[0081] 3) Curing and molding of metal ion-coordinated liquid acrylate resins and their composites:
[0082] Add 0.3 wt% of benzoyl peroxide to the obtained copper ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then combine it with fiber-reinforced material, place it at room temperature for 7 h to cure, and demold to obtain fiber-reinforced thermoplastic composite material.
[0083] Example 3
[0084] A liquid acrylate resin with metal ion coordination toughening is prepared by the following steps:
[0085] 1) Synthesis of metal ion coordination promoters;
[0086] 100g of accelerator (N,N-dimethylaniline) was added to a reagent bottle containing 500mL of ethanol, followed by zinc chloride with an accelerator content of 2wt%. The mixture was refluxed and stirred at 70°C. After the zinc chloride was completely dissolved, benzoyl peroxide with an accelerator content of 1wt% was added, and the mixture was stirred and reacted at 60°C for 4 hours. 2000mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was dried in a vacuum drying oven (-0.08MPa) at 60°C for 10 hours to obtain the zinc ion coordination accelerator.
[0087] 2) Preparation of metal ion-coordinated liquid acrylate resin;
[0088] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 15wt% acrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The temperature was lowered to 40°C, and 0.5wt% zinc ion coordination promoter was added. The mixture was stirred for another 40 minutes, followed by 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer. After stirring until homogeneous, the mixture was cooled to room temperature to obtain zinc ion coordinated liquid acrylate resin.
[0089] 3) Curing and molding of metal ion-coordinated liquid acrylate resin;
[0090] Add 0.3 wt% of benzoyl peroxide to the obtained zinc ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then pour it into a mold, place it at room temperature to cure for 7 h, and demold to obtain the resin casting.
[0091] Example 4
[0092] A liquid acrylate resin with metal ion coordination toughening is prepared by the following steps:
[0093] 1) Synthesis of metal ion coordination promoters;
[0094] 100g of accelerator N,N-dimethylaniline was added to a reagent bottle containing 500mL of ethanol, followed by ferric chloride (2wt% accelerator content). The mixture was refluxed and stirred at 70°C. After the ferric chloride was completely dissolved, ammonium persulfate (1wt% accelerator content) was added, and the mixture was stirred and reacted at 60°C for 6 hours. 2000mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was dried in a vacuum drying oven (-0.08MPa) at 60°C for 10 hours to obtain the ferric ion coordination accelerator.
[0095] 2) Preparation of metal ion-coordinated liquid acrylate resin;
[0096] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 15wt% acrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The temperature was lowered to 40°C, and 0.5wt% iron ion coordination accelerator monomer was added. The mixture was stirred for another 40 minutes, and then 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain iron ion coordinated liquid acrylate resin.
[0097] 3) Curing and molding of metal ion-coordinated liquid acrylate resins and their composites;
[0098] Add 0.3 wt% benzoyl peroxide to the obtained iron ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then combine it with fiber-reinforced material, place it at room temperature for 7 h to cure, and demold to obtain fiber-reinforced thermoplastic composite material.
[0099] Example 5
[0100] A liquid acrylate resin with metal ion coordination toughening is prepared by the following steps:
[0101] 1) Synthesis of metal ion coordination promoters;
[0102] 100g of accelerator (N,N-dimethylaniline) was added to a reagent bottle containing 500mL of ethanol, followed by 2wt% ferric chloride. The mixture was refluxed and stirred at 70°C. After the ferric chloride was completely dissolved, 1wt% ammonium persulfate was added, and the mixture was stirred and reacted at 60°C for 6 hours. 2000mL of deionized water was added, and the mixture was filtered to obtain a precipitate. The precipitate was dried in a vacuum drying oven (-0.08MPa) at 60°C for 10 hours to obtain the ferric ion coordination accelerator.
[0103] 2) Preparation of metal ion-coordinated liquid acrylate resin;
[0104] 100g of methyl methacrylate monomer was added to a three-necked flask, followed by 15wt% methacrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The mixture was then cooled to 40°C, and 0.5wt% iron ion coordination promoter monomer was added. The mixture was stirred for another 40 minutes, and 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain iron ion coordinated liquid acrylate resin.
[0105] 3) Curing and molding of metal ion-coordinated liquid acrylate resin;
[0106] Add 0.3 wt% benzoyl peroxide to the obtained iron ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then pour it into a mold, place it at room temperature to cure for 7 h, and demold to obtain the resin casting.
[0107] Comparative Example 1
[0108] A conventional liquid acrylate resin is prepared in a manner largely the same as in Example 1, except that a conventional N,N-dimethylaniline accelerator is used instead of the iron ion coordination accelerator, and the amount added is 0.5 wt% of the monomer content.
[0109] Comparative Example 2
[0110] A liquid acrylate resin with iron coordination is prepared by the following steps:
[0111] 1) Preparation of metal ion-coordinated liquid acrylate resin;
[0112] 100g of methyl methacrylate monomer was added to a three-necked flask, along with 15wt% acrylic acid monomer. The mixture was then purged with nitrogen and stirred at 80°C for 3 hours. The temperature was lowered to 40°C, and 0.01wt% ferric chloride monomer and 0.5wt% N,N-dimethylaniline monomer were added. The mixture was stirred for another 40 minutes, and then 0.3wt% pentaerythritol tetrakis(3-mercaptopropionic acid) monomer was added. After stirring until homogeneous, the mixture was cooled to room temperature to obtain an iron-coordinated liquid acrylate resin.
[0113] 2) Curing and molding of metal ion-coordinated liquid acrylate resin;
[0114] Add 0.3 wt% benzoyl peroxide to the obtained iron ion coordinated liquid acrylate resin, stir at room temperature for 20 min, place it in a vacuum device, evacuate to a vacuum gauge pressure of -0.07 MPa, maintain for 8 min to remove air bubbles in the resin, then pour it into a mold, place it at room temperature to cure for 7 h, and demold to obtain the resin casting.
[0115] The morphology images of the metal ion-coordinated liquid acrylate resin obtained in Example 1 of this invention and the traditional liquid acrylate resin are shown below. Figure 1 As shown, by Figure 1 It can be seen that both traditional liquid acrylate resins and metal ion-coordinated liquid acrylate resins can cure normally. Traditional liquid acrylate resins turn pale yellow after curing, while metal ion-coordinated liquid acrylate resins, due to Fe... 3+ The presence of the metal ion coordination accelerator results in a purple color after curing. The cured resin surface is smooth with no obvious defects, indicating that good curing of the resin can still be achieved after adding the metal ion coordination accelerator.
[0116] The infrared spectra of the metal ion-coordinated liquid acrylate resin obtained in Example 1 of this invention and the traditional liquid acrylate resin are as follows: Figure 2 As shown, by Figure 2 It can be seen that the infrared spectrum of the metal ion-coordinated liquid acrylate resin in Example 1 shows a value of 693 cm⁻¹. -1 The new absorption peak is the Fe-N coordination bond absorption peak, indicating that the metal ion and the promoter have been successfully coordinated.
[0117] The compressive strength and impact toughness of the metal ion-coordinated liquid acrylate resin obtained in Example 1, the conventional liquid acrylate resin obtained in Comparative Example 1, and the iron-coordinated liquid acrylate resin obtained in Comparative Example 2 are as follows: Figure 3 As shown, by Figure 3As can be seen, in Example 1, the metal ion-coordinated liquid acrylate resin showed a 30% increase in compressive strength and a 32% increase in impact toughness compared to the traditional liquid acrylate resin, indicating a significant improvement in strength and toughness. In Comparative Example 2, the metal ion-coordinated liquid acrylate resin prepared by directly introducing metal chlorides showed a 30% decrease in compressive strength and a 6% increase in impact toughness compared to the traditional liquid acrylate resin, indicating a decrease in the overall mechanical properties of the resin when metal chlorides are directly used for coordination.
[0118] A photograph of the chemical recovery of the metal ion-coordinated liquid acrylate resin obtained in Example 1 of this invention is shown below. Figure 4 As shown, by Figure 4 It can be seen that the metal ion coordinated liquid acrylate resin in Example 1 can be completely dissolved after adding an appropriate amount of organic solvent (e.g., acetone), indicating that the metal ion coordinated liquid acrylate resin can be chemically recycled and reused through solvent method.
[0119] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0120] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.
[0121] This invention is not limited to the embodiments described above. Those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications are also considered within the scope of protection of this invention. Contents not described in detail in this specification are prior art known to those skilled in the art.
Claims
1. A method for preparing a metal ion-coordinated toughened liquid acrylate resin, characterized in that, Includes the following steps: 1) Synthesis of metal ion coordination promoters: The accelerator was added to an alcohol solvent, followed by the addition of a metal coordination compound. The mixture was then refluxed and stirred until the metal coordination compound was completely dissolved. Peroxide was added and the mixture was heated and stirred to react. After post-treatment, a metal ion coordination accelerator was obtained. 2) Preparation of metal ion-coordinated liquid acrylate resin: Methyl methacrylate monomer and acrylic monomer are added to a reaction vessel, and the mixture is heated and stirred under a protective atmosphere, then cooled. A metal ion coordination promoter is then added and stirred, followed by the addition of an oxygen inhibition agent and stirring until homogeneous, to obtain the metal ion-coordinated toughened liquid acrylate resin. The accelerator is N,N-dimethylaniline, N,N-diethylaniline, or N,N-dimethyl-p-toluidine; The metal coordination compound is one or more of ferric chloride, zinc chloride, copper chloride, chromium chloride, ferric nitrate, zinc nitrate, and copper nitrate; its addition amount is 0.5~5 wt% of the accelerator mass. The peroxide is one or more of benzoyl peroxide, ammonium persulfate, and potassium persulfate; Step 1) The heating and stirring process is carried out at a temperature of 55~65℃ for 2~6 hours. The amount of the metal ion coordination promoter is 0.1 to 1 wt% of the mass of methyl methacrylate monomer.
2. The preparation method according to claim 1, characterized in that, The amount of peroxide added is 0.5 to 1.5 wt% of the accelerator mass.
3. The preparation method according to claim 1, characterized in that, The acrylic monomer is one or more of acrylic acid and methacrylic acid, and its amount is 10 to 25 wt% of the mass of methyl methacrylate monomer.
4. The preparation method according to claim 1, characterized in that, Step 2) The heating and stirring process is carried out at a temperature of 70~90℃ for 2~4 hours.
5. A method for curing and molding the metal ion-coordinated toughened liquid acrylate resin according to any one of claims 1 to 4, characterized in that, The process includes the following steps: adding an initiator to the obtained metal ion-coordinated liquid acrylate resin, stirring at room temperature, degassing under vacuum, then casting or combining it with fiber-reinforced materials, curing at room temperature to obtain the corresponding resin molded specimens or fiber-reinforced thermoplastic composite materials.
6. A method for recycling molded specimens obtained from the curing and molding method of the metal ion-coordination toughened liquid acrylate resin according to claim 5, characterized in that: The obtained molded specimens are dissolved in an organic solvent, and then the thermoplastic matrix in the solution is precipitated by evaporation, precipitation or heating and purified to obtain regenerated thermoplastic resin material.