CN118684836B - Wind power blade regeneration composite material and preparation method and application thereof - Google Patents
Wind power blade regeneration composite material and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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Abstract
本发明属于风电叶片材料技术领域，具体涉及一种风电叶片再生复合材料及其制备方法和应用。本发明将风电叶片粒料进行第一辐照，得到活性填料；将所述活性填料、不饱和聚酯树脂和交联增强剂混合，得到混合料；将所述混合料在模具中进行压制，得到预成型坯体；在第二辐照和施压的条件下，将所述预成型坯体进行交联固化，得到所述风电叶片再生复合材料。本发明实现了风电叶片材料的循环利用以及再生复合材料的制备，得到的风电叶片再生复合材料具有优异的力学性能，同时对风电叶片废料的回收再利用具有绿色、高效、对环境友好以及节省资源的优势，具有一定的经济效益和应用价值。The present invention belongs to the technical field of wind turbine blade materials, and specifically relates to a wind turbine blade recycled composite material and a preparation method and application thereof. The present invention subjects wind turbine blade granules to a first irradiation to obtain an active filler; the active filler, an unsaturated polyester resin and a cross-linking enhancer are mixed to obtain a mixture; the mixture is pressed in a mold to obtain a preformed body; under the conditions of a second irradiation and pressure, the preformed body is cross-linked and cured to obtain the wind turbine blade recycled composite material. The present invention realizes the recycling of wind turbine blade materials and the preparation of recycled composite materials. The obtained wind turbine blade recycled composite material has excellent mechanical properties. At the same time, the recycling and reuse of wind turbine blade waste has the advantages of being green, efficient, environmentally friendly and resource-saving, and has certain economic benefits and application value.
Description
Technical Field
The invention belongs to the technical field of wind power blade materials, and particularly relates to a wind power blade regeneration composite material, and a preparation method and application thereof.
Background
Although wind power generation is a clean renewable energy source, the whole unit equipment can generate a large amount of wind power blade wastes which need to be treated after the production process and the retirement. The combination of the reinforcing fiber (mainly glass fiber at present) and the polymer matrix (mainly epoxy resin at present) occupies most of the mass of the wind power blade material, the content of the reinforcing fiber in the wind power blade material is about 60-70wt%, and the content of the polymer matrix is about 30-40wt%. The wind power blade waste is difficult to degrade naturally, has extremely strong pollution, is treated in conventional modes such as random stacking, direct landfill, simple incineration and the like, is not an effective solution, occupies a large amount of land resources, generates secondary pollution and causes serious harm to the environment. Therefore, from the viewpoints of environmental protection and resource utilization, the optimal treatment method for the wind power blade material is recycling.
The related treatment technologies of wind power blade recycling at present comprise a heat recovery method, a chemical recovery method and a physical recovery method, wherein the heat recovery method relates to high-temperature treatment and can be mainly divided into combustion or incineration (only used for energy recovery) and fluidized bed combustion (mainly used for reinforcing fiber) and anaerobic combustion (namely pyrolysis), the heat recovery method can recover energy, oil and filler without using solvents and catalysts, but the size and performance of the recovery materials are correspondingly reduced, the fiber products possibly contain oxidized residues or carbon, cannot be completely harmless, and emissions and carbon dioxide are generated, so that the environment is negatively affected. Among the chemical recovery methods, the solvent recovery method is the main one studied in many cases. The method adopts a solvent to break macromolecular bonds of the resin at a certain temperature and pressure, thereby achieving the purpose of separating and recycling the resin and the glass fiber. Therefore, the recovery of single oligomer and filler is realized, the shape, size, components and mechanical properties of the recovered filler are kept unchanged, but a large amount of organic solvent and catalyst are used in the recovery process, the environment is directly adversely affected by the large amount of volatilization of the organic solvent, and the residual organic solvent is newly increased to form dangerous waste, so that the chemical recovery method is difficult to recycle on a large scale, and a large amount of resources, manpower, material resources and financial resources are consumed for the treatment of the dangerous waste, so that the chemical method is often unrepeatable. The physical recovery method mainly comprises disassembly and reuse and mechanical crushing and comprehensive utilization, and the recovered wind power blade material can be used as a filler or a matrix for producing secondary materials. However, the current physical recovery method is generally to directly add the crushed wind power blade as an inert filler into other base materials for molding and utilization, and the inert filler and the base materials have no acting force, so that the mechanical strength of the base materials is not obviously improved, and even the mechanical properties of the base materials are greatly reduced, which greatly limits the application of the wind power blade regenerated materials.
Disclosure of Invention
The invention aims to provide a wind power blade regeneration composite material, a preparation method and application thereof, and the wind power blade regeneration composite material provided by the invention has excellent mechanical properties, can realize green, efficient and value-added recovery and regeneration of wind power blade waste, is environment-friendly, saves resources, and has certain economic benefit and application value.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a wind power blade regeneration composite material, which comprises the following steps:
carrying out first irradiation on wind power blade granules to obtain active filler;
Mixing the active filler, unsaturated polyester resin and crosslinking reinforcing agent to obtain a mixture; the unsaturated polyester resin comprises one or more of para-benzene unsaturated polyester resin, bisphenol A unsaturated polyester resin and meta-benzene unsaturated polyester resin; the mass ratio of the wind power blade granules to the polyester resin is (1:1) - (7:3); the mass of the crosslinking enhancer accounts for 2-3% of the total mass of the wind power blade granules and the polyester resin;
pressing the mixture in a mould to obtain a preformed blank;
and under the conditions of second irradiation and pressure application, carrying out cross-linking and curing on the preformed blank body to obtain the wind power blade regenerated composite material.
Preferably, the wind power blade granules are obtained by crushing wind power blade materials, and the particle size of the wind power blade granules is 0.2-2 mm.
Preferably, the first irradiation is performed by Co-60 gamma rays, the dose of the first irradiation is 10-300 kGray, and the irradiation time is 3-10 min.
Preferably, the crosslinking enhancer comprises one or more of methyl methacrylate, diallyl phthalate and propane trimethacrylate.
Preferably, the mixing is performed in a mixer, wherein the temperature of the mixing is 60-100 ℃ and the time is 5-10 min.
Preferably, the mixing is performed under stirring, and the stirring speed is 20-30 rad/min.
Preferably, the pressing temperature is 60-100 ℃, the pressing pressure is 5-10 MPa, and the heat preservation and pressure maintaining time is 3-8 min.
Preferably, the second irradiation is performed by Co-60 gamma rays, the dose of the second irradiation is 10-300 kGy, and the irradiation time is 10-25 min; the pressure during crosslinking and curing is 8-10 MPa.
The invention provides the wind power blade regenerated composite material prepared by the preparation method.
The invention provides application of the wind power blade regeneration composite material as an artificial board.
The invention provides a preparation method of a wind power blade regeneration composite material, which comprises the following steps: carrying out first irradiation on wind power blade granules to obtain active filler; mixing the active filler, unsaturated polyester resin and crosslinking reinforcing agent to obtain a mixture; the unsaturated polyester resin comprises one or more of para-benzene unsaturated polyester resin, bisphenol A unsaturated polyester resin and meta-benzene unsaturated polyester resin; the mass ratio of the wind power blade granules to the polyester resin is (1:1) - (7:3); the mass of the crosslinking enhancer accounts for 2-3% of the total mass of the wind power blade granules and the polyester resin; pressing the mixture in a mould to obtain a preformed blank; and under the conditions of second irradiation and pressure application, carrying out cross-linking and curing on the preformed blank body to obtain the wind power blade regenerated composite material. The invention adopts an irradiation method to prepare a high-performance wind power blade regeneration composite material, firstly wind power blade granules are subjected to first irradiation, active free radicals can be generated on a polymer matrix (epoxy resin) molecular chain in the wind power blade granules, and then the active free radicals are converted into active fillers capable of undergoing chemical crosslinking reaction; then, the obtained active filler, unsaturated polyester resin and crosslinking reinforcing agent are mixed to obtain a preformed blank, then, crosslinking and curing are carried out under the conditions of second irradiation and pressure, and under the conditions of second irradiation, the dosage proportion relation of the active filler, the unsaturated polyester resin and the crosslinking reinforcing agent is optimized, the crosslinking reinforcing agent absorbs high-energy radiation and decomposes to generate free radicals, and at the moment, the active free radicals carried on epoxy resin molecular chains in the active filler can act together with the crosslinking reinforcing agent to initiate free radical polymerization of the unsaturated polyester resin, so that in the crosslinking system of the unsaturated polyester, the epoxy molecular chains with the active free radicals also participate in the crosslinking reaction, and the active filler and the crosslinking reinforcing agent participate in the crosslinking system, so that the wind power blade regenerated composite material with a three-dimensional network structure is finally formed, and the mechanical property of the composite material can be obviously enhanced. On the other hand, the method provided by the invention avoids the process of separating the epoxy resin from the reinforcing fiber (glass fiber) in the wind power blade granules, retains the glass fiber component in the composite material, and further improves the mechanical strength of the composite material. In conclusion, the recycling of the wind power blade material and the preparation of the regenerated composite material are realized, the obtained wind power blade regenerated composite material has excellent mechanical properties, and meanwhile, the method has the advantages of being green, efficient, environment-friendly and resource-saving in recycling of wind power blade waste, and has certain economic benefit and application value.
Detailed Description
The invention provides a preparation method of a wind power blade regeneration composite material, which comprises the following steps:
carrying out first irradiation on wind power blade granules to obtain active filler;
Mixing the active filler, unsaturated polyester resin and crosslinking reinforcing agent to obtain a mixture; the unsaturated polyester resin comprises one or more of para-benzene unsaturated polyester resin, bisphenol A unsaturated polyester resin and meta-benzene unsaturated polyester resin; the mass ratio of the wind power blade granules to the polyester resin is (1:1) - (7:3); the mass of the crosslinking enhancer accounts for 2-3% of the total mass of the wind power blade granules and the polyester resin;
pressing the mixture in a mould to obtain a preformed blank;
and under the conditions of second irradiation and pressure application, carrying out cross-linking and curing on the preformed blank body to obtain the wind power blade regenerated composite material.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The method comprises the steps of carrying out first irradiation on wind power blade granules to obtain active filler. In the specific embodiment of the invention, the wind power blade granules are obtained by crushing wind power blade materials, and the wind power blade materials are wind power blade wastes which are generated in the production process and after the retirement of wind power generation unit equipment and need to be treated. In the present invention, the pulverization is preferably performed in a pulverizer, and the operational conditions of the pulverization preferably include: the rotating speed of the main shaft is 4500r/min, the feeding granularity is 6mm, the crushing fineness is 60-150 meshes, and the motor power is 4kW. In a specific embodiment of the present invention, the pulverizer used for pulverizing is a universal pulverizer provided by Jiangsu Chitong mechanical manufacturing Co., ltd, model number 20B.
In the present invention, the pulverization gives a pulverized product. According to the invention, the crushed product obtained after crushing is screened to obtain the wind power blade granules, and in the invention, the screening is preferably carried out by adopting an SDB-200 top impact type vibrating screen. The operating conditions of the screening preferably include: the maximum diameter of the sieve is 200mm, the stacking height of the sieve is 400mm, the radius of gyration is 12.5mm, the shaking frequency of the sieve is 221r/min, the vibration frequency is 147r/min, the vertical amplitude is 5mm, the timing range is 0-60 min, the motor power is 0.37kW, the voltage is 380V, the rotating speed is 2800kg, and the weight is 130kg.
In the invention, the particle size of the wind power blade granules is preferably 0.2-2 mm.
In the invention, the first irradiation is preferably performed by Co-60 gamma rays, and the dose of the first irradiation is preferably 10-300 kGray, more preferably 10-200 kGray, further preferably 10-100 kGray, most preferably 10-20 kGray, and particularly preferably 10kGray, 12kGray, 14kGray or 16kGray; the irradiation time is preferably 3 to 10min, more preferably 5 to 8min, and particularly preferably 5min, 6min, 7min and 8min. In the present invention, in the first irradiation process: active free radicals can be generated on molecular chains of epoxy resin in wind power blade granules, and the obtained active filler can participate in crosslinking reaction of unsaturated matrix materials, so that a three-dimensional network crosslinking structure formed by three systems (unsaturated polyester resin, epoxy resin molecular chains with active free radicals and crosslinking reinforcing agents) is formed in subsequent crosslinking curing reaction.
After the active filler is obtained, the active filler, the unsaturated polyester resin and the crosslinking reinforcing agent are mixed to obtain the mixture. In the present invention, the unsaturated polyester resin preferably includes one or more of a para-type unsaturated polyester resin, a bisphenol a-type unsaturated polyester resin, and an meta-type unsaturated polyester resin. The crosslinking enhancer preferably comprises one or more of methyl methacrylate, diallyl phthalate and propane trimethacrylate, more preferably propane trimethacrylate. The mass ratio of the wind power blade granules to the polyester resin is preferably (1:1) - (7:3), more preferably 1:1, 1.5:1 or 7:3. The weight percentage of the crosslinking enhancer to the total weight of the wind power blade granules and the polyester resin is 1.5-3%, and 3%, 2.5% or 2% is particularly preferred. The mixing is preferably performed in a mixer, the temperature of the mixing is preferably 60-100 ℃, more preferably 60-85 ℃, and the time is preferably 5-10 min. The mixing is performed under stirring, and the stirring rotation speed is preferably 20-30 rad/min.
After the mixture is obtained, the mixture is pressed in a die to obtain a preformed blank. In the present invention, the mold is preferably an aluminum mold. In a subsequent second irradiation process, the irradiated radiation may penetrate the aluminum mold to irradiate the preform in the mold. In the invention, the pressing temperature is preferably 60-100 ℃, and the pressing temperature is preferably consistent with the temperature in the mixing process; the pressure is preferably 5-10 MPa, and particularly preferably 8MPa; the holding time is preferably 3-8 min, and particularly preferably 5min.
The invention can make the mixture fully flow and fill the whole die by pressing.
After the preformed blank is obtained, the preformed blank is subjected to crosslinking and solidification under the conditions of second irradiation and pressure application, and the wind power blade regenerated composite material is obtained. In the present invention, the crosslinking curing process is preferably performed under room temperature conditions. In the invention, the second irradiation is preferably performed by Co-60 gamma rays, and the dose of the second irradiation is preferably 10-300 kGy, more preferably 10-150 kGy, further preferably 10-100 kGy, most preferably 10-50 kGy, and particularly preferably 25kGy, 20kGy, 15kGy or 10kGy; the irradiation time is preferably 10 to 25 minutes, more preferably 10 to 20 minutes, particularly preferably 16 minutes, 14 minutes, 12 minutes or 10 minutes. The pressure of crosslinking and curing is preferably 8-10 MPa, and particularly preferably 8MPa.
In the invention, in the second irradiation process, the monomer in the crosslinking enhancer can absorb radiation energy to decompose to generate free radicals, so that the curing crosslinking reaction of the unsaturated polyester resin is initiated, and in the crosslinking reaction process, the epoxy resin molecular chain (active filler) carrying active free radicals can also be added into the crosslinking reaction of the unsaturated polyester resin, so that a three-dimensional network crosslinking structure formed by three systems (the unsaturated polyester resin, the epoxy resin molecular chain carrying active free radicals and the crosslinking enhancer) is finally formed.
In the invention, after the crosslinking and curing reaction is finished, the mould is opened to take out the target wind power blade regenerated composite material product.
The invention provides the wind power blade regenerated composite material prepared by the preparation method.
The wind power blade regeneration composite material provided by the invention has a three-dimensional network cross-linked structure, contains reinforcing fibers, and has excellent mechanical properties.
The invention provides application of the wind power blade regeneration composite material as an artificial board. The specific application method of the wind power blade regeneration composite material has no special requirements.
Compared with the prior art, the invention has the following remarkable beneficial effects:
the method for preparing the high-performance wind power blade regeneration composite material by adopting the irradiation method avoids the process of separating glass fibers from resin and operation treatment, realizes hundred percent recycling, reduces resource waste and environmental pollution, and greatly saves production cost.
The preparation of the regenerated composite material of the invention forms a novel three-dimensional network crosslinked structure by the crosslinking reaction between the active filler and the unsaturated polyester resin matrix, adopts the crosslinking reaction of the epoxy resin and the unsaturated polyester resin under Co-60 gamma ray irradiation, simultaneously does not damage glass fibers, and retains the mechanical properties of the glass fibers. The cross-linking reaction between the two resins greatly improves the compatibility of the system, and the mechanical property, the thermal stability, the wear resistance, the solvent resistance and the creep resistance of the system are improved to different degrees. And all materials of the invention are easy to obtain, the cost is relatively low, and the preparation method is simple and clear.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
In the following examples and comparative examples: the recycled wind power blade is from Jerusalem environmental protection technology Co., ltd, the mass percentage of glass fiber in the recycled wind power blade is 60-70%, the mass percentage of epoxy resin is 30-40%, and the performance parameters of the recycled wind power blade comprise: the tensile strength is 70-75 MPa, the bending strength is 115-120 MPa, the impact strength is 35-40J/cm 2, and the test method of the mechanical properties of the recovered wind power blade is the same as the test method of the data in Table 1. The unsaturated polyester resin is p-benzene unsaturated polyester resin, and the manufacturer is Tianhe resin Co. The crosslinking enhancer is propane triacrylate and the manufacturer of the propane triacrylate is Nantong Runfeng petrochemical industry Co., ltd, and the CAS number is: 15625-89-5, which is yellow transparent liquid in appearance.
In the following examples and comparative examples: the method is characterized in that a universal pulverizer provided by Jiangsu Chitong mechanical manufacturing Co., ltd is adopted for the pulverization of the recovered wind power blades, and the model is 20B; the crushing operation conditions comprise: the rotating speed of the main shaft is 4500r/min, the feeding granularity is 6mm, the crushing fineness is 60-150 meshes, and the motor power is 4kW. The particle size of the crushed wind power blade particles is less than or equal to 5mm.
Screening of the crushed recovered wind power blades adopts an SDB-200 top impact type vibrating screen, and the operation conditions of screening comprise: the maximum diameter of the sieve is 200mm, the stacking height of the sieve is 400mm, the radius of gyration is 12.5mm, the shaking frequency of the sieve is 221r/min, the vibration frequency is 147r/min, the vertical amplitude is 5mm, the timing range is 0-60 min, the motor power is 0.37kW, the voltage is 380V, the rotating speed is 2800kg, and the weight is 130kg. And the particle size of the wind power blade granules obtained after sieving is 1-2 mm.
Example 1
In the embodiment, after the recovered wind power blade material is crushed and sieved, 500g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 5min, the irradiation dose is 10KGray, and the granules are converted into active fillers. Then placing the mixture with 500g of unsaturated polyester resin and 30g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target mould, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the mould. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 25kGy, after penetrating through a die to irradiate granules for 16min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Example 2
In the embodiment, after the recovered wind power blade material is crushed and sieved, 600g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 6min, the irradiation dose is 12KGray, and the granules are converted into active fillers. Then placing the mixture with 400g of unsaturated polyester resin and 25g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target die, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the die. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 20kGy, after penetrating through a die and irradiating granules for 14min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Example 3
In the embodiment, after the recovered wind power blade material is crushed and sieved, 700g of granules are weighed, and Co-60 gamma rays are released by an irradiation device for irradiation for 7min, wherein the irradiation dose is 14KGray, and the granules are converted into active fillers. The pellets were then placed in a mixer with 300g of unsaturated polyester resin and 20g of crosslinking enhancer to mix them well (the mixing temperature was 60 ℃, the time was 10min, the rotational speed was 30 rad/min), after thorough mixing, the mixture was injected into the target mold, heated and pressurized to 60 ℃,8MPa, and the heat and pressure were maintained for 5min to fill the mold with the mixture. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 15kGy, after penetrating through a die to irradiate granules for 12min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Example 4
In the embodiment, after the recovered wind power blade material is crushed and sieved, 600g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 5min, the irradiation dose is 10KGray, and the granules are converted into active fillers. Then placing the mixture with 400g of unsaturated polyester resin and 25g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target die, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the die. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 25kGy, after penetrating through a die to irradiate granules for 16min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Example 5
In the embodiment, after the recovered wind power blade material is crushed and sieved, 700g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 5min, the irradiation dose is 10KGray, and the granules are converted into active fillers. Then placing the mixture with 300g of unsaturated polyester resin and 20g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target die, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the die. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 25kGy, after penetrating through a die to irradiate granules for 16min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Comparative example 1
In the embodiment, after the recovered wind power blade material is crushed and sieved, 800g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 5min, the irradiation dose is 10KGray, and the granules are converted into active fillers. Then placing the mixture with 200g of unsaturated polyester resin and 15g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target die, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the die. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 25kGy, after penetrating through a die to irradiate granules for 16min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Comparative example 2
In the embodiment, after the recovered wind power blade material is crushed and sieved, 800g of granules are weighed, co-60 gamma rays are released by an irradiation device for irradiation for 8min, the irradiation dose is 16KGray, and the granules are converted into active fillers. Then placing the mixture with 200g of unsaturated polyester resin and 15g of crosslinking enhancer in a mixer to be uniformly mixed (the mixing temperature is 60 ℃, the time is 10min, the rotating speed is 30 rad/min), fully mixing, then injecting the mixture into a target die, heating and pressurizing to 60 ℃,8MPa, and preserving heat and pressure for 5min to enable the mixture to be full of the die. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 10kGy, after penetrating through a die to irradiate granules for 10min, the crosslinking enhancer absorbs radiation energy to decompose and generate free radicals, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Comparative example 3
In this comparative example, 1000g of unsaturated polyester resin and 30g of crosslinking enhancer were placed in a mixer to be uniformly mixed (the mixing temperature was 60 ℃, the time was 10 minutes, the rotation speed was 30 rad/min), and after sufficient mixing, the mixture was injected into a target mold, heated and pressurized to 60 ℃,8MPa, and the heat and pressure were maintained for 5 minutes to fill the mold with the mixture. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 25kGy, after penetrating through a die and irradiating the mixture for 16min, the crosslinking enhancer absorbs radiation energy and is converted into active monomers, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
Comparative example 4
In this comparative example, 600g of unirradiated wind power blade pellets, 400g of unsaturated polyester resin and 25g of crosslinking enhancer were placed in a mixer to be uniformly mixed (the mixing temperature was 60 ℃, the time was 10min, the rotation speed was 30 rad/min), and after sufficient mixing, the mixture was injected into a target mold, heated and pressurized to 60 ℃,8MPa, and the heat and pressure were maintained for 5min to allow the mixture to fill the mold. Co-60 gamma rays are released through an irradiation device, the irradiation dose is 20kGy, after penetrating through a die and irradiating the mixture for 14min, the crosslinking enhancer absorbs radiation energy and is converted into active monomers, the crosslinking reaction of an epoxy resin molecular chain with active free radicals and unsaturated polyester resin is initiated, and in the curing crosslinking reaction process, the pressure is increased to 8MPa, so that the product is compact, and the product defects are reduced. And after the reaction is completed, opening the die and taking out the regenerated composite material plate.
The mechanical properties of the composite materials prepared in examples 1 to 5 and comparative examples 1 to 4 are shown in Table 1, in which: tensile strength test method: GB/T1040.1-2006, method for testing bending strength: GB/T1449-2005, method for testing impact strength: GB/T1043.2-2018, test method for Tg (glass transition temperature): GB/T33061.11-2022 test method for thermal decomposition temperature: GB/T37631-2019.
TABLE 1 mechanical property data of regenerated composite materials prepared from wind turbine blade recovery materials
As can be seen from Table 1, in comparison with example 1, example 4, example 5 and comparative example 1, the present invention provides a product having significantly improved tensile strength, flexural strength and impact strength properties as compared with the product prepared in comparative example 1 by reasonably controlling the mass ratio relationship of the active filler, the unsaturated polyester resin and the crosslinking enhancer.
Compared with pure unsaturated polyester resin (comparative example 3), the mechanical property and the thermal stability of the regenerated composite material prepared by the invention are better improved, and the recycled wind power blade material not only realizes the hundred percent utilization, but also recycles the glass fiber fabric. Compared with the pure unsaturated polyester resin (comparative example 3), the regenerated composite material (comparative example 4) prepared from the non-irradiated granules is improved by about 10-20% in thermodynamic performance, but the wind power blade granules are not irradiated and are inert fillers, so that a certain mechanical property of the wind power blade regenerated composite material is slightly reduced. On the other hand, if the mass ratio of the wind power blade granules is too high, the improvement amplitude of the performance is reduced (the result of comparative example 1), and the regenerated composite material with excellent mechanical property and thermal stability is obtained by reasonably adjusting the mass ratio of the granules to the unsaturated polyester resin.
The method for preparing the high-performance wind power blade regeneration composite material by using the irradiation method provided by the invention realizes the green, efficient and value-added recovery of the recovered wind power blade, avoids the separation process of glass fiber and resin, reserves the mechanical strength of the glass fiber, saves resources, and has important economic significance and application value.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (9)
1. The preparation method of the wind power blade regeneration composite material is characterized by comprising the following steps of:
carrying out first irradiation on wind power blade granules to obtain active filler;
mixing the active filler, unsaturated polyester resin and crosslinking reinforcing agent to obtain a mixture; the unsaturated polyester resin comprises one or more of para-benzene unsaturated polyester resin, bisphenol A unsaturated polyester resin and meta-benzene unsaturated polyester resin; the mass ratio of the wind power blade granules to the polyester resin is (1:1) - (7:3); the crosslinking enhancer is one or more of methyl methacrylate, diallyl phthalate and trimethylol propane triacrylate; the mass of the crosslinking enhancer accounts for 2-3% of the total mass of the wind power blade granules and the polyester resin;
pressing the mixture in a mould to obtain a preformed blank;
and under the conditions of second irradiation and pressure application, carrying out cross-linking and curing on the preformed blank body to obtain the wind power blade regenerated composite material.
2. The preparation method of claim 1, wherein the wind power blade granules are obtained by crushing wind power blade materials, and the particle size of the wind power blade granules is 0.2-2 mm.
3. The preparation method according to claim 1 or 2, wherein the first irradiation is performed by Co-60 gamma rays, the dose of the first irradiation is 10-300 kGray, and the irradiation time is 3-10 min.
4. The preparation method according to claim 1, wherein the mixing is performed in a mixer, and the mixing is performed at a temperature of 60-100 ℃ for 5-10 min.
5. The preparation method according to claim 1, wherein the mixing is performed under stirring, and the stirring speed is 20-30 rad/min.
6. The preparation method according to claim 1, wherein the pressing temperature is 60-100 ℃, the pressing pressure is 5-10 mpa, and the holding time is 3-8 min.
7. The preparation method according to claim 1, wherein the second irradiation is performed by Co-60 gamma rays, the dose of the second irradiation is 10-300 kgy, and the irradiation time is 10-25 min; the pressure condition during crosslinking and curing is 8-10 MPa.
8. The wind power blade regenerated composite material prepared by the preparation method of any one of claims 1-7.
9. Use of the wind power blade regeneration composite material according to claim 8 as an artificial board.
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