Leaf glass fiber regenerated RPC type wear-resistant and rut-resistant rubber and plastic composite auxiliary material

Abstract

The invention relates to the technical field of road engineering materials, in particular to a blade glass fiber regenerated RPC type wear-resistant and rut-resistant rubber and plastic composite auxiliary material. The material is prepared from the following components in parts by weight: 40 to 60 parts of regenerated polyethylene, 20 to 40 parts of modified wind driven generator blade regenerated glass fiber powder, 10 to 20 parts of rubber powder, 3 to 8 parts of maleic anhydride grafted polyethylene, 5 to 10 parts of styrene-butadiene-styrene block copolymer (SBS), 1 to 3 parts of polyethylene wax and 5 to 10 parts of calcium powder. The preparation process of the modified regenerated polyethylene comprises the steps of isocyanate esterification and porous microspheroidization. The modified wind driven generator blade regenerated glass fiber powder is prepared by performing acid etching on wind driven generator blade regenerated glass fiber powder, performing plasma activation, and compounding polyfunctional group titanate and a polyamino silane coupling agent. The leaf glass fiber regenerated RPC type wear-resistant and rut-resistant rubber and plastic composite auxiliary material prepared by the preparation method disclosed by the invention has the advantages that various properties of an asphalt pavement are remarkably improved, meanwhile, green cyclic utilization of waste resources is realized, and remarkable economic and social benefits are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of road engineering materials, and in particular to a blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material. Background Art

[0002] In the field of road engineering materials, with the continuous growth of traffic volume and the increasing vehicle load, the requirements for asphalt pavement performance are becoming more and more stringent. Traditional asphalt pavement anti-rutting agents mostly rely on single polymer modification, such as SBS. However, this type of anti-rutting agent has problems such as high cost and poor aging resistance, which makes it difficult to meet the long-term performance and economic requirements of modern road construction.

[0003] At the same time, the treatment of glass fiber composite materials in discarded wind turbine blades has become a major problem. The recycling rate is less than 5%. A large number of discarded blades are idle or landfilled, which not only causes waste of resources but also brings environmental pressure. If the glass fiber powder after conventional physical crushing is directly applied to road materials, the interface bonding between the glass fiber and the polymer matrix is ​​weak and the dispersion is uneven, resulting in a decrease in material performance and the inability to effectively play the reinforcing role of the glass fiber.

[0004] In terms of glass fiber powder modification, existing technologies mostly use simple silane coupling agent treatment. This treatment method has a single modification effect and is difficult to solve the problem of interfacial stress concentration between glass fiber and polymer matrix, which limits the application effect of glass fiber in high-performance road materials. Therefore, it is urgent to develop a material that can effectively utilize the glass fiber powder of discarded wind turbine blades and significantly improve the wear resistance, rutting resistance and durability of asphalt pavement. Summary of the invention

[0005] In view of this, the purpose of the present invention is to propose a blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material to solve the problems of high cost and poor aging resistance of traditional asphalt pavement anti-rutting agents; low recovery rate and difficult disposal of glass fiber composite materials in discarded wind turbine blades; single modification effect of conventional glass fiber powder modification methods; weak interface bonding between glass fiber and polymer matrix, and stress concentration, etc., to ultimately achieve green recycling of waste resources and significantly improve the performance of asphalt pavement.

[0006] Based on the above purpose, the present invention provides a blade glass fiber recycled RPC type wear-resistant and anti-rutting rubber-plastic composite auxiliary material, which is prepared by the following raw materials in parts by weight: modified recycled polyethylene: 40-60 parts, modified wind turbine blade recycled glass fiber powder: 20-40 parts, rubber powder: 10-20 parts, maleic anhydride grafted polyethylene: 3-8 parts, styrene-butadiene-styrene block copolymer (SBS): 5-10 parts, polyethylene wax: 1-3 parts, calcium powder: 5-10 parts;

[0007] The specific preparation method of the modified recycled polyethylene is as follows:

[0008] (1) Under nitrogen protection, the recycled polyethylene is heated to 160 - 180 °C and stirred for 1 - 3 h. Then, benzoyl peroxide and isocyanatoethyl methacrylate are added, and the mixture is stirred for 1 - 3 h. After cooling to room temperature, methanol is added. After filtration, washing, and drying, isocyanatoethylated recycled polyethylene is obtained.

[0009] (2) The isocyanatoethylated recycled polyethylene obtained in step (1) is mixed with xylene, heated to 100 - 120 °C and continuously stirred for 2 - 4 h. Then, methanol is added, and stirring is continued for 1 - 3 h. While stirring, it is cooled to room temperature. After centrifugation, washing, and drying, modified recycled polyethylene is obtained.

[0010] The specific preparation method of the modified recycled glass fiber powder for wind turbine blades is as follows:

[0011] (a) The recycled glass fiber powder for wind turbine blades is added to an oxalic acid solution, and ultrasonic treatment is carried out at 50 - 60 °C for 25 - 35 min. After filtration, washing, and drying, acid-etched recycled glass fiber powder for wind turbine blades is obtained.

[0012] (b) The acid-etched recycled glass fiber powder for wind turbine blades obtained in step (a) is placed in a low-temperature oxygen plasma treatment device and treated at a power of 200 - 300 w for 5 - 10 min to obtain plasma-activated recycled glass fiber powder for wind turbine blades.

[0013] (c) Isopropyltris(dodecylbenzenesulfonyl) titanate and ethanol are mixed, deionized water is added, and the temperature is raised to 40 - 60 °C and reacted for 2 - 4 h. Then, the plasma-activated recycled glass fiber powder for wind turbine blades obtained in step (b) is added, and the temperature is raised to 80 - 100 °C and reacted for 2 - 4 h. After cooling to room temperature, filtration, washing, and drying are carried out to obtain titanate-modified recycled glass fiber powder for wind turbine blades.

[0014] (d) Diethylenetriaminopropyltrimethoxysilane, the titanate-modified recycled glass fiber powder for wind turbine blades obtained in step (c), and deionized water are mixed, the temperature is raised to 80 - 100 °C and reacted for 5 - 7 h. After filtration, washing, and drying, modified recycled glass fiber powder for wind turbine blades is obtained.

[0015] Preferably, the rubber powder is made from waste tires and has a fineness of 40 - 60 mesh.

[0016] Preferably, the calcium powder refers to the calcium powder for the rubber industry with a fineness of 400 mesh, a whiteness of 93%, and a calcium content of 96%.

[0017] Preferably, the recycled polyethylene in step (1) refers to waste of polyethylene plastic products, such as plastic bags, plastic films, disposable plastic tableware, etc. After being recycled, it is finally obtained through a series of treatment processes, including mixing, grinding, washing, separation, drying and other steps.

[0018] Preferably, the weight ratio of the recycled polyethylene, dibenzoyl peroxide, isocyanatoethyl methacrylate and methanol in step (1) is 1-3:0.01-0.06:0.1-0.6:15-25.

[0019] Preferably, the weight ratio of the isocyanated recycled polyethylene, xylene and methanol in step (2) is 1-3:15-25:20-30.

[0020] Preferably, the weight ratio of the recycled glass fiber powder of wind turbine blades and oxalic acid solution in step (a) is 1-3:8-36, and the concentration of the oxalic acid solution is 5%.

[0021] Preferably, the weight ratio of isopropyltri(dodecylbenzenesulfonyl) titanate, plasma-activated recycled glass fiber powder of wind turbine blades, ethanol and deionized water in step (c) is 0.1-0.3:1-3:15-25:8-12.

[0022] Preferably, the weight ratio of diethylenetriaminopropyltrimethoxysilane, titanate-modified recycled glass fiber powder of wind turbine blades and deionized water in step (d) is 0.1-0.3:1-3:15-25.

[0023] Furthermore, the present invention also provides a preparation method of the above-mentioned rubber-plastic composite auxiliary material for wear resistance and rutting resistance of recycled glass fiber of blades, and the specific preparation process is as follows:

[0024] S1: Mix and stir evenly the modified recycled polyethylene, modified recycled glass fiber powder of wind turbine blades, rubber powder, maleic anhydride grafted polyethylene, styrene-butadiene-styrene block copolymer (SBS), polyethylene wax and calcium powder to obtain a mixture.

[0025] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion.

[0026] S3: Cool the product extruded in step S2 with water, dry it with air, and cut it to obtain a rubber-plastic composite auxiliary material for wear resistance and rutting resistance of recycled glass fiber of blades.

[0027] Preferably, the temperatures of each zone in the twin-screw extruder in step S2 are: feeding zone: 100-140 °C, melting zone: 170-190 °C, mixing zone: 160-180 °C, metering zone: 190-200 °C.

[0028] Preferably, in step S2, the head temperature of the twin-screw extruder is 185°C, and the screw speed is 180 - 220 rpm.

[0029] Advantages of the present invention:

[0030] 1. Significantly improve the road performance: The material significantly enhances the performance of asphalt mixtures. It can optimize the internal structure of asphalt mixtures, strengthen the skeleton effect, greatly improve the rutting resistance of the road surface under vehicle loads, reduce rutting diseases, and ensure smooth driving. In low-temperature environments, it can improve the flexibility of asphalt mixtures, enhance their crack resistance, and reduce the possibility of cracks on the road surface. Moreover, the material can enhance the wear resistance of the road surface, reduce wear and tear, and extend the service life of the road. At the same time, it also enhances the adhesion between asphalt and aggregates, improves water stability, reduces the damage of water to the road surface, and comprehensively improves the road surface quality.

[0031] 2. Promote the recycling of resources: The present invention finds a new way for waste resources. The treatment of waste wind turbine blades and waste tires has always been a difficult problem. In the past, they were mostly discarded or landfilled, which not only wasted resources but also polluted the environment. The present invention turns these waste materials into treasures, using the recycled glass fiber powder of wind turbine blades and waste tire rubber powder to prepare the rubber-plastic composite auxiliary material. This not only reduces the emission of waste materials, relieves the environmental pressure, but also realizes the recycling of resources, conforms to the concept of green development, and provides a new practical example for sustainable development.

[0032] 3. Have economic cost advantages: Economically, the present invention has obvious advantages. On the one hand, using waste materials to prepare auxiliary materials greatly reduces the raw material cost and improves the profit margin of enterprises. On the other hand, because the material significantly improves the road surface performance, the frequency of road maintenance and replacement is significantly reduced. Road maintenance costs are high and affect traffic. After using this material, these costs and losses are reduced. In the long run, both the preparation of materials in the early stage and the road maintenance in the later stage can save a large amount of funds, and it has good economic prospects in the field of road construction and maintenance. Specific embodiments

[0033] To make the purpose, technical solutions and advantages of the present invention clearer and more understandable, the following further details the present invention in combination with specific embodiments.

[0034] Example 1: A specific preparation method of modified recycled polyethylene is as follows:

[0035] (1) Under nitrogen protection, heat 500 g of recycled polyethylene to 160°C and stir for 1 h, add 5 g of benzoyl peroxide and 50 g of isocyanatoethyl methacrylate, stir for 1 h, cool to room temperature, add 7.5 L of methanol, filter, wash, and dry to obtain isocyanatoethylated recycled polyethylene;

[0036] (2) Mix 500 g of isocyanated recycled polyethylene obtained in step (1) with 7.5 L of xylene, heat up to 100 °C and continuously stir for 2 h, then add 10 L of methanol, continue stirring for 1 h, keep stirring and cool to room temperature, and obtain modified recycled polyethylene after centrifugation, washing and drying;

[0037] The specific preparation method of a modified wind turbine blade recycled glass fiber powder is as follows:

[0038] (a) Add 250 g of wind turbine blade recycled glass fiber powder to 2 L of 5% oxalic acid solution, perform ultrasonic treatment at 50 °C for 25 min, and obtain acid-etched wind turbine blade recycled glass fiber powder after filtration, washing and drying;

[0039] (b) Place 250 g of the acid-etched wind turbine blade recycled glass fiber powder obtained in step (a) in a low-temperature oxygen plasma treatment device, and treat it at a power of 200 w for 5 min to obtain plasma-activated wind turbine blade recycled glass fiber powder;

[0040] (c) Mix 25 g of isopropyltris(dodecylbenzenesulfonyl) titanate with 3.75 L of ethanol, add 2 L of deionized water, heat up to 40 °C, react for 2 h, then add 250 g of the plasma-activated wind turbine blade recycled glass fiber powder obtained in step (b), heat up to 80 °C, react for 2 h, cool to room temperature, and obtain titanate-modified wind turbine blade recycled glass fiber powder after filtration, washing and drying;

[0041] (d) Mix 25 g of diethylenetriaminepropyltrimethoxysilane, 250 g of the titanate-modified wind turbine blade recycled glass fiber powder obtained in step (c) and 3.75 L of deionized water, heat up to 80 °C, react for 5 h, and obtain modified wind turbine blade recycled glass fiber powder after filtration, washing and drying.

[0042] The specific preparation process of a blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material is as follows:

[0043] S1: Mix 400 g of modified recycled polyethylene, 200 g of modified wind turbine blade recycled glass fiber powder, 100 g of 40-mesh rubber powder, 30 g of maleic anhydride grafted polyethylene, 50 g of styrene-butadiene-styrene block copolymer (SBS), 10 g of polyethylene wax and 50 g of calcium powder evenly to obtain a mixture;

[0044] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are: feeding zone: 100 °C, melting zone: 170 °C, mixing zone: 160 °C, metering zone: 190 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 180 rpm;

[0045] S3: Cooling the product extruded in step S2 with water, drying it, and cutting it to obtain a blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material.

[0046] Example 2: A specific preparation method of modified recycled polyethylene is as follows:

[0047] (1) Under nitrogen protection, 500 g of regenerated polyethylene was heated to 170° C. and stirred for reaction for 2 h, 10 g of dibenzoyl peroxide and 100 g of methacrylate isocyanate were added, and the mixture was stirred for reaction for 2 h. The mixture was cooled to room temperature, 5 L of methanol was added, and the mixture was filtered, washed, and dried to obtain isocyanate-treated regenerated polyethylene;

[0048] (2) 500 g of the isocyanate-treated regenerated polyethylene obtained in step (1) and 5 L of xylene were mixed, the temperature was raised to 110° C. and stirred for 3 h, 6.25 L of methanol was added, and the mixture was stirred for 2 h. The mixture was cooled to room temperature while being stirred, and the modified regenerated polyethylene was obtained after centrifugation, washing, and drying;

[0049] A specific preparation method of modified wind turbine blade regenerated glass fiber powder is as follows:

[0050] (a) adding 500 g of wind turbine blade regenerated glass fiber powder into 5 L of 5% oxalic acid solution, ultrasonically treating at 55° C. for 30 min, filtering, washing, and vacuum drying at 80° C. for 5 h to obtain acid-etched wind turbine blade regenerated glass fiber powder;

[0051] (b) placing 500 g of the acid-etched wind turbine blade regenerated glass fiber powder obtained in step (a) in a low-temperature oxygen plasma treatment device and treating it at a power of 250 w for 7.5 min to obtain plasma-activated wind turbine blade regenerated glass fiber powder;

[0052] (c) 50 g of isopropyl tri(dodecylbenzenesulfonyl) titanate and 5 L of ethanol were mixed, 2.5 L of deionized water was added, the temperature was raised to 50° C., the reaction was carried out for 3 h, and then 500 g of plasma-activated wind turbine blade regenerated glass fiber powder obtained in step (b) was added, the temperature was raised to 90° C., the reaction was carried out for 3 h, the mixture was cooled to room temperature, filtered, washed, and dried to obtain titanate-modified wind turbine blade regenerated glass fiber powder;

[0053] (d) Mix 50 g of diethylenetriaminopropyltrimethoxysilane, 500 g of the titanate-modified wind turbine blade regenerated glass fiber powder obtained in step (c) and 5 L of deionized water, heat to 90° C., react for 6 h, filter, wash and dry to obtain the modified wind turbine blade regenerated glass fiber powder.

[0054] The specific preparation process of a blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material is as follows:

[0055] S1: Mix 500 g of modified recycled polyethylene, 300 g of modified recycled glass fiber powder from wind turbine blades, 150 g of 50-mesh rubber powder, 55 g of maleic anhydride grafted polyethylene, 70 g of styrene-butadiene-styrene block copolymer (SBS), 20 g of polyethylene wax, and 75 g of calcium powder evenly by stirring to obtain a mixture.

[0056] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are as follows: feeding zone: 120 °C, melting zone: 180 °C, mixing zone: 170 °C, metering zone: 195 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 200 rpm.

[0057] S3: After water cooling, air drying, and cutting the product extruded in step S2, a rubber-plastic composite auxiliary material with wear resistance and rutting resistance for blades and glass fiber regeneration RPC is obtained.

[0058] Example 3: A specific preparation method of modified recycled polyethylene is as follows:

[0059] (1) Under nitrogen protection, heat 600 g of recycled polyethylene to 180 °C and stir for 3 h. Add 12 g of dibenzoyl peroxide and 120 g of isocyanatoethyl methacrylate, stir for 3 h, cool to room temperature, add 5 L of methanol, filter, wash, and dry to obtain isocyanatoesterified recycled polyethylene.

[0060] (2) Mix 600 g of the isocyanatoesterified recycled polyethylene obtained in step (1) with 5 L of xylene, heat to 120 °C and stir continuously for 4 h, then add 6 L of methanol, continue stirring for 3 h, keep stirring and cool to room temperature, centrifuge, wash, and dry to obtain modified recycled polyethylene.

[0061] A specific preparation method of modified recycled glass fiber powder from wind turbine blades is as follows:

[0062] (a) Add 450 g of recycled glass fiber powder from wind turbine blades to 5.4 L of 5% oxalic acid solution, perform ultrasonic treatment at 60 °C for 35 min, filter, wash, and dry to obtain acid-etched recycled glass fiber powder from wind turbine blades.

[0063] (b) Place 450 g of the acid-etched recycled glass fiber powder from wind turbine blades obtained in step (a) in a low-temperature oxygen plasma treatment device and treat it at a power of 300 w for 10 min to obtain plasma-activated recycled glass fiber powder from wind turbine blades.

[0064] (c) Mix 45 g of isopropyltris(dodecylbenzenesulfonyl) titanate with 3.75 L of ethanol, add 1.8 L of deionized water, heat up to 60 °C, react for 4 h, then add 450 g of the plasma-activated regenerated glass fiber powder of wind turbine blades obtained in step (b), heat up to 100 °C, react for 4 h, cool to room temperature, filter, wash, and dry to obtain the titanate-modified regenerated glass fiber powder of wind turbine blades;

[0065] (d) Mix 45 g of diethylenetriaminepropyltrimethoxysilane, 450 g of the titanate-modified regenerated glass fiber powder of wind turbine blades obtained in step (c), and 3.75 L of deionized water, heat up to 100 °C, react for 7 h, filter, wash, and dry to obtain the modified regenerated glass fiber powder of wind turbine blades.

[0066] The specific preparation process of a blade glass fiber regenerated RPC type wear-resistant and rut-resistant rubber-plastic composite auxiliary material is as follows:

[0067] S1: Mix 600 g of modified recycled polyethylene, 400 g of modified regenerated glass fiber powder of wind turbine blades, 200 g of 60-mesh rubber powder, 80 g of maleic anhydride-grafted polyethylene, 100 g of styrene-butadiene-styrene block copolymer (SBS), 30 g of polyethylene wax, and 100 g of calcium powder evenly by stirring to obtain a mixed material;

[0068] S2: Add the mixed material in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are: feeding zone: 140 °C, melting zone: 190 °C, mixing zone: 180 °C, metering zone: 200 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 220 rpm;

[0069] S3: Cool the product extruded in step S2 with water, dry it by blowing, and cut it to obtain a blade glass fiber regenerated RPC type wear-resistant and rut-resistant rubber-plastic composite auxiliary material.

[0070] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that the modified recycled polyethylene is not subjected to isocyanation treatment. The specific steps are as follows: The specific preparation method of a modified recycled polyethylene is as follows: Mix 500 g of recycled polyethylene with 5 L of xylene, heat up to 110 °C and stir continuously for 3 h, then add 6.25 L of methanol, continue to stir for 2 h, keep stirring and cool to room temperature, centrifuge, wash, and dry to obtain the modified recycled polyethylene;

[0071] The specific preparation method of a modified regenerated glass fiber powder of wind turbine blades is as follows:

[0072] (a) Add 500 g of recycled glass fiber powder from wind turbine blades to 5 L of 5% oxalic acid solution, ultrasonically treat at 55 °C for 30 min, filter, wash, and vacuum dry at 80 °C for 5 h to obtain acid-etched recycled glass fiber powder from wind turbine blades;

[0073] (b) Place 500 g of the acid-etched recycled glass fiber powder from wind turbine blades obtained in step (a) in a low-temperature oxygen plasma treatment device, and treat it at a power of 250 w for 7.5 min to obtain plasma-activated recycled glass fiber powder from wind turbine blades;

[0074] (c) Mix 50 g of isopropyltri(dodecylbenzenesulfonyl) titanate with 5 L of ethanol, add 2.5 L of deionized water, heat to 50 °C, react for 3 h, then add 500 g of the plasma-activated recycled glass fiber powder from wind turbine blades obtained in step (b), heat to 90 °C, react for 3 h, cool to room temperature, filter, wash, and dry to obtain titanate-modified recycled glass fiber powder from wind turbine blades;

[0075] (d) Mix 50 g of diethylenetriaminepropyltrimethoxysilane, 500 g of the titanate-modified recycled glass fiber powder from wind turbine blades obtained in step (c), and 5 L of deionized water, heat to 90 °C, react for 6 h, filter, wash, and dry to obtain modified recycled glass fiber powder from wind turbine blades.

[0076] The specific preparation process of a leaf glass fiber recycled RPC-type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material is as follows:

[0077] S1: Mix 500 g of modified recycled polyethylene, 300 g of modified recycled glass fiber powder from wind turbine blades, 150 g of 50-mesh rubber powder, 55 g of maleic anhydride-grafted polyethylene, 70 g of styrene-butadiene-styrene block copolymer (SBS), 20 g of polyethylene wax, and 75 g of calcium powder evenly to obtain a mixture;

[0078] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are: feeding zone: 120 °C, melting zone: 180 °C, mixing zone: 170 °C, metering zone: 195 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 200 rpm;

[0079] S3: Cool, dry, and cut the product extruded in step S2 to obtain a leaf glass fiber recycled RPC-type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material.

[0080] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that diethylenetriaminepropyltrimethoxysilane is not added. The specific steps are as follows: The specific preparation method of a modified recycled polyethylene is as follows:

[0081] (1) Under nitrogen protection, heat 500 g of recycled polyethylene to 170 °C and stir for 2 h. Add 10 g of benzoyl peroxide and 100 g of isocyanatoethyl methacrylate, stir for 2 h, cool to room temperature, add 5 L of methanol, filter, wash, and dry to obtain isocyanato-functionalized recycled polyethylene.

[0082] (2) Mix 500 g of the isocyanato-functionalized recycled polyethylene obtained in step (1) with 5 L of xylene, heat to 110 °C and stir continuously for 3 h. Then add 6.25 L of methanol, continue to stir for 2 h, keep stirring and cool to room temperature, centrifuge, wash, and dry to obtain modified recycled polyethylene.

[0083] A specific preparation method of modified wind turbine blade recycled glass fiber powder is as follows:

[0084] (a) Add 500 g of wind turbine blade recycled glass fiber powder to 5 L of 5% oxalic acid solution, perform ultrasonic treatment at 55 °C for 30 min, filter, wash, and vacuum dry at 80 °C for 5 h to obtain acid-etched wind turbine blade recycled glass fiber powder.

[0085] (b) Place 500 g of the acid-etched wind turbine blade recycled glass fiber powder obtained in step (a) in a low-temperature oxygen plasma treatment device and treat it at a power of 250 w for 7.5 min to obtain plasma-activated wind turbine blade recycled glass fiber powder.

[0086] (c) Mix 50 g of isopropyltri(dodecylbenzenesulfonyl) titanate with 5 L of ethanol, add 2.5 L of deionized water, heat to 50 °C, react for 3 h. Then add 500 g of the plasma-activated wind turbine blade recycled glass fiber powder obtained in step (b), heat to 90 °C, react for 3 h, cool to room temperature, filter, wash, and dry to obtain modified wind turbine blade recycled glass fiber powder.

[0087] A specific preparation process of a blade glass fiber recycled RPC-type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material is as follows:

[0088] S1: Mix 500 g of modified recycled polyethylene, 300 g of modified wind turbine blade recycled glass fiber powder, 150 g of 50-mesh rubber powder, 55 g of maleic anhydride-grafted polyethylene, 70 g of styrene-butadiene-styrene block copolymer (SBS), 20 g of polyethylene wax, and 75 g of calcium powder evenly to obtain a mixture.

[0089] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are: feeding zone: 120 °C, melting zone: 180 °C, mixing zone: 170 °C, metering zone: 195 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 200 rpm.

[0090] S3: Cooling the product extruded in step S2 with water, drying it, and cutting it to obtain a blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material.

[0091] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that isopropyl tri(dodecylbenzenesulfonyl) titanate is replaced by n-nonyl titanium oxide. The specific steps are as follows: A specific preparation method of a modified recycled polyethylene is as follows:

[0092] (1) Under nitrogen protection, 500 g of regenerated polyethylene was heated to 170° C. and stirred for reaction for 2 h, 10 g of dibenzoyl peroxide and 100 g of methacrylate isocyanate were added, and the mixture was stirred for reaction for 2 h. The mixture was cooled to room temperature, 5 L of methanol was added, and the mixture was filtered, washed, and dried to obtain isocyanate-treated regenerated polyethylene;

[0093] (2) 500 g of the isocyanate-treated regenerated polyethylene obtained in step (1) and 5 L of xylene were mixed, the temperature was raised to 110° C. and stirred for 3 h, 6.25 L of methanol was added, and the mixture was stirred for 2 h. The mixture was cooled to room temperature while being stirred, and the modified regenerated polyethylene was obtained after centrifugation, washing, and drying;

[0094] A specific preparation method of modified wind turbine blade regenerated glass fiber powder is as follows:

[0095] (a) adding 500 g of wind turbine blade regenerated glass fiber powder into 5 L of 5% oxalic acid solution, ultrasonically treating at 55° C. for 30 min, filtering, washing, and vacuum drying at 80° C. for 5 h to obtain acid-etched wind turbine blade regenerated glass fiber powder;

[0096] (b) placing 500 g of the acid-etched wind turbine blade regenerated glass fiber powder obtained in step (a) in a low-temperature oxygen plasma treatment device and treating it at a power of 250 w for 7.5 min to obtain plasma-activated wind turbine blade regenerated glass fiber powder;

[0097] (c) 50 g of n-nonyl titanium oxide and 5 L of ethanol were mixed, 2.5 L of deionized water was added, the temperature was raised to 50 ° C, the reaction was carried out for 3 h, and then 500 g of plasma-activated wind turbine blade regenerated glass fiber powder obtained in step (b) was added, the temperature was raised to 90 ° C, the reaction was carried out for 3 h, and the mixture was cooled to room temperature, filtered, washed, and dried to obtain titanate-modified wind turbine blade regenerated glass fiber powder;

[0098] (d) Mix 50 g of diethylenetriaminopropyltrimethoxysilane, 500 g of the titanate-modified wind turbine blade regenerated glass fiber powder obtained in step (c) and 5 L of deionized water, heat to 90° C., react for 6 h, filter, wash and dry to obtain the modified wind turbine blade regenerated glass fiber powder.

[0099] The specific preparation process of a rubber-plastic composite auxiliary material with wear resistance and rutting resistance for leaf glass fiber regeneration RPC is as follows:

[0100] S1: Mix 500 g of modified recycled polyethylene, 300 g of modified wind turbine blade recycled glass fiber powder, 150 g of 50-mesh rubber powder, 55 g of maleic anhydride grafted polyethylene, 70 g of styrene-butadiene-styrene block copolymer (SBS), 20 g of polyethylene wax, and 75 g of calcium powder evenly by stirring to obtain a mixture;

[0101] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are as follows: feeding zone: 120 °C, melting zone: 180 °C, mixing zone: 170 °C, metering zone: 195 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 200 rpm;

[0102] S3: After water cooling, air drying, and cutting the product extruded in step S2, a rubber-plastic composite auxiliary material with wear resistance and rutting resistance for leaf glass fiber regeneration RPC is obtained.

[0103] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that diethylenetriaminepropyltrimethoxysilane is replaced by 3-aminopropyltrimethoxysilane. The specific steps are as follows: The specific preparation method of a modified recycled polyethylene is as follows:

[0104] (1) Under nitrogen protection, heat 500 g of recycled polyethylene to 170 °C and stir for 2 h, add 10 g of dibenzoyl peroxide and 100 g of isocyanatoethyl methacrylate, stir for 2 h, cool to room temperature, add 5 L of methanol, filter, wash, and dry to obtain isocyanatoesterified recycled polyethylene;

[0105] (2) Mix 500 g of the isocyanatoesterified recycled polyethylene obtained in step (1) with 5 L of xylene, heat to 110 °C and stir continuously for 3 h, then add 6.25 L of methanol, continue to stir for 2 h, keep stirring and cool to room temperature, centrifuge, wash, and dry to obtain modified recycled polyethylene;

[0106] The specific preparation method of a modified wind turbine blade recycled glass fiber powder is as follows:

[0107] (a) Add 500 g of wind turbine blade recycled glass fiber powder to 5 L of 5% oxalic acid solution, perform ultrasonic treatment at 55 °C for 30 min, filter, wash, and vacuum dry at 80 °C for 5 h to obtain acid-etched wind turbine blade recycled glass fiber powder;

[0108] (b) Place the 500 g of acid-etched recycled glass fiber powder of wind turbine blades obtained in step (a) in a low-temperature oxygen plasma treatment device, and treat it at a power of 250 w for 7.5 min to obtain plasma-activated recycled glass fiber powder of wind turbine blades;

[0109] (c) Mix 50 g of isopropyltris(dodecylbenzenesulfonyl) titanate and 5 L of ethanol, add 2.5 L of deionized water, heat up to 50 °C, react for 3 h, then add the 500 g of plasma-activated recycled glass fiber powder of wind turbine blades obtained in step (b), heat up to 90 °C, react for 3 h, cool to room temperature, filter, wash, and dry to obtain titanate-modified recycled glass fiber powder of wind turbine blades.

[0110] (d) Mix 50 g of 3-aminopropyltrimethoxysilane, 500 g of the titanate-modified recycled glass fiber powder of wind turbine blades obtained in step (c), and 5 L of deionized water, heat up to 90 °C, react for 6 h, filter, wash, and dry to obtain modified recycled glass fiber powder of wind turbine blades.

[0111] The specific preparation process of a leaf glass fiber recycled RPC-type wear-resistant and rut-resistant rubber-plastic composite auxiliary material is as follows:

[0112] S1: Mix 500 g of modified recycled polyethylene, 300 g of modified recycled glass fiber powder of wind turbine blades, 150 g of 50-mesh rubber powder, 55 g of maleic anhydride grafted polyethylene, 70 g of styrene-butadiene-styrene block copolymer (SBS), 20 g of polyethylene wax, and 75 g of calcium powder evenly to obtain a mixture;

[0113] S2: Add the mixture in step S1 to a twin-screw extruder for melt extrusion. The temperatures of each zone in the twin-screw extruder are: feeding zone: 120 °C, melting zone: 180 °C, mixing zone: 170 °C, metering zone: 195 °C, the temperature of the twin-screw extruder head is 185 °C, and the screw speed is 200 rpm;

[0114] S3: Cool, dry, and cut the product extruded in step S2 to obtain a leaf glass fiber recycled RPC-type wear-resistant and rut-resistant rubber-plastic composite auxiliary material.

[0115] Performance testing

[0116] Design basis and test standards for asphalt mixture mix design

[0117] (1) "Technical Specifications for Highway Asphalt Pavement Construction" (JTG F40-2004)

[0118] (2) "Test Procedures for Highway Engineering Aggregates" (JTG 3432-2024)

[0119] (3) "Testing Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011)

[0120] The asphalt in the asphalt mixture is A-grade 70# asphalt, and the added reinforcing agent is blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material. The indoor test mixing temperature is 180°C, the specimen molding temperature is 165°C, and the asphalt mixture ratio is shown in Table 1:

[0121] Table 1 Asphalt mixture ratio

[0122]

[0123] The blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary materials prepared in Examples 1-3 and Comparative Examples 1-4 were respectively used to prepare test specimens according to the asphalt mixture proportions in Table 1 and the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011).

[0124] Rutting test: Use HYCZ-1 fully automatic asphalt mixture rutting tester to test each specimen in accordance with the "Highway Engineering Asphalt and Asphalt Mixture Test Procedure" (JTG E20-2011). Read the rutting deformation d1 and d2 at 45min (t1) and 60min (t2) with an accuracy of 0.01mm. The dynamic stability of the asphalt mixture specimen is calculated as follows:

[0125] Where: DS—dynamic stability of asphalt mixture (times / mm);

[0126] d1—deformation corresponding to time t1 (mm);

[0127] d2—deformation corresponding to time t2 (mm);

[0128] C1—Testing machine type coefficient, the crank connecting rod drives the loading wheel to and fro operation mode is 1.0;

[0129] C2—specimen coefficient, the test specimen with a length and width of 300 mm prepared in the laboratory is 1.0;

[0130] N is the reciprocating rolling speed of the test wheel, usually 42 times / min. The experimental results are shown in Table 2.

[0131] Low temperature bending test: A universal material testing machine was used to test each specimen in accordance with the “Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering” (JTG E20-2011), and the low temperature bending failure strain of each specimen was recorded. The experimental results are shown in Table 2.

[0132] Abrasion resistance experiment: Mix the mixtures of Examples 1-3 and Comparative Examples 1-4 evenly according to the asphalt mixture mix ratio in Table 1. Under the conditions of a mixing temperature of 180 °C and a forming temperature of 165 °C, make cylindrical specimens with a diameter of 100 mm and a height of 50 mm. Dry them in an oven at 60 °C until they reach a constant weight. After taking them out and cooling them to room temperature, weigh the initial mass m of the specimens with an electronic balance 0 , accurate to 0.01 g. Put the specimens into the cylinder of the Los Angeles abrasion testing machine, and at the same time add 12 steel balls with a diameter of 46.8 mm. Set the parameters of the testing machine, with a rotation speed of 30-35 r / min and a rotation number of 500 times. Start the testing machine to conduct the abrasion test. After the test is over, take out the specimens, gently brush off the debris on the surface with a brush, and then blow them clean with a hair dryer. Put the specimens into the oven again, dry them at 60 °C until they reach a constant weight. After taking them out and cooling them to room temperature, weigh the mass m after abrasion with an electronic balance 1 , accurate to 0.01 g, and calculate the abrasion loss Q of the specimens. The calculation formula is Q = (m 0 - m 1 ) / m 0 × 100%. The experimental results are shown in Table 2.

[0133] Water stability experiment: Use an automatic Marshall test instrument to conduct experiments on each specimen in accordance with the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011), and record the freeze-thaw splitting strength of each specimen. The experimental results are shown in Table 2.

[0134] Table 2 Performance test results

[0135]

[0136] Data analysis: It can be seen from Examples 1-3 in Table 2 that the asphalt mixture prepared by using the leaf glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material of the present invention as a reinforcing agent has excellent rutting resistance, good low-temperature performance, good abrasion resistance, and strong water stability.

[0137] It can be seen from Comparative Example 1 and Example 2 in Table 2 that the asphalt mixture prepared by using the leaf glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material as a reinforcing agent in the present invention has the advantages of better rutting resistance, better low-temperature performance, better wear resistance, and stronger water stability. This may be because after the modified recycled polyethylene is isocyanated, in the high-temperature environment of the twin-screw extruder, the isocyanate groups introduced on its molecular chain can chemically react with the hydroxyl groups on the surface of the modified glass fiber powder and the amino groups on the silane coupling agent, so that they are tightly bonded together by chemical bonds. This chemical bonding method is more effective and stable than ordinary physical mixing. It can build a more stable network structure inside the material and enhance the overall mechanical properties of the material. When subjected to vehicle load, this stable structure can effectively resist deformation and improve rutting resistance; in a low-temperature environment, the presence of chemical bonds enhances the interaction between molecular chains, making the material more flexible, reducing the risk of brittle fracture, and improving low-temperature performance. At the same time, the tight chemical bonding makes the material surface denser, improving wear resistance; and it can effectively prevent water intrusion and improve the water stability of the material.

[0138] It can be seen from Comparative Example 2 and Example 2 in Table 2 that the asphalt mixture prepared by using the leaf glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material as a reinforcing agent in the present invention has better performance in all aspects. This may be because the silane coupling agent condenses with the hydroxyl groups on the surface of the glass fiber to form Si-O-Si bonds, thus forming a bridge between the glass fiber powder and the polymer matrix and enhancing the interfacial bonding force between the two. This enhanced interfacial bonding force helps to build a more stable structure inside the material; at the same time, the amino groups of the silane coupling agent react with the isocyanate groups of the recycled polyethylene to form a crosslinked network, further improving the bonding firmness between the recycled polyethylene and the glass fiber powder; finally, the amino groups form hydrogen bonds with the polar groups of the polymer matrix, such as the styrene segments of SBS, enhancing the stress conduction efficiency of the material. In Comparative Example 2, due to the lack of silane coupling agent, the glass fiber and the matrix only rely on the physical adsorption of titanate, and the interfacial bonding force is weak, resulting in stress concentration and uneven dispersion, and ultimately a significant decline in performance.

[0139] As can be seen from Comparative Example 3 and Example 2 in Table 2, the asphalt mixture prepared by the present invention using the leaf glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material as a reinforcing agent has more advantages in terms of rutting resistance, low-temperature performance, wear resistance and water stability. This may be because the introduction of the rigid structure of the benzene ring is lacking. Isopropyl tris(dodecylbenzenesulfonyl) titanate contains the rigid structure of the benzene ring, which can enhance the interaction between the modified wind turbine blade recycled glass fiber powder and the polymer matrix. The rigidity of the benzene ring forms a more regular structure inside the material. Under the action of vehicle loads, this structure can effectively resist deformation and improve rutting resistance; at low temperatures, the benzene ring can restrict the excessive movement of molecular chains, avoid material embrittlement and enhance low-temperature performance. At the same time, the rigid structure improves the overall strength of the material, making it more wear-resistant during the friction process; it can also optimize the internal structure of the material, reduce the channels for water intrusion and enhance water stability. However, Comparative Example 3 lacks the rigid structure of the benzene ring, the regularity of the internal structure of the material becomes worse, and the interaction between the components weakens, resulting in inferior performance in the above aspects compared with Example 2.

[0140] As can be seen from Comparative Example 4 and Example 2 in Table 2, the asphalt mixture prepared by the present invention using the leaf glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material as a reinforcing agent has more excellent comprehensive performance. This may be because diethylenetriaminepropyltrimethoxysilane contains multiple amino groups, which can react with the isocyanate groups in multiple modified recycled polyethylenes at the same time to form a high-density cross-linked network. The formation of the high-density cross-linked structure enhances the network structure inside the material, can effectively disperse stress and improve rutting resistance; at the same time, the high-density cross-linked structure can restrict the movement of molecular chains, increase the flexibility of the material, reduce the risk of brittle fracture and enhance low-temperature performance; and the high-density cross-linked structure makes the material as a whole more dense, reduces the particle shedding during the wear process and enhances wear resistance; finally, the high-density cross-linked structure can effectively prevent the penetration of water and improve the water stability of the material. However, in Comparative Example 4, diethylenetriaminepropyltrimethoxysilane is replaced by 3-aminopropyltrimethoxysilane, and the number of its amino groups is relatively small, and the cross-linking effect is not as good as that of diethylenetriaminepropyltrimethoxysilane, resulting in a decline in the comprehensive performance of the material.

[0141] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is only exemplary 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 can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material, characterized in that: The invention comprises the following raw materials in parts by weight: modified recycled polyethylene: 40-60 parts, modified wind turbine blade recycled glass fiber powder: 20-40 parts, rubber powder: 10-20 parts, maleic anhydride grafted polyethylene: 3-8 parts, styrene-butadiene-styrene block copolymer (SBS): 5-10 parts, polyethylene wax: 1-3 parts, calcium powder: 5-10 parts; The specific preparation method of the modified recycled polyethylene is as follows: (1) heating the regenerated polyethylene to 160-180° C. under nitrogen protection, stirring and reacting for 1-3 hours, adding dibenzoyl peroxide and methacrylate isocyanate, stirring and reacting for 1-3 hours, cooling to room temperature, adding methanol, filtering, washing, and drying to obtain isocyanate-treated regenerated polyethylene; (2) mixing the isocyanate-treated regenerated polyethylene obtained in step (1) with xylene, heating to 100-120° C. and stirring for 2-4 h, adding methanol, stirring for 1-3 h, cooling to room temperature while stirring, centrifuging, washing, and drying to obtain modified regenerated polyethylene; 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 to an oxalic acid solution, ultrasonically treating at 50-60° C. for 25-35 min, filtering, washing, and drying to obtain acid-etched regenerated glass fiber powder of wind turbine blades; (b) placing the acid-etched wind turbine blade regenerated glass fiber powder obtained in step (a) in a low-temperature oxygen plasma treatment device, treating it at a power of 200-300w for 5-10min to obtain plasma-activated wind turbine blade regenerated glass fiber powder; (c) mixing isopropyl tri(dodecylbenzenesulfonyl) titanate and ethanol, adding deionized water, heating to 40-60° C., reacting for 2-4 hours, adding the plasma-activated wind turbine blade regenerated glass fiber powder obtained in step (b), heating to 80-100° C., reacting for 2-4 hours, cooling to room temperature, filtering, washing, and drying to obtain titanate-modified wind turbine blade regenerated glass fiber powder; (d) Mixing diethylenetriaminopropyltrimethoxysilane, the titanate-modified wind turbine blade regenerated glass fiber powder obtained in step (c) and deionized water, heating to 80-100° C., reacting for 5-7 hours, filtering, washing and drying to obtain the modified wind turbine blade regenerated glass fiber powder.

2. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1 is characterized in that: The rubber powder is processed from waste tires and has a fineness of 40-60 meshes.

3. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: The calcium powder refers to calcium powder for use in the rubber industry with a fineness of 400 meshes, a whiteness of 93%, and a calcium content of 96%.

4. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: The recycled polyethylene in step (1) refers to waste polyethylene plastic products, such as plastic bags, plastic films, disposable plastic tableware, etc., which are recycled and then go through a series of processing processes, including mixing, grinding, washing, separation, drying and other steps to finally obtain.

5. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: In the step (1), the weight ratio of the regenerated polyethylene, dibenzoyl peroxide, methacrylate isocyanate and methanol is 1-3:0.01-0.06:0.1-0.6:15-25.

6. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: In the step (2), the weight ratio of the isocyanate-regenerated polyethylene, xylene and methanol is 1-3:15-25:20-30.

7. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: 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, and the concentration of the oxalic acid solution is 5%.

8. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: In the step (c), the weight ratio of isopropyl tri(dodecylbenzenesulfonyl) titanate, plasma activated wind turbine blade regenerated glass fiber powder, ethanol and deionized water is 0.1-0.3:1-3:15-25:8-12.

9. The blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to claim 1, characterized in that: In the step (d), the weight ratio of diethylenetriaminopropyltrimethoxysilane, titanate-modified wind turbine blade regenerated glass fiber powder and deionized water is 0.1-0.3:1-3:15-25.

10. A method for preparing a blade glass fiber recycled RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: mixing and stirring the modified recycled polyethylene, modified wind turbine blade recycled glass fiber powder, rubber powder, maleic anhydride grafted polyethylene, styrene-butadiene-styrene block copolymer (SBS), polyethylene wax and calcium powder to obtain a mixture; S2: adding the mixed material in step S1 to a twin-screw extruder for melt extrusion; S3: Cooling the product extruded in step S2 with water, drying it, and cutting it to obtain a blade glass fiber regeneration RPC type wear-resistant and rutting-resistant rubber-plastic composite auxiliary material; In step S2, the temperature of each zone in the twin-screw extruder is: feeding zone: 100-140°C, melting zone: 170-190°C, mixing zone: 160-180°C, metering zone: 190-200°C, the head temperature of the twin-screw extruder is 185°C, and the screw speed is 180-220rpm.

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