Permeable floor for upgrading renewable resources of wind power generation blades

Abstract

The invention belongs to the technical field of environment-friendly functional materials, and particularly relates to a permeable floor for upgrading renewable resources of wind power generation blades. The material comprises the following components in parts by weight: 30-40 parts of wood flour, 40-50 parts of regenerated polyethylene, 10-20 parts of modified wind driven generator blade regenerated glass fiber powder, 8-12 parts of sodium bicarbonate, 1-2 parts of a coupling agent, 1-2 parts of a lubricant and 1-2 parts of an antioxidant. Through a special modification treatment process, the waste wind power generation blades are converted into renewable resources with high additional value, and the water permeable floor with excellent performance is prepared. The floor provided by the invention not only has good mechanical properties and water permeability, but also has remarkable antibacterial ability, can effectively inhibit bacterium breeding, and provides a healthier and safer living environment for people. The product has wide application prospects in various places such as urban footpaths, hospitals, laboratories and the like, and meanwhile, the dual purposes of recycling resources and protecting the environment are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of environmentally friendly functional materials, and in particular to a permeable floor for upgrading the recycled resources of wind power generation blades. Background Art

[0002] With the transformation of the global energy structure, wind power generation has been widely used and developed as a clean and renewable energy utilization method. However, after the wind turbine blades reach the end of their service life, the problem of the disposal of discarded blades has become increasingly prominent. These blades are mainly made of composite materials and are difficult to degrade naturally. If they are directly discarded, they will not only occupy a large amount of land resources, but may also cause long-term pollution to the environment. Therefore, how to effectively recycle and utilize discarded wind turbine blades has become an important issue in the current environmental protection field.

[0003] In the process of developing environmentally friendly materials, permeable flooring, as a new type of building material, has received extensive attention due to its good permeability and environmental characteristics. Traditional permeable flooring materials are mostly made of natural stone or ordinary plastic, etc. However, these materials consume a lot of energy during the production process, and their environmental friendliness needs to be improved. In addition, traditional floors have obvious deficiencies in antibacterial properties and are prone to breeding bacteria, especially in humid environments. This not only affects the service life of the floor, but may also pose a potential threat to people's health. Therefore, it is of great practical significance to develop a permeable flooring material that has good performance, can realize the recycling of waste resources, and has antibacterial capabilities. Summary of the invention

[0004] In view of this, the purpose of the present invention is to propose a permeable floor upgraded from the recycled resources of wind power blades to solve the problems of difficult disposal of discarded blades, high energy consumption in the preparation process of permeable floors, unfriendly to the environment, and lack of self-antibacterial ability of traditional floors. Based on the above purpose, the present invention provides a permeable floor upgraded from the recycled resources of wind power blades, comprising the following raw materials in parts by weight: wood powder: 30-40 parts, recycled polyethylene: 40-50 parts, modified wind turbine blade recycled glass fiber powder: 10-20 parts, sodium bicarbonate: 8-12 parts, coupling agent: 1-2 parts, lubricant: 1-2 parts, antioxidant: 1-2 parts; The specific preparation method of the modified wind turbine blade regenerated glass fiber powder is as follows: (a) adding the regenerated glass fiber powder of wind turbine blades into an oxalic acid solution, ultrasonically treating at 50-60° C. for 25-35 min, filtering, washing, and drying to obtain acid-etched glass fiber powder; (b) under nitrogen protection, the acid-etched glass fiber powder obtained in step (a) is added to deionized water and stirred for 20-30 minutes, potassium persulfate and 4-vinyl-1-naphthol are added, the temperature is raised to 60-80° C., the reaction is stirred for 4-8 hours, and the modified glass fiber powder intermediate A is obtained by filtering, washing and drying; (c) mixing carboxylated nanocellulose, trimethylsilyl chloride, triethylamine and tetrahydrofuran, stirring at room temperature for 2-4 hours, adding ethylenediamine, stirring for 2-4 hours, adding 11-mercapto-undecanoic acid, heating to 60-70° C., reacting for 4-6 hours, adding dilute hydrochloric acid after returning to room temperature until the pH value is 5, stirring for 1-3 hours, filtering, washing and drying to obtain modified nanocellulose; (d) adding the modified glass fiber powder intermediate A obtained in step (b) and the modified nanocellulose obtained in step (c) to cyclohexane and stirring for 20-30 minutes, then adding a catalyst, heating to 80-100° C. and reflux reaction for 8-12 hours, filtering, washing, and drying to obtain modified glass fiber powder B; (e) adding the modified glass fiber powder B obtained in step (d) into a silver nitrate solution, placing the mixture in a constant temperature oscillator, oscillating and reacting at 30-40° C. for 4-6 hours, filtering, washing and drying to obtain a modified wind turbine blade regenerated glass fiber powder.

[0005] Preferably, the recycled polyethylene refers to waste polyethylene plastic products, which are recycled and then go through a series of processing processes, including mixing, grinding, washing, separation, and drying steps to finally obtain.

[0006] Preferably, the coupling agent is one of KH-550, KH-560 or KH-570.

[0007] Preferably, the antioxidant refers to antioxidant 1010 or antioxidant 168.

[0008] Preferably, in the step (a), the weight ratio of the regenerated glass fiber powder of the wind turbine blade to the oxalic acid solution is 1-3:8-36.

[0009] Preferably, the concentration of the oxalic acid solution in step (a) is 5%.

[0010] Preferably, in step (b), the weight ratio of the acid-etched glass fiber powder, potassium persulfate, 4-vinyl-1-naphthol and deionized water is 1-3:0.01-0.06:0.1-0.3:12-18.

[0011] Preferably, in step (c), the weight ratio of carboxylated nanocellulose, trimethylsilyl chloride, triethylamine, tetrahydrofuran, ethylenediamine and 11-mercapto-undecanoic acid is 1:1-1.5:0.05-0.1:15-25:1-1.5:0.2-0.5.

[0012] Preferably, the dilute hydrochloric acid in step (c) refers to hydrochloric acid with a concentration of 3%.

[0013] Preferably, in the step (d), the weight ratio of the modified glass fiber powder intermediate A, the modified nanocellulose, the catalyst and the cyclohexane is 1-3:0.1-0.3:0.01-0.06:15-25, and the catalyst refers to sulfuric acid with a concentration of 98%.

[0014] Preferably, in the step (e), the weight ratio of the modified glass fiber powder B to the silver nitrate solution is 1-3:10-45.

[0015] Preferably, the concentration of the silver nitrate solution in step (e) is 0.05-0.1 mol / L Furthermore, the present invention also provides a method for preparing the above-mentioned permeable floor for upgrading the recycled resources of wind power generation blades. The specific preparation process is as follows: S1. Crushing the recycled polyethylene into 100-200 mesh recycled polyethylene powder; S2. The recycled polyethylene powder, wood powder and modified wind turbine blade regenerated glass fiber powder in step S1 are added to a stirring kettle and stirred at 200-300 rpm for 10-20 min, then a coupling agent, polyethylene wax and an antioxidant are added, the speed is increased to 400-500 rpm and stirred for 10-20 min, and finally sodium bicarbonate is added and stirred for 10-20 min to obtain a mixture; S3. Put the mixture obtained in step S2 into a permeable floor mold for upgrading the recycled resources of wind power blades that has been preheated at 100-120°C in advance, pre-press it at 5-8MPa for 5-8min under a hydraulic press, then increase the pressure to 12-15MPa, increase the temperature to 180-200°C, maintain the pressure for 15-20min, and obtain a permeable floor for upgrading the recycled resources of wind power blades after demolding.

[0016] Beneficial effects of the present invention: 1. The permeable floor upgraded from recycled wind turbine blades of the present invention realizes high value-added recycling of waste by preparing modified glass fiber powder using discarded wind turbine blades. This innovative resource recycling method not only effectively solves the problem of handling discarded blades and reduces the pressure on the environment, but also provides a new type of reinforcement material for the production of permeable floors. The modified glass fiber powder plays an excellent reinforcing role in the floor, significantly improving the mechanical properties of the floor, making it show better stability and durability when under heavy pressure, extending the service life of the floor, reducing maintenance costs, and having significant economic and environmental benefits.

[0017] 2. The permeable floor of the present invention has excellent water permeability and can effectively promote the rapid penetration of rainwater. This is due to the unique porous structure design in the floor material, which provides a convenient channel for the flow of water and greatly improves the water permeability efficiency. Against the background of accelerated urbanization, the application of this permeable floor helps to alleviate the problem of urban waterlogging and reduce the burden on urban drainage systems. At the same time, good water permeability can also replenish groundwater and maintain the balance of urban water circulation, which is of great significance to the protection and improvement of the urban ecological environment. In addition, the permeable floor can also effectively reduce the surface temperature of the city, reduce the urban heat island effect, and create a more comfortable and livable living environment for residents.

[0018] 3. The permeable floor upgraded from the recycled resources of wind turbine blades of the present invention also has excellent antibacterial properties. Through a special chemical modification process, antibacterial components such as silver ions are successfully loaded into the floor material. These components can effectively inhibit the growth and reproduction of bacteria and have significant antibacterial effects on a variety of common bacteria. This feature makes the floor of the present invention have broad application prospects in places with high requirements for sanitary conditions, such as hospitals, laboratories, and food processing plants. The use of antibacterial floors can not only reduce the spread of bacteria and reduce the risk of cross-infection, but also effectively keep the environment clean and sanitary, providing people with a healthier and safer living and working environment, and has important social value. DETAILED DESCRIPTION

[0019] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0020] Example 1: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 200 g of wind turbine blade regenerated glass fiber powder was added to 1.6 L of 5% oxalic acid solution, ultrasonically treated at 50 °C for 25 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 200 g of the acid-etched glass fiber powder obtained in step (a) was added to 2.4 L of deionized water and stirred for 20 min, and then 2 g of potassium persulfate and 20 g of 4-vinyl-1-naphthol were added, the temperature was raised to 60 ° C, and the reaction was stirred for 4 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) 30 g of carboxylated nanocellulose, 30 g of trimethylsilyl chloride, 1.5 g of triethylamine and 450 g of tetrahydrofuran were mixed, stirred at room temperature for 2 h, 30 g of ethylenediamine was added, stirred for 2 h, 6 g of 11-mercapto-undecanoic acid was added, the temperature was raised to 60 ° C, reacted for 4 h, and after returning to room temperature, 3% dilute hydrochloric acid was added until pH = 5, stirred for 1 h, filtered, washed, and dried to obtain modified nanocellulose; (d) adding 200 g of the modified glass fiber powder intermediate A obtained in step (b) and 20 g of the modified nanocellulose obtained in step (c) to 3 L of cyclohexane and stirring for 20 min, then adding 2 g of 98% sulfuric acid, heating to 80 ° C and reflux reaction for 8 h, filtering, washing and drying to obtain modified glass fiber powder B; (e) Add 200 g of the modified glass fiber powder B obtained in step (d) to 2 L of a 0.05 mol / L silver nitrate solution, place the mixture in a constant temperature oscillator, oscillate at 30° C. for 4 h, filter, wash, and dry to obtain a modified wind turbine blade regenerated glass fiber powder.

[0021] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 800g of recycled polyethylene was crushed into 100 mesh recycled polyethylene powder; S2. 800g of recycled polyethylene powder, 600g of wood powder and 200g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 200rpm for 10min, then 20g of KH-560, 10g of polyethylene wax and 20g of antioxidant 1010 were added, the speed was increased to 400rpm and stirred for 10min, and finally 160g of sodium bicarbonate was added and stirred for 10min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold for upgrading the recycled resources of wind power blades that has been preheated at 100°C, pre-press at 5MPa for 5 minutes under a hydraulic press, then increase the pressure to 12MPa, raise the temperature to 180°C, and maintain the pressure for 15 minutes. After demolding, a permeable floor for upgrading the recycled resources of wind power blades is obtained.

[0022] Example 2: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 500 g of wind turbine blade regenerated glass fiber powder was added to 5 L of 5% oxalic acid solution, ultrasonically treated at 55 °C for 30 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 500 g of the acid-etched glass fiber powder obtained in step (a) was added to 3.75 L of deionized water and stirred for 25 min, and then 10 g of potassium persulfate and 50 g of 4-vinyl-1-naphthol were added, the temperature was raised to 70 ° C, and the reaction was stirred for 6 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) 60 g of carboxylated nanocellulose, 75 g of trimethylsilyl chloride, 4.5 g of triethylamine and 1.2 kg of tetrahydrofuran were mixed, stirred at room temperature for 3 h, 75 g of ethylenediamine was added, stirred for 3 h, 21 g of 11-mercapto-undecanoic acid was added, the temperature was raised to 65 ° C, reacted for 5 h, and after returning to room temperature, 3% dilute hydrochloric acid was added until pH = 5, stirred for 2 h, filtered, washed and dried to obtain modified nanocellulose; (d) adding 500 g of the modified glass fiber powder intermediate A obtained in step (b) and 50 g of the modified nanocellulose obtained in step (c) to 5 L of cyclohexane and stirring for 25 min, adding 10 g of 98% sulfuric acid, heating to 90 ° C and reflux reaction for 10 h, filtering, washing and drying to obtain modified glass fiber powder B; (e) 500 g of the modified glass fiber powder B obtained in step (d) was added to 5 L of a 0.75 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 35° C. for 5 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0023] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 900g of recycled polyethylene was crushed into 150 mesh recycled polyethylene powder; S2. 900g of recycled polyethylene powder, 700g of wood flour and 300g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 250rpm for 15min, then 30g of KH-560, 30g of polyethylene wax and 30g of antioxidant 1010 were added, the speed was increased to 450rpm and stirred for 15min, and finally 200g of sodium bicarbonate was added and stirred for 15min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold preheated at 110°C, pre-press at 6.5MPa for 6.5min under a hydraulic press, then increase the pressure to 14MPa, raise the temperature to 190°C, maintain the pressure for 17.5min, and obtain a permeable floor after demoulding.

[0024] Example 3: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 450 g of wind turbine blade regenerated glass fiber powder was added to 5.4 L of 5% oxalic acid solution, ultrasonically treated at 60 °C for 35 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 450 g of the acid-etched glass fiber powder obtained in step (a) was added to 2.7 L of deionized water and stirred for 30 min, and then 9 g of potassium persulfate and 45 g of 4-vinyl-1-naphthol were added, the temperature was raised to 80 ° C, and the reaction was stirred for 8 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing and drying; (c) 50 g of carboxylated nanocellulose, 75 g of trimethylsilyl chloride, 5 g of triethylamine and 1.25 kg of tetrahydrofuran were mixed, stirred at room temperature for 4 h, 75 g of ethylenediamine was added, stirred for 4 h, 25 g of 11-mercapto-undecanoic acid was added, the temperature was raised to 70 ° C, reacted for 6 h, and after returning to room temperature, 3% dilute hydrochloric acid was added until pH = 5, stirred for 3 h, filtered, washed and dried to obtain modified nanocellulose; (d) adding 450 g of the modified glass fiber powder intermediate A obtained in step (b) and 45 g of the modified nanocellulose obtained in step (c) to 3.75 L of cyclohexane and stirring for 30 min, then adding 9 g of 98% sulfuric acid, heating to 100 ° C and reflux reaction for 12 h, filtering, washing and drying to obtain modified glass fiber powder B; (e) 450 g of the modified glass fiber powder B obtained in step (d) was added to 6.75 L of a 0.1 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 40° C. for 6 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0025] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. Crushing 1Kg of recycled polyethylene into 200 mesh recycled polyethylene powder; S2. 1Kg of recycled polyethylene powder, 800g of wood powder and 400g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 300rpm for 20min, then 40g of KH-560, 40g of polyethylene wax and 40g of antioxidant 1010 were added, the speed was increased to 500rpm and stirred for 20min, and finally 240g of sodium bicarbonate was added and stirred for 20min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold for upgrading the recycled resources of wind power blades that has been preheated at 120°C, pre-press at 8MPa for 8min under a hydraulic press, then increase the pressure to 15MPa, raise the temperature to 200°C, and maintain the pressure for 20min. After demolding, a permeable floor for upgrading the recycled resources of wind power blades is obtained.

[0026] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that 4-vinyl-1-naphthol is replaced by p-hydroxystyrene. The specific steps are as follows: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 500 g of wind turbine blade regenerated glass fiber powder was added to 5 L of 5% oxalic acid solution, ultrasonically treated at 55 °C for 30 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 500 g of the acid-etched glass fiber powder obtained in step (a) was added to 3.75 L of deionized water and stirred for 25 min, and then 10 g of potassium persulfate and 50 g of p-hydroxystyrene were added, the temperature was raised to 70° C., and the reaction was stirred for 6 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) 60 g of carboxylated nanocellulose, 75 g of trimethylsilyl chloride, 4.5 g of triethylamine and 1.2 kg of tetrahydrofuran were mixed, stirred at room temperature for 3 h, 75 g of ethylenediamine was added, stirred for 3 h, 21 g of 11-mercapto-undecanoic acid was added, the temperature was raised to 65 ° C, reacted for 5 h, and after returning to room temperature, 3% dilute hydrochloric acid was added until pH = 5, stirred for 2 h, filtered, washed and dried to obtain modified nanocellulose; (d) adding 500 g of the modified glass fiber powder intermediate A obtained in step (b) and 50 g of the modified nanocellulose obtained in step (c) to 5 L of cyclohexane and stirring for 25 min, adding 10 g of 98% sulfuric acid, heating to 90 ° C and reflux reaction for 10 h, filtering, washing and drying to obtain modified glass fiber powder B; (e) 500 g of the modified glass fiber powder B obtained in step (d) was added to 5 L of a 0.75 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 35° C. for 5 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0027] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 900g of recycled polyethylene was crushed into 150 mesh recycled polyethylene powder; S2. 900g of recycled polyethylene powder, 700g of wood flour and 300g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 250rpm for 15min, then 30g of KH-560, 30g of polyethylene wax and 30g of antioxidant 1010 were added, the speed was increased to 450rpm and stirred for 15min, and finally 200g of sodium bicarbonate was added and stirred for 15min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold preheated at 110°C, pre-press at 6.5MPa for 6.5min under a hydraulic press, then increase the pressure to 14MPa, raise the temperature to 190°C, maintain the pressure for 17.5min, and obtain a permeable floor after demoulding.

[0028] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that 11-mercapto-undecanoic acid is replaced with undecanoic acid. The specific steps are as follows: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 500 g of wind turbine blade regenerated glass fiber powder was added to 5 L of 5% oxalic acid solution, ultrasonically treated at 55 °C for 30 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 500 g of the acid-etched glass fiber powder obtained in step (a) was added to 3.75 L of deionized water and stirred for 25 min, and then 10 g of potassium persulfate and 50 g of 4-vinyl-1-naphthol were added, the temperature was raised to 70 ° C, and the reaction was stirred for 6 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) 60 g of carboxylated nanocellulose, 75 g of trimethylsilyl chloride, 4.5 g of triethylamine and 1.2 kg of tetrahydrofuran were mixed, stirred at room temperature for 3 h, 75 g of ethylenediamine was added, stirred for 3 h, 21 g of undecanoic acid was added, the temperature was raised to 65 ° C, reacted for 5 h, and after returning to room temperature, 3% dilute hydrochloric acid was added until pH = 5, stirred for 2 h, filtered, washed and dried to obtain modified nanocellulose; (d) adding 500 g of the modified glass fiber powder intermediate A obtained in step (b) and 50 g of the modified nanocellulose obtained in step (c) to 5 L of cyclohexane and stirring for 25 min, adding 10 g of 98% sulfuric acid, heating to 90 ° C and reflux reaction for 10 h, filtering, washing and drying to obtain modified glass fiber powder B; (e) 500 g of the modified glass fiber powder B obtained in step (d) was added to 5 L of a 0.75 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 35° C. for 5 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0029] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 900g of recycled polyethylene was crushed into 150 mesh recycled polyethylene powder; S2. 900g of recycled polyethylene powder, 700g of wood flour and 300g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 250rpm for 15min, then 30g of KH-560, 30g of polyethylene wax and 30g of antioxidant 1010 were added, the speed was increased to 450rpm and stirred for 15min, and finally 200g of sodium bicarbonate was added and stirred for 15min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold preheated at 110°C, pre-press at 6.5MPa for 6.5min under a hydraulic press, then increase the pressure to 14MPa, raise the temperature to 190°C, maintain the pressure for 17.5min, and obtain a permeable floor after demoulding.

[0030] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that 11-mercapto-undecanoic acid is not compounded with nanocellulose but directly added to the glass fiber powder. The specific steps are as follows: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: A specific preparation method of modified wind turbine blade regenerated glass fiber powder is as follows: (a) 500 g of wind turbine blade regenerated glass fiber powder was added to 5 L of 5% oxalic acid solution, ultrasonically treated at 55 °C for 30 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 500 g of the acid-etched glass fiber powder obtained in step (a) was added to 3.75 L of deionized water and stirred for 25 min, and then 10 g of potassium persulfate and 50 g of 4-vinyl-1-naphthol were added, the temperature was raised to 70 ° C, and the reaction was stirred for 6 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) adding 50 g of 11-mercapto-undecanoic acid, 500 g of the modified glass fiber powder intermediate A obtained in step (b), and 50 g of carboxylated nanocellulose to 5 L of cyclohexane and stirring for 25 min, adding 10 g of 98% sulfuric acid, heating to 90 ° C. and reflux reaction for 10 h, filtering, washing, and drying to obtain modified glass fiber powder B; (d) 500 g of the modified glass fiber powder B obtained in step (c) was added to 5 L of a 0.75 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 35° C. for 5 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0031] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 900g of recycled polyethylene was crushed into 150 mesh recycled polyethylene powder; S2. 900g of recycled polyethylene powder, 700g of wood flour and 300g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 250rpm for 15min, then 30g of KH-560, 30g of polyethylene wax and 30g of antioxidant 1010 were added, the speed was increased to 450rpm and stirred for 15min, and finally 200g of sodium bicarbonate was added and stirred for 15min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold preheated at 110°C, pre-press at 6.5MPa for 6.5min under a hydraulic press, then increase the pressure to 14MPa, raise the temperature to 190°C, maintain the pressure for 17.5min, and obtain a permeable floor after demoulding.

[0032] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that carboxylated nanocellulose is replaced by nanocellulose, and the specific steps are as follows: A specific preparation method of a modified wind turbine blade regenerated glass fiber powder is as follows: (a) 500 g of wind turbine blade regenerated glass fiber powder was added to 5 L of 5% oxalic acid solution, ultrasonically treated at 55 °C for 30 min, filtered, washed, and dried to obtain acid-etched glass fiber powder; (b) under nitrogen protection, 500 g of the acid-etched glass fiber powder obtained in step (a) was added to 3.75 L of deionized water and stirred for 25 min, and then 10 g of potassium persulfate and 50 g of 4-vinyl-1-naphthol were added, the temperature was raised to 70 ° C, and the reaction was stirred for 6 h, and the modified glass fiber powder intermediate A was obtained by filtering, washing, and drying; (c) 500 g of the modified glass fiber powder intermediate A obtained in step (b) and 50 g of 11-mercapto-undecanoic acid were added to 5 L of cyclohexane and stirred for 25 min, and then 10 g of 98% sulfuric acid was added, the temperature was raised to 90 ° C and refluxed for 10 h, filtered, washed, and dried to obtain modified glass fiber powder B; (d) 500 g of the modified glass fiber powder B obtained in step (c) was added to 5 L of a 0.75 mol / L silver nitrate solution, placed in a constant temperature oscillator, and oscillated at 35° C. for 5 h. The modified wind turbine blade regenerated glass fiber powder was filtered, washed, and dried to obtain.

[0033] A method for preparing a permeable floor for upgrading wind turbine blade renewable resources, the specific preparation process is as follows: S1. 900g of recycled polyethylene was crushed into 150 mesh recycled polyethylene powder; S2. 900g of recycled polyethylene powder, 700g of wood flour, 50g of nanocellulose and 300g of modified wind turbine blade regenerated glass fiber powder in step S1 were added to a stirred tank and stirred at 250rpm for 15min, then 30g of KH-560, 30g of polyethylene wax and 30g of antioxidant 1010 were added, the speed was increased to 450rpm and stirred for 15min, and finally 200g of sodium bicarbonate was added and stirred for 15min to obtain a mixture; S3. Place the mixture obtained in step S2 into a permeable floor mold preheated at 110°C, pre-press at 6.5MPa for 6.5min under a hydraulic press, then increase the pressure to 14MPa, raise the temperature to 190°C, maintain the pressure for 17.5min, and obtain a permeable floor after demoulding.

[0034] Performance Testing

[0035] 1. Mechanical properties test: The permeable floor samples prepared in Examples 1-3 and Comparative Examples 1-4 were cut into a size of 10 cm × 10 cm × 5 cm, ensuring that the surface of the samples was flat, and the samples were placed on the lower pressure plate of a universal material testing machine. The loading speed was set to 1 mm / min, and the maximum load F (N) when the samples were damaged was recorded. The compressive strength of the samples was calculated according to the formula σ = A / F, where σ is the compressive strength (MPa), F is the maximum load (N), and A is the cross-sectional area of ​​the sample (cm²). The experimental data are shown in Table 1.

[0036] 2. Water permeability test: Cut the water permeable floor samples prepared in Examples 1-3 and Comparative Examples 1-4 into a size of 10 cm × 10 cm × 5 cm, ensure that the sample surface is flat, fix the sample in a water permeability coefficient test device, ensure the sealing between the sample and the device, inject 500 ml of water into the upper part of the device, record the initial volume of water, start the timer, record the time for water to completely pass through the sample, and calculate the water permeability coefficient based on the recorded data. The formula is as follows: , where K is the water permeability (cm / s), Q is the amount of water passing through the sample (cm³), A is the area of ​​the sample (cm²), and t is the time (s). The experimental results are shown in Table 1.

[0037] 3. Antibacterial effect test: The permeable floor samples prepared in Examples 1-3 and Comparative Examples 1-4 were cut into a size of 10 cm × 10 cm × 5 cm, and the sample surface was ensured to be flat. The concentration of the mixed bacterial solution was about 1 × 10 6CFU / ml, the mixed bacterial suspension includes Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa. The mixed bacterial suspension is evenly coated on the surface of the permeable floor sample and placed in an incubator for 24 hours at 37°C. After the incubation, the sample is taken out and the colony count is recorded as N t ; Spread the mixed bacterial suspension evenly on the nutrient agar medium with the same size as the permeable floor sample, and culture it at 37℃ for 24 hours. After the culture is completed, take out the culture medium, count the colonies and record them as N0, and calculate the antibacterial rate = , the experimental results are shown in Table 1.

[0038] Table 1 Performance test results

[0039] Data analysis: From the data of Examples 1-3 in Table 1, it can be seen that the permeable floor upgraded from wind turbine blade renewable resources prepared by the present invention has good mechanical properties, good water permeability and excellent antibacterial ability, among which Example 2 has the best performance, with a compressive strength of 32.0 MPa, a water permeability of 0.18 cm / s and an antibacterial rate of up to 98.3%, which shows that Example 2 improves the physical structure of the material while improving the mechanical properties of the material, so that the material has good spatial pores and thus improves the water permeability, and the silver ions combined by chemical methods greatly improve the antibacterial ability of the material, so that it has broad application prospects whether it is in urban trails in life or in hospitals and laboratory environments with requirements for antibacterial rates or in use environments with high requirements for road strength.

[0040] From the data of Example 2 and Comparative Example 1 in Table 1, it can be seen that the permeable floor prepared by the present invention for upgrading the wind turbine blade renewable resources has the advantages of higher compressive strength, water permeability and antibacterial rate. This may be because Comparative Example 1 replaces 4-vinyl-1-naphthol with p-hydroxystyrene, and the naphthalene ring has a larger rigid structure than the benzene ring. After 4-vinyl-1-naphthol participates in the reaction, its naphthalene ring structure helps to enhance the rigid connection inside the material, so that the material can better resist deformation when under pressure, thereby improving the compressive strength; at the same time, the presence of the naphthalene ring structure may support the microscopic pore structure of the material, making its pores more conducive to the passage of water, thereby improving the water permeability; in terms of antibacterial, the naphthalene ring structure and subsequent processes such as loading silver ions synergistically make the material have better antibacterial properties, and after the replacement of p-hydroxystyrene, this favorable rigid structure cannot be formed, resulting in performance degradation.

[0041] It can be seen from the data of Example 2 and Comparative Example 2 in Table 1 that the permeable floor prepared by the present invention for upgrading wind turbine blade renewable resources is in sharp contrast to that of Comparative Example 2 in terms of antibacterial performance. This may be because the thiol structure can react chemically with silver ions to stably load silver ions. This chemical bonding method allows the silver ions to be firmly bound to the material structure and not easily fall off. The large amount of stably present silver ions effectively improves the antibacterial ability of the material. In Comparative Example 2, due to the loss of the thiol group, the silver ions may only be loaded on the material by physical methods. This physical loading method is not stable enough, and the silver ions are easy to fall off, which not only leads to a reduction in antibacterial components but also affects the stability of the internal structure of the material, resulting in a decrease in compressive strength and water permeability coefficient.

[0042] It can be seen from the data of Example 2 and Comparative Example 3 in Table 1 that the permeable floor prepared by the present invention using recycled resources of wind turbine blades performs better in various performances. This may be because after 11-mercapto-undecanoic acid is grafted onto nanocellulose, the nanocellulose structure is made more complete and the interaction within the nanocellulose is enhanced. When the composited nanocellulose is added to the glass fiber powder, it can better cooperate with the glass fiber powder to build a more stable network structure inside the material. At the same time, the long-chain structure may affect the aggregation state of the nanocellulose, making it more evenly distributed in the material, thereby forming a channel that is conducive to water penetration when the material is formed. Finally, thanks to the large specific surface area of ​​nanocellulose, the contact area between the 11-mercapto-undecanoic acid composite silver ions and the outside world is significantly increased. When contacting bacteria, more and more stably present silver ions can better exert an antibacterial effect, thereby greatly improving the antibacterial rate.

[0043] From the data of Example 2 and Comparative Example 4 in Table 1, it can be seen that the permeable floor of a wind turbine blade renewable resource upgrade prepared by the present invention has the advantages of higher water permeability coefficient and antibacterial rate. This may be because in terms of compressive strength, the carboxylated nanocellulose in Example 2 can undergo grafting reaction with the surface of glass fiber powder and other components through carboxyl groups to form a strong chemical bond, build a stable three-dimensional network structure, effectively enhance the internal binding force of the material, and enable the material to better withstand pressure, while the ordinary nanocellulose and glass fiber powder in Comparative Example 4 are only physically mixed, and the binding force between the two is weak. When subjected to pressure, the internal structure of the material is easily destroyed. In terms of water permeability, when the carboxylated nanocellulose is grafted on the surface of the glass fiber powder, the presence of the carboxyl group affects the microstructure inside the material, prompting the formation of more regular and better connected pores, providing a convenient channel for water penetration. In terms of antibacterial performance, the carboxyl groups on the surface of the carboxylated nanocellulose in Example 2 are negatively charged, and have an electrostatic attraction with the positively charged silver ions, which can make the silver ions evenly dispersed and firmly loaded in the material, greatly increasing the probability of contact with bacteria. Comparative Example 4 relies on physical mixing, and the silver ions are not tightly combined with ordinary nanocellulose and glass fiber powder, are easily lost, and are unevenly distributed, and cannot play an antibacterial role.

[0044] It should be understood by those skilled in the art that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. A permeable floor for upgrading wind turbine blade renewable resources, characterized in that: The raw materials include the following parts by weight: wood flour: 30-40 parts, recycled polyethylene: 40-50 parts, modified wind turbine blade recycled glass fiber powder: 10-20 parts, sodium bicarbonate: 8-12 parts, coupling agent: 1-2 parts, polyethylene wax: 1-2 parts, antioxidant: 1-2 parts; The specific preparation method of the modified wind turbine blade regenerated glass fiber powder is as follows: (a) adding the regenerated glass fiber powder of wind turbine blades into an oxalic acid solution, ultrasonically treating at 50-60° C. for 25-35 min, filtering, washing, and drying to obtain acid-etched glass fiber powder; (b) under nitrogen protection, potassium persulfate, the acid-etched glass fiber powder obtained in step (a), 4-vinyl-1-naphthol and deionized water are mixed, the temperature is raised to 60-80° C., stirred for reaction for 4-8 hours, filtered, washed and dried to obtain a modified glass fiber powder intermediate A; (c) mixing carboxylated nanocellulose, trimethylsilyl chloride, triethylamine and tetrahydrofuran, stirring at room temperature for 2-4 hours, adding ethylenediamine, stirring for 2-4 hours, adding 11-mercapto-undecanoic acid, heating to 60-70° C., reacting for 4-6 hours, adding dilute hydrochloric acid after returning to room temperature until the pH value is 5, stirring for 1-3 hours, filtering, washing and drying to obtain modified nanocellulose; (d) mixing the modified glass fiber powder intermediate A obtained in step (b), the modified nanocellulose obtained in step (c), the catalyst and cyclohexane, heating to 80-100° C. and reflux reaction for 8-12 hours, filtering, washing and drying to obtain modified glass fiber powder B; (e) adding the modified glass fiber powder B obtained in step (d) into a silver nitrate solution, placing the mixture in a constant temperature oscillator, oscillating and reacting at 30-40° C. for 4-6 hours, filtering, washing and drying to obtain a modified wind turbine blade regenerated glass fiber powder.

2. The permeable floor for upgrading wind turbine blade recycling resources according to claim 1 is characterized in that: The recycled polyethylene refers to the waste of polyethylene plastic products, which is finally obtained after being recycled and then undergoing a series of processing processes, including mixing, grinding, washing, separation, and drying steps.

3. The permeable floor for upgrading wind turbine blade recycling resources according to claim 1 is characterized in that: The coupling agent refers to one of KH-550, KH-560 or KH-570.

4. The permeable floor for upgrading wind turbine blade recycling resources according to claim 1 is characterized in that: The antioxidant refers to antioxidant 1010 or antioxidant 168.

5. The permeable floor for upgrading wind turbine blade recycling resources according to claim 1 is characterized in that: In the step (a), the weight ratio of the wind turbine blade regenerated glass fiber powder to the oxalic acid solution is 1-3:8-36, and the concentration of the oxalic acid solution is 5%.

6. The permeable floor for upgrading wind turbine blade renewable resources according to claim 1 is characterized in that: In the step (b), the weight ratio of the acid-etched glass fiber powder, potassium persulfate, 4-vinyl-1-naphthol and deionized water is 1-3:0.01-0.06:0.1-0.3:12-18.

7. The permeable floor for upgrading wind turbine blade recycling resources according to claim 1 is characterized in that: In the step (c), the weight ratio of carboxylated nanocellulose, trimethylsilyl chloride, triethylamine, tetrahydrofuran, ethylenediamine and 11-mercapto-undecanoic acid is 1:1-1.5:0.05-0.1:15-25:1-1.5:0.2-0.5, and the dilute hydrochloric acid refers to hydrochloric acid with a concentration of 3%.

8. The permeable floor for upgrading wind turbine blade renewable resources according to claim 1 is characterized in that: In the step (d), the weight ratio of the modified glass fiber powder intermediate A, the modified nanocellulose, the catalyst and the cyclohexane is 1-3:0.1-0.3:0.01-0.06:15-25, and the catalyst refers to sulfuric acid with a concentration of 98%.

9. The permeable floor for upgrading wind turbine blade renewable resources according to claim 1, characterized in that: In the step (e), the weight ratio of the modified glass fiber powder B to the silver nitrate solution is 1-3:10-45, and the concentration of the silver nitrate solution is 0.05-0.1 mol / L.

10. A method for preparing a permeable floor for upgrading wind turbine blade renewable resources according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Crushing the recycled polyethylene into 100-200 mesh recycled polyethylene powder; S2. The recycled polyethylene powder, wood powder and modified wind turbine blade regenerated glass fiber powder in step S1 are added to a stirring kettle and stirred at 200-300 rpm for 10-20 min, then a coupling agent, polyethylene wax and an antioxidant are added, the speed is increased to 400-500 rpm and stirred for 10-20 min, and finally sodium bicarbonate is added and stirred for 10-20 min to obtain a mixture; S3. Put the mixture obtained in step S2 into a permeable floor mold for upgrading the recycled resources of wind power blades that has been preheated at 100-120°C in advance, pre-press it at 5-8MPa for 5-8min under a hydraulic press, then increase the pressure to 12-15MPa, increase the temperature to 180-200°C, maintain the pressure for 15-20min, and obtain a permeable floor for upgrading the recycled resources of wind power blades after demolding.

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