Environment-friendly plastic-wood composite material based on modification of marine plastic garbage and wood flour and preparation method of environment-friendly plastic-wood composite material
By leveraging the synergistic effect of modified compatibilizers and solutions, the problem of poor interfacial bonding between plastics and wood flour was solved, forming a hydrophobic structure that improved the water resistance and mechanical properties of wood-plastic composites, thus expanding their application range.
Patent Information
- Application Number
- CN202610550864.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-24
- Publication Date
- 2026-05-26
AI Technical Summary
In traditional wood-plastic composites, the poor interfacial bonding between plastic and wood flour leads to insufficient mechanical properties and structural stability. The hydrophilicity of wood flour causes the material to absorb water, swell, and deform in size, limiting its application range.
By employing the synergistic effect of modified compatibilizers and modified solutions, the interfacial compatibility is improved through the preparation of nano-silica, functionalized MAPE, and modified solutions, and a hydrophobic protective structure is formed inside the material, combined with marine plastics, wood flour, and flame-retardant fillers.
It significantly improves the interfacial compatibility between plastics and wood flour, enhances the water resistance and mechanical properties of the material, expands its application range to outdoor and humid environments, and meets the requirements of landscaping, outdoor building materials and other applications.
Smart Images
Figure CN122080663A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of environmentally friendly materials technology, specifically to an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification, and its preparation method. Background Technology
[0002] The technological development of wood-plastic composite materials began in the late 1990s. The domestic industry has experienced a phased leap from technology introduction and scale expansion to innovation-driven development. Early technologies mainly involved simple blending and extrusion of plastics such as polyethylene (PE) and polypropylene (PP) with wood flour, resulting in limited product performance and applications only in non-structural scenarios such as garden landscapes. After 2010, with the introduction of advanced equipment such as twin-screw extruders and the initial application of coupling agents and compatibilizers, the industry began to achieve breakthroughs in formula optimization and surface treatment technologies. Functional modification technologies such as flame retardancy and UV resistance gradually matured, and product categories extended to interior wall panels, logistics pallets, and so on.
[0003] Traditional compatibilizers are mostly commercial products such as MAPE (maleic anhydride-grafted polyethylene), which have limited modification effects, resulting in interfacial defects in the composite material. Wood fibers are prone to agglomeration, and stress cannot be effectively transferred, thus affecting the mechanical properties and structural stability of the material. The surface of wood fibers is rich in polar hydroxyl functional groups and has strong hydrophilicity, while the plastic matrix such as polyethylene and high-density polyethylene is a non-polar hydrophobic material. The large difference in polarity between the two makes it difficult to form a good interfacial bond. Therefore, in response to the problems mentioned above, this invention proposes an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification and its preparation method. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification, and its preparation method, in order to solve the problems mentioned in the background art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification includes the following steps: S1. Mix 50-65 parts of recycled marine plastic, 4-5 parts of high-toughness polyester resin, 8-10 parts of modified compatibilizer, 14-18 parts of wood flour, 4-8 parts of flame-retardant filler, 0.5-0.8 parts of coupling agent, and 3-4 parts of lubricant for 5-10 minutes to obtain a mixture. S2. Extruding and granulating the mixture to obtain wood-plastic composite particles, and hot-pressing the wood-plastic composite particles at 170-180℃ and 10-15MPa for 7-9 minutes to obtain environmentally friendly wood-plastic composite material. The modified compatibilizer is prepared through the following steps: S11. Add nano-silica to anhydrous ethanol, ultrasonically disperse for 30-36 min, add silane coupling agent, react at 60-70℃ for 3-4 h, add butyl acetate and disperse for 30-40 min, then add hyperbranched polyester and dibutyltin dilaurate, react at 80-86℃ for 4-5 h with stirring, after the reaction is completed, centrifuge to separate the precipitate, wash the precipitate 2-3 times with butyl acetate, and vacuum dry to obtain modified nano-silica; S12. Add MAPE to xylene, heat to 110-120℃, stir, then add benzophenone, N-hydroxymethylacrylamide and glycidyl methacrylate, irradiate with ultraviolet light under nitrogen protection for 4-5 hours, add BPO and triethylamine, continue stirring at constant temperature for 1-2 hours to obtain functionalized MAPE solution. S13. Add the modified solution to the functionalized MAPE solution and mix, then add the modified nano-silica. Heat to 120-130℃ and stir for 4-5 hours to obtain the reaction solution. Pour the reaction solution into excess anhydrous ethanol to precipitate the precipitate. Filter and collect the precipitate for purification. Vacuum dry the purified precipitate to obtain the modified compatibilizer.
[0006] Furthermore, the modified solution in step S13 is prepared through the following steps: S131. Stir and mix butyl acetate and anhydrous diethyl ether, keep warm at 40-50℃ under nitrogen protection for 5-10 min, add p-dodecylbenzaldehyde and stir to dissolve, then add sodium borohydride in portions, continue stirring and reacting for 3-4 h, let stand to separate the layers, and take the upper organic phase A. S132. Heat organic phase A to 65-75℃, add polyoxyethylene monomethyl ether, stir and mix, then add concentrated sulfuric acid dropwise to adjust the pH to 2-3, then add triethylamine, stir and react at a constant temperature for 4-5 hours, then cool to room temperature, add saturated sodium carbonate solution, stir and neutralize the pH to 7-8, let stand and separate into layers, and take the upper organic phase B. S133. Organic phase B is subjected to vacuum distillation. After adsorption and drying with anhydrous magnesium sulfate for 2-3 hours, unreacted low-boiling-point reagents are distilled off at 70-75℃. The temperature is then raised to 120-125℃ to collect the fraction. The fraction is recrystallized with petroleum ether at 70-80℃, filtered, and then subjected to vacuum distillation again to obtain the modified solution.
[0007] Furthermore, in step S11, the mass ratio of nano-silica, anhydrous ethanol, silane coupling agent, butyl acetate, hyperbranched polyester and dibutyltin dilaurate is 100:(800-1200):(15-20):(1100-1300):(50-60):(1-2).
[0008] Furthermore, in step S12, the mass ratio of MAPE, xylene, benzophenone, N-hydroxymethylacrylamide, glycidyl methacrylate, BPO and triethylamine is 100:(700-800):(8-10):(30-40):(20-25):(3-5):(1-2).
[0009] Furthermore, in step S13, the mass ratio of functionalized MAPE, modified solution, and modified nano-silica is 100:(300-400):(15-25).
[0010] Furthermore, in step S131, the mass ratio of butyl acetate, anhydrous diethyl ether, p-dodecylbenzaldehyde, and sodium borohydride is 100:(30-40):(8-10):(2-2.5).
[0011] Furthermore, in step S132, the mass ratio of organic phase A, polyoxyethylene monomethyl ether, and triethylamine is 100:(12-15):(1-1.2).
[0012] Furthermore, in step S133, the mass ratio of organic phase B, anhydrous magnesium sulfate, and petroleum ether is 100:(3-5):(80-100).
[0013] Furthermore, the wood flour is one or more of sawdust, shavings, bamboo powder and rice husk powder, with a mesh size of 40-80 mesh and a moisture content of ≤2%, and is used after drying. The recycled marine plastic is mainly composed of high-density polyethylene and polyethylene, and is used after sorting, washing, drying and crushing.
[0014] Furthermore, the environmentally friendly wood-plastic composite material is prepared according to any one of the preparation methods described above.
[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention utilizes the synergistic effect of modified compatibilizers and modified solutions to enable the modified compatibilizers to simultaneously possess the ability to bind with components of different properties, such as marine plastics, wood flour, and flame-retardant fillers. This effectively improves the inherent poor interfacial compatibility between plastics and wood flour, allowing inorganic fillers, wood components, and plastic substrates to bond tightly together. This avoids the problem of loose internal structure caused by uneven component dispersion and weak interfacial bonding in traditional wood-plastic composite materials. 2. The modification process of this invention improves the interfacial bonding while forming a hydrophobic protective structure inside the material, effectively blocking water penetration. This solves the problems of water absorption, swelling, and dimensional deformation caused by the hydrophilicity of wood flour, significantly improving the water resistance and environmental adaptability of the material. This allows it to be used in various environments such as outdoor damp and water-adjacent areas. In addition, the tight bonding of each component ensures the mechanical properties of the material, meeting the strength requirements of different scenarios such as garden landscapes, outdoor building materials, and municipal facilities, thus expanding the application range of wood-plastic composite materials. Attached Figure Description
[0016] Figure 1 This is a schematic diagram of the preparation process of the environmentally friendly wood-plastic composite material in this invention; Figure 2 This is a schematic diagram of the preparation process of the modified compatibilizer in this invention; Figure 3 This is a schematic diagram of the preparation process of the modified solution in this invention. Detailed Implementation
[0017] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0018] Please see Figures 1-3 The present invention provides a technical solution: Example 1: A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification includes the following steps: I. Preparation of the modified solution: S131: Add 100g of butyl acetate and 30g of anhydrous diethyl ether to a four-necked flask, mix with magnetic stirring, keep warm at 40℃ under nitrogen protection for 5min, add 8g of p-dodecylbenzaldehyde and stir until completely dissolved, add 2g of sodium borohydride in 3 portions, continue stirring and react for 3h, let stand to separate the layers, and take the upper organic phase A.
[0019] S132: Heat organic phase A to 65℃, add 12g of polyoxyethylene monomethyl ether to every 100g of organic phase A and stir to mix, add concentrated sulfuric acid to adjust the pH to 2, add 1g of triethylamine, stir and react at a constant temperature for 4h, cool to room temperature, add saturated sodium carbonate solution and stir to neutralize to pH=7, let stand to separate the layers, and take the upper organic phase B.
[0020] S133: Add organic phase B to a vacuum distillation apparatus, add 3g of anhydrous magnesium sulfate to every 100g of organic phase B for adsorption and drying for 2h, distill off unreacted low-boiling point reagents at 70℃ and -0.08MPa, collect the fraction by heating to 120℃, recrystallize the fraction with 80g of petroleum ether at 70℃, filter and distill again under vacuum to obtain the modified solution.
[0021] II. Preparation of modified compatibilizers: S11: Add 100g of nano-silica and 800g of anhydrous ethanol to a reaction flask, sonicate for 30min, add 15g of silane coupling agent (KH-570), stir at 60℃ for 3h, add 1100g of butyl acetate, sonicate for 30min, then add 50g of hyperbranched polyester and 1g of dibutyltin dilaurate, stir at 80℃ and 500rpm for 4h, after the reaction is completed, centrifuge to separate the precipitate, wash twice with butyl acetate, and vacuum dry at 80℃ for 6h to obtain modified nano-silica.
[0022] S12: Add 100g MAPE and 700g xylene to a reaction flask, heat to 110℃ and stir until completely dissolved, add 8g benzophenone, 30g N-hydroxymethylacrylamide and 20g glycidyl methacrylate, irradiate with 365nm ultraviolet light for 4h under nitrogen protection, add 3g BPO and 1g triethylamine, and continue stirring at a constant temperature for 1h to obtain a functionalized MAPE solution.
[0023] S13: Add 300g of modified solution to every 100g of functionalized MAPE solution and stir to mix. Then add 15g of modified nano-silica, heat to 120℃ and stir at 500rpm for 4h. Slowly pour the reaction solution into excess anhydrous ethanol to precipitate the precipitate. Filter and collect the precipitate. After Soxhlet extraction and purification, dry under vacuum at 80℃ for 6h to obtain the modified compatibilizer.
[0024] III. Preparation of environmentally friendly wood-plastic composite materials: S1: Take 5000g of recycled marine plastic, 400g of high-toughness polyester resin, 800g of modified compatibilizer, 1400g of wood flour, 400g of flame retardant filler (magnesium hydroxide-aluminum hydroxide composite filler with a mass ratio of 3:1), 50g of titanate coupling agent, and 300g of lubricant (oxidized polyethylene wax) and add them to a high-speed mixer. Stir at low speed for 5 minutes until all components are evenly mixed to obtain a mixture.
[0025] S2: The mixture is fed into a twin-screw extruder for extrusion granulation (zone 1 145℃, zone 2 155℃, zone 3 165℃, zone 4 170℃, zone 5 175℃, zone 6 180℃, die head 180℃, die opening 175℃, main machine speed 180rpm, vacuum exhaust is turned on) to obtain wood-plastic composite granules. The wood-plastic composite granules are placed in a hot press and hot-pressed at 170℃ and 10MPa for 7 minutes. After cooling and demolding, environmentally friendly wood-plastic composite material is obtained.
[0026] Example 2: A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification includes the following steps: I. Preparation of the modified solution: S131: Add 100g of butyl acetate and 33g of anhydrous diethyl ether to a four-necked flask, stir magnetically to mix, keep warm at 43℃ under nitrogen protection for 7min, add 8.5g of p-dodecylbenzaldehyde and stir until completely dissolved, add 2.2g of sodium borohydride in 3 portions, continue stirring and react for 3.3h, let stand to separate the layers, and take the upper organic phase A.
[0027] S132: Heat organic phase A to 68℃, add 13g of polyoxyethylene monomethyl ether to every 100g of organic phase A and stir to mix, add concentrated sulfuric acid dropwise to adjust the pH to 2.3, add 1.1g of triethylamine, stir and react at a constant temperature for 4.3h, cool to room temperature, add saturated sodium carbonate solution and stir to neutralize to pH=7.3, let stand to separate into layers, and take the upper organic phase B.
[0028] S133: Add organic phase B to a vacuum distillation apparatus, add 3.5g of anhydrous magnesium sulfate to every 100g of organic phase B for adsorption and drying for 2.3h, distill off unreacted low-boiling point reagents at 72℃ and -0.08MPa, collect the fraction by heating to 122℃, recrystallize the fraction with 85g of petroleum ether at 73℃, filter, and distill again under vacuum to obtain the modified solution.
[0029] II. Preparation of modified compatibilizers: S11: Add 100g of nano-silica and 900g of anhydrous ethanol to a reaction flask, sonicate for 32min, add 16g of silane coupling agent KH-570, stir at 63℃ for 3.3h, add 1150g of butyl acetate, sonicate for 33min, then add 53g of hyperbranched polyester and 1.3g of dibutyltin dilaurate, stir at 82℃ and 500rpm for 4.3h, after the reaction is completed, centrifuge to separate the precipitate, wash twice with butyl acetate, and vacuum dry at 80℃ for 6h to obtain modified nano-silica.
[0030] S12: Add 100g MAPE and 730g xylene to a reaction flask, heat to 113℃ and stir until completely dissolved, add 8.5g benzophenone, 33g N-hydroxymethylacrylamide and 22g glycidyl methacrylate, irradiate with 365nm ultraviolet light under nitrogen protection for 4.3h, add 3.5g BPO and 1.3g triethylamine, and continue stirring at a constant temperature for 1.3h to obtain a functionalized MAPE solution.
[0031] S13: Add 330g of modified solution to every 100g of functionalized MAPE solution and stir to mix. Then add 18g of modified nano-silica and heat to 123℃ and stir at 500rpm for 4.3h. Slowly pour the reaction solution into excess anhydrous ethanol to precipitate the precipitate. Filter and collect the precipitate. After Soxhlet extraction and purification, dry under vacuum at 80℃ for 6h to obtain the modified compatibilizer.
[0032] III. Preparation of environmentally friendly wood-plastic composite materials: S1: Take 5500g of recycled marine plastic, 430g of high-toughness polyester resin, 850g of modified compatibilizer, 1500g of wood flour, 500g of flame retardant filler, 60g of titanate coupling agent, and 330g of lubricant and add them to a high-speed mixer. Stir at low speed for 7 minutes until all components are evenly mixed to obtain a mixture.
[0033] S2: The mixture is fed into a twin-screw extruder for extrusion granulation (zone 1 145℃, zone 2 155℃, zone 3 165℃, zone 4 170℃, zone 5 175℃, zone 6 180℃, die head 180℃, die opening 175℃, main machine speed 180rpm, vacuum exhaust is turned on) to obtain wood-plastic composite granules. The wood-plastic composite granules are placed in a hot press and hot-pressed at 172℃ and 12MPa for 8 minutes. After cooling and demolding, environmentally friendly wood-plastic composite material is obtained.
[0034] Example 3: A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification includes the following steps: I. Preparation of the modified solution: S131: Add 100g butyl acetate and 37g anhydrous diethyl ether to a four-necked flask, stir magnetically to mix, keep warm at 47℃ under nitrogen protection for 8min, add 9.5g p-dodecylbenzaldehyde and stir until completely dissolved, add 2.4g sodium borohydride in 3 portions, continue stirring and react for 3.7h, let stand to separate the layers, and take the upper organic phase A.
[0035] S132: Heat organic phase A to 72℃, add 14g of polyoxyethylene monomethyl ether to every 100g of organic phase A and stir to mix, add concentrated sulfuric acid dropwise to adjust the pH to 2.7, add 1.15g of triethylamine, stir and react at a constant temperature for 4.7h, cool to room temperature, add saturated sodium carbonate solution and stir to neutralize to pH=7.7, let stand to separate into layers, and take the upper organic phase B.
[0036] S133: Add organic phase B to a vacuum distillation apparatus, add 4.5g of anhydrous magnesium sulfate to every 100g of organic phase B for adsorption and drying for 2.7h, distill off unreacted low-boiling-point reagents at 74℃ and -0.08MPa, collect the fraction by heating to 124℃, recrystallize the fraction with 95g of petroleum ether at 78℃, filter, and distill again under vacuum to obtain the modified solution.
[0037] II. Preparation of modified compatibilizers: S11: Add 100g of nano-silica and 1100g of anhydrous ethanol to a reaction flask, sonicate for 35min, add 19g of silane coupling agent KH-570, stir at 68℃ for 3.7h, add 1250g of butyl acetate, sonicate for 38min, then add 58g of hyperbranched polyester and 1.8g of dibutyltin dilaurate, stir at 85℃ and 500rpm for 4.7h, after the reaction is completed, centrifuge to separate the precipitate, wash with butyl acetate 3 times, and vacuum dry at 80℃ for 6h to obtain modified nano-silica.
[0038] S12: Add 100g MAPE and 780g xylene to a reaction flask, heat to 118℃ and stir until completely dissolved, add 9.5g benzophenone, 38g N-hydroxymethylacrylamide and 24g glycidyl methacrylate, irradiate with 365nm ultraviolet light under nitrogen protection for 4.8h, add 4.5g BPO and 1.8g triethylamine, and continue stirring at a constant temperature for 1.8h to obtain a functionalized MAPE solution.
[0039] S13: Add 380g of modified solution to every 100g of functionalized MAPE solution and stir to mix. Then add 23g of modified nano-silica and heat to 128℃. Stir at 500rpm for 4.8h. Slowly pour the reaction solution into excess anhydrous ethanol to precipitate. Filter and collect the precipitate. After Soxhlet extraction and purification, dry under vacuum at 80℃ for 6h to obtain the modified compatibilizer.
[0040] III. Preparation of environmentally friendly wood-plastic composite materials: S1: Take 6200g of recycled marine plastic, 480g of high-toughness polyester resin, 950g of modified compatibilizer, 1700g of wood flour, 700g of flame retardant filler, 75g of titanate coupling agent, and 380g of lubricant and add them to a high-speed mixer. Stir at low speed for 9 minutes until all components are evenly mixed to obtain a mixture.
[0041] S2: The mixture is fed into a twin-screw extruder for extrusion granulation (zone 1 145℃, zone 2 155℃, zone 3 165℃, zone 4 170℃, zone 5 175℃, zone 6 180℃, die head 180℃, die opening 175℃, main machine speed 180rpm, vacuum exhaust is turned on) to obtain wood-plastic composite granules. The wood-plastic composite granules are placed in a hot press and hot-pressed at 178℃ and 14MPa for 8.5min. After cooling and demolding, environmentally friendly wood-plastic composite material is obtained.
[0042] Example 4: A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification includes the following steps: I. Preparation of the modified solution: S131: Add 100g of butyl acetate and 40g of anhydrous diethyl ether to a four-necked flask, stir magnetically to mix, keep warm at 50℃ under nitrogen protection for 10min, add 10g of p-dodecylbenzaldehyde and stir until completely dissolved, add 2.5g of sodium borohydride in 3 portions, continue stirring and react for 4h, let stand to separate the layers, and take the upper organic phase A.
[0043] S132: Heat organic phase A to 75℃, add 15g of polyoxyethylene monomethyl ether to every 100g of organic phase A and stir to mix, add concentrated sulfuric acid to adjust the pH to 3, add 1.2g of triethylamine, stir and react at a constant temperature for 5h, cool to room temperature, add saturated sodium carbonate solution and stir to neutralize to pH=8, let stand to separate the layers, and take the upper organic phase B.
[0044] S133: Add organic phase B to a vacuum distillation apparatus, add 5g of anhydrous magnesium sulfate to every 100g of organic phase B for adsorption and drying for 2h, distill off unreacted low-boiling point reagents at 75℃ and -0.09MPa, collect the fraction by heating to 125℃, recrystallize the fraction with 100g of petroleum ether at 80℃, filter, and distill again under vacuum to obtain the modified solution.
[0045] II. Preparation of modified compatibilizers: S11: Add 100g of nano-silica and 1200g of anhydrous ethanol to a reaction flask, sonicate for 36min, add 20g of silane coupling agent KH-570, stir at 70℃ for 4h, add 1300g of butyl acetate, sonicate for 40min, then add 60g of hyperbranched polyester and 2g of dibutyltin dilaurate, stir at 86℃ and 500rpm for 5h, after the reaction is completed, centrifuge to separate the precipitate, wash with butyl acetate 3 times, and vacuum dry at 80℃ for 6h to obtain modified nano-silica.
[0046] S12: Add 100g MAPE and 800g xylene to a reaction flask, heat to 120℃ and stir until completely dissolved, add 10g benzophenone, 40g N-hydroxymethylacrylamide and 25g glycidyl methacrylate, irradiate with 365nm ultraviolet light for 5h under nitrogen protection, add 5g BPO and 2g triethylamine, and continue stirring at a constant temperature for 2h to obtain a functionalized MAPE solution.
[0047] S13: Add 400g of modified solution to every 100g of functionalized MAPE solution and stir to mix. Then add 25g of modified nano-silica, heat to 130℃ and stir at 500rpm for 5h. Slowly pour the reaction solution into excess anhydrous ethanol to precipitate the precipitate. Filter and collect the precipitate. After Soxhlet extraction and purification, dry under vacuum at 80℃ for 6h to obtain the modified compatibilizer.
[0048] III. Preparation of environmentally friendly wood-plastic composite materials: S1: Take 6500g of recycled marine plastic, 500g of high-toughness polyester resin, 1000g of modified compatibilizer, 1800g of wood flour, 800g of flame retardant filler, 80g of titanate coupling agent, and 400g of lubricant and add them to a high-speed mixer. Stir at low speed for 10 minutes until all components are evenly mixed to obtain a mixture.
[0049] S2: The mixture is fed into a twin-screw extruder for extrusion granulation (zone 1 145℃, zone 2 155℃, zone 3 165℃, zone 4 170℃, zone 5 175℃, zone 6 180℃, die head 180℃, die opening 175℃, main machine speed 180rpm, vacuum exhaust is turned on) to obtain wood-plastic composite granules. The wood-plastic composite granules are placed in a hot press and hot-pressed at 180℃ and 15MPa for 9 minutes. After cooling and demolding, environmentally friendly wood-plastic composite material is obtained.
[0050] Comparative Example 1 Comparative Example 1 differs from Example 1 in that the modified compatibilizer is replaced with MAPE, and the remaining steps are exactly the same as in Example 1.
[0051] Comparative Example 2 Comparative Example 2 differs from Example 1 in that the modified solution is replaced with butyl acetate, and the remaining steps are exactly the same as in Example 1.
[0052] Comparative Example 3 Compared with Example 1, Comparative Example 3 omits step S132 and directly adds organic phase A from step S131 to step S133 for vacuum distillation. The remaining steps are exactly the same as in Example 1.
[0053] The environmentally friendly wood-plastic composite materials prepared in Examples 1-4 and Comparative Examples 1-3 were tested according to the industry standards for wood-plastic composite materials (GB / T24137-2021 "Wood-plastic Composite Materials", GB / T1040.2-2006 "Determination of Tensile Properties of Plastics", GB / T9341-2008 "Determination of Bending Properties of Plastics", etc.), covering the four core performance tests of mechanical properties, flame retardancy, water resistance, and thermal stability. All test samples were taken from the prepared composite material products, and the sampling specifications met the requirements of the corresponding standards.
[0054] Samples were cut from the same location of the environmentally friendly wood-plastic composite products prepared in Examples 1-4 and Comparative Examples 1-3, according to the standard requirements of each test item. The sample surface was free of defects such as cracks, burrs, and missing corners. After cutting, the samples were placed in a constant temperature and humidity environment of 23°C and 50% relative humidity for 24 hours before various performance tests were conducted.
[0055] I. Mechanical property testing (a) Tensile property testing (in accordance with GB / T1040.2-2006, specimen type 1A) Calibrate the electronic universal testing machine, set the tensile rate to 50 mm / min, and zero the force and displacement values. Clamp the specimen in the upper and lower fixtures of the testing machine, ensuring that the specimen axis coincides with the center line of the fixtures without any skew or looseness. Start the testing machine and perform a tensile test on the specimen until it breaks. Record the maximum tensile force (N) and elongation at break (%) when the specimen breaks. Calculate the tensile strength according to the formula: in, Tensile strength, in MPa. Maximum tensile force, in N. The cross-sectional area of the sample is in mm. 2 .
[0056] (ii) Bending performance test (based on GB / T9341-2008, simply supported beam method) Calibrate the electronic universal testing machine, set the bending rate to 2 mm / min, and the support span to 16 times the specimen thickness. Zero the equipment and place the specimen stably on the two support points of the testing machine, ensuring that the specimen width direction is perpendicular to the loading head and the loading head is directly above the midpoint of the specimen. Start the testing machine, and apply pressure downwards at a uniform speed until the specimen cracks or the deflection reaches 15% of the specimen thickness. Record the maximum bending force (N) and calculate the bending strength according to the formula: in, Flexural strength, in MPa. Maximum bending force, in N. To support the span, the unit is mm. The width of the sample is in mm. The sample thickness is in mm. Specific test results are shown in Table 1 below: Table 1 The data in Table 1 show that Examples 1-4 are significantly better than Comparative Examples 1-3 in terms of mechanical properties. Examples 2 and 3, with intermediate ratios, have slightly better performance than Examples 1 and 4 with extreme ratios, demonstrating the rationality and synergy of the modified process ratio. In the example group, Example 3 has the best maximum tensile force, tensile strength, maximum bending force, and bending strength. Comparative Example 1, due to the direct use of unmodified MAPE, has extremely poor interfacial compatibility and the worst mechanical properties. Comparative Example 2 uses ordinary butyl acetate instead of the modified solution, and Comparative Example 3 omits the hydrophilic group grafting step of the modified solution. Although both have some modification effect, their mechanical properties are still far lower than those of the example group due to insufficient dispersibility and interfacial bonding. This indicates that the complete preparation process of the modified compatibilizer and the modified solution is the key to improving the mechanical properties of the material. The three work together to achieve a tight bond between the marine plastic, wood flour, and flame-retardant filler components, effectively solving the technical defects of poor interfacial bonding and low mechanical strength in traditional wood-plastic composites.
[0057] II. Water resistance test (based on GB / T24137-2021) Weigh the initial mass of the sample using an electronic analytical balance. Record the initial dimensions (length) of the sample. ,width ,thickness The samples were completely immersed in deionized water at 23°C, with no contact between samples and a minimum distance of 20 mm between the sample and the water surface and the bottom of the container. After soaking for 24 hours, the samples were removed, and the surface moisture was quickly absorbed with clean absorbent paper. The mass of the sample after soaking was immediately measured. ), and measure the dimensions (length) of the sample after immersion. ,width ,thickness ), calculate the water absorption rate according to the formula: Calculate the rate of dimensional change using the formula (taking the thickness direction as an example): The specific test results are shown in Table 2 below: Table 2 As can be seen from the data in Table 2, the water resistance of the environmentally friendly wood-plastic composite materials in Examples 1-4 is far superior to that in Comparative Examples 1-3. The water absorption rate and the dimensional change rate in the thickness direction are significantly reduced. Examples 2 and 3 show the best water resistance, which confirms the advantage of the intermediate ratio modification process in improving the water resistance of the material. Comparative Example 1 has the worst water resistance because it lacks a modified compatibilizer, the hydrophilic groups of the wood flour are exposed, and there are gaps at the interfaces of each component, making it easy for water to penetrate. Comparative Examples 2 and 3 have the worst water resistance because the preparation process of the modified solution is incomplete and the hydrophobic modification effect is insufficient. The water absorption rate and dimensional change rate are still at a high level. This shows that the modification process of the present invention effectively blocks the penetration of water into the material by forming a hydrophobic layer at the interfaces of each component. It solves the problem of poor water resistance and dimensional deformation after water absorption caused by the hydrophilicity of wood flour in traditional wood-plastic composite materials, and greatly improves the environmental adaptability and service life of the material.
[0058] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification, characterized in that, Includes the following steps: S1. Mix 50-65 parts of recycled marine plastic, 4-5 parts of high-toughness polyester resin, 8-10 parts of modified compatibilizer, 14-18 parts of wood flour, 4-8 parts of flame-retardant filler, 0.5-0.8 parts of coupling agent, and 3-4 parts of lubricant for 5-10 minutes to obtain a mixture. S2. Extruding and granulating the mixture to obtain wood-plastic composite particles, and hot-pressing the wood-plastic composite particles at 170-180℃ and 10-15MPa for 7-9 minutes to obtain environmentally friendly wood-plastic composite material. The modified compatibilizer is prepared through the following steps: S11. Add nano-silica to anhydrous ethanol, ultrasonically disperse for 30-36 min, add silane coupling agent, react at 60-70℃ for 3-4 h, add butyl acetate and disperse for 30-40 min, then add hyperbranched polyester and dibutyltin dilaurate, react at 80-86℃ for 4-5 h with stirring, after the reaction is completed, centrifuge to separate the precipitate, wash the precipitate 2-3 times with butyl acetate, and vacuum dry to obtain modified nano-silica; S12. Add MAPE to xylene, heat to 110-120℃, stir, then add benzophenone, N-hydroxymethylacrylamide and glycidyl methacrylate, irradiate with ultraviolet light under nitrogen protection for 4-5 hours, add BPO and triethylamine, continue stirring at constant temperature for 1-2 hours to obtain functionalized MAPE solution. S13. Add the modified solution to the functionalized MAPE solution and mix, then add the modified nano-silica. Heat to 120-130℃ and stir for 4-5 hours to obtain the reaction solution. Pour the reaction solution into excess anhydrous ethanol to precipitate the precipitate. Filter and collect the precipitate for purification. Vacuum dry the purified precipitate to obtain the modified compatibilizer.
2. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 1, characterized in that, The modified solution in step S13 is prepared through the following steps: S131. Stir and mix butyl acetate and anhydrous diethyl ether, keep warm at 40-50℃ under nitrogen protection for 5-10 min, add p-dodecylbenzaldehyde and stir to dissolve, then add sodium borohydride in portions, continue stirring and reacting for 3-4 h, let stand to separate the layers, and take the upper organic phase A. S132. Heat organic phase A to 65-75℃, add polyoxyethylene monomethyl ether, stir and mix, then add concentrated sulfuric acid dropwise to adjust the pH to 2-3, then add triethylamine, stir and react at a constant temperature for 4-5 hours, then cool to room temperature, add saturated sodium carbonate solution, stir and neutralize the pH to 7-8, let stand and separate into layers, and take the upper organic phase B. S133. Organic phase B is subjected to vacuum distillation. After adsorption and drying with anhydrous magnesium sulfate for 2-3 hours, unreacted low-boiling-point reagents are distilled off at 70-75℃. The temperature is then raised to 120-125℃ to collect the fraction. The fraction is recrystallized with petroleum ether at 70-80℃, filtered, and then subjected to vacuum distillation again to obtain the modified solution.
3. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 1, characterized in that, In step S11, the mass ratio of nano-silica, anhydrous ethanol, silane coupling agent, butyl acetate, hyperbranched polyester and dibutyltin dilaurate is 100:(800-1200):(15-20):(1100-1300):(50-60):(1-2).
4. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 1, characterized in that, In step S12, the mass ratio of MAPE, xylene, benzophenone, N-hydroxymethylacrylamide, glycidyl methacrylate, BPO and triethylamine is 100:(700-800):(8-10):(30-40):(20-25):(3-5):(1-2).
5. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 1, characterized in that, In step S13, the mass ratio of functionalized MAPE, modified solution, and modified nano-silica is 100:(300-400):(15-25).
6. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 2, characterized in that, In step S131, the mass ratio of butyl acetate, anhydrous diethyl ether, p-dodecylbenzaldehyde, and sodium borohydride is 100:(30-40):(8-10):(2-2.5).
7. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 2, characterized in that, In step S132, the mass ratio of organic phase A, polyoxyethylene monomethyl ether, and triethylamine is 100:(12-15):(1-1.2).
8. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 2, characterized in that, In step S133, the mass ratio of organic phase B, anhydrous magnesium sulfate, and petroleum ether is 100:(3-5):(80-100).
9. The method for preparing an environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification according to claim 1, characterized in that, The wood flour is one or more of sawdust, shavings, bamboo powder and rice husk powder, with a mesh size of 40-80 mesh and a moisture content of ≤2%. It is used after drying. The recycled marine plastic is mainly composed of high-density polyethylene and polyethylene, and is used after sorting, washing, drying and crushing.
10. An environmentally friendly wood-plastic composite material based on marine plastic waste and wood flour modification, characterized in that, The environmentally friendly wood-plastic composite material is prepared by the preparation method according to any one of claims 1-9.