CN117534959A - Method for preparing PA 6-polyolefin alloy master batch by using wind power blade recycled fibers - Google Patents
Method for preparing PA 6-polyolefin alloy master batch by using wind power blade recycled fibers Download PDFInfo
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- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for preparing PA 6-polyolefin alloy master batch by wind power blade recycled fiber and a product thereof. The method for preparing the PA 6-polyolefin alloy master batch by using the wind power blade recycled fiber comprises the following steps: s1: low temperature plasma modification; s2: preparing a solution; s3: soaking and standing; s4: drying the materials; s5: pretreatment and ageing; s6: drying; s7: plasma treatment; s8: plasma treatment or corona modification; s9: dissolving DCP; s10: mixing and stirring uniformly; s11: dissolving DCP and MAH in an acetone solution; s12: spraying and stirring the solution uniformly; s13: granulating. The invention is beneficial to overcoming the defects that the recycled fiber of the wind power blade is not well utilized, and the recycled fiber cannot be well organically combined with PA6, basalt fiber, polyolefin and the like, and the performance is poor in the prior art. The PA 6-polyolefin alloy master batch prepared by the wind power blade recycled fiber can be used for preparing a composite material with better performance.
Description
Technical Field
The invention belongs to the technical field of composite material manufacturing, relates to a method for preparing PA 6-polyolefin alloy master batch by using wind power blade recovery fibers, and particularly relates to a method for preparing PA 6-polyolefin alloy master batch by compounding wind power blade recovery fibers and basalt fibers.
Background
The rapid development of the Chinese wind power industry is about to face the challenges of retirement of large-scale wind power blades, and the harmless treatment, high-value utilization and resource utilization of the waste wind power blades become key problems of sustainable development of the wind power industry. At present, the main components of the retired wind power blade are epoxy resin and glass fiber, and meanwhile, the retired wind power blade also contains a small amount of materials such as metal, bassal wood, foam and the like. However, since epoxy resin is a thermosetting material, recycling and reuse are difficult to achieve. Worldwide, the main waste wind power blade recycling technologies include physical recycling, heat recycling and chemical recycling. The heat recovery equipment has high cost and is easy to generate toxic and harmful waste gas; high chemical recovery energy consumption and large solvent consumption. Therefore, these techniques are difficult to industrialize, and physical recycling has a greater industrialization potential. However, due to the limitation of the recycling process, only cured epoxy resin powder and glass fiber short fibers (purity 60-90%) containing cured epoxy resin can be obtained by cutting, crushing, grinding and other methods at present, the recycled fiber components of the obtained materials are not pure, and the recycling process has a plurality of defects through a mechanical recycling process, so that the material can be used in the low-value field only. The application field and the performance of the recycled materials are limited, how the waste wind power blades are utilized in a harmless and high-valued mode is greatly influenced, and the sustainable development of the wind power industry is greatly influenced. How to improve the material characteristics and the process of the waste wind power blade so as to greatly improve the performance of the composite material and apply the composite material to the higher-end field becomes a key problem of whether the waste wind power blade can be applied with high value.
The cost of general-purpose plastics such as PP, PP, PVC is low, the strength and modulus are also low, and glass fiber, basalt fiber, carbon fiber and the like are generally added for reinforcement. The engineering plastic PA6 has higher strength, is suitable for the engineering field, but has higher cost. Although the recycled fiber of the wind power blade contains glass fiber, the reinforcing effect on the thermoplastic resin is poor, and the industrialization application of the recycled fiber is limited. The carbon fiber has good reinforcing effect, but the cost is far higher than that of other fibers. In contrast, basalt fiber has better reinforcing effect and moderate cost, belongs to a new environment-friendly material, and is widely applied in the fields of composite materials, buildings, shipbuilding, heat insulation and the like.
Theoretically, by combining the advantages of these materials, materials with better properties can be developed, but the sources, molecular structures and materials of these materials are different, and it is not easy to combine them. The simple mixing and shaping of these materials does not allow the complementary advantages of the materials, and even mutual exclusion of the materials occurs, which necessarily does not allow excellent materials to be obtained. How to carry out material modification and process improvement on the waste wind power blade and how to better realize the organic combination of the wind power blade recovery fiber, PA6, basalt fiber and the like, thereby greatly improving the strength of the composite material, enabling the composite material to be applied to the field of higher ends, and being a key problem of whether the waste wind power blade can be applied to the field of high-valued composite materials.
The lack of related technologies in the prior art serves as a reference, and a new technical scheme is necessary to be provided to solve the problem of resource utilization of waste wind power blades and the problem of how to realize high-value application of related resources, and to make a contribution to sustainable development of industries such as wind power industry, composite materials and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing PA 6-polyolefin alloy master batch by using waste wind power blade recovery fibers, which overcomes the defects of the prior material, has more reasonable process and better product performance and can effectively utilize the wind power blade recovery fibers.
The technical scheme of the method for preparing PA 6-polyolefin alloy master batch by using wind power blade recycled fibers adopted by the invention comprises the following steps: s1, low-temperature plasma modification: modifying the wind power blade recycled fiber by a low-temperature plasma treatment process to obtain a material A; s2, preparing a solution: preparing absolute ethyl alcohol and distilled water into a solution B, and adding a silane coupling agent into the solution B to prepare a solution C; s3, soaking and standing: placing the material A in the solution C, soaking the material A in the solution C, and performing a storage process treatment; s4, drying materials: the material treated in the step S3 is further placed in drying equipment for drying to obtain a material D; s5, pretreatment and display: placing basalt fibers in the solution C, soaking the basalt fibers in the solution C, and performing a ageing process; s6, drying: the material treated in the step S5 is further placed in drying equipment for drying to obtain a modified primary product E; s7, plasma treatment: carrying out low-temperature plasma treatment process modification on the material D to obtain a material F; s8 plasma treatment or corona modification: modifying the modified primary product E by using a low-temperature plasma processor or a corona machine through powder to obtain a modified intermediate product G; s9 DCP dissolution: dissolving DCP in an acetone solution to obtain a solution H; s10, mixing and stirring uniformly: spraying the solution H into the material F, and uniformly stirring to obtain a material I; spraying the solution H into the modified intermediate product G, and uniformly stirring to obtain a modified basalt fiber final product J; s11DCP and MAH are dissolved: dissolving DCP and MAH in an acetone solution to obtain a solution K; s12, spraying and uniformly stirring the solution: spraying the solution K into PA6 and polyolefin, and uniformly stirring to obtain a material L; s13, granulating: granulating the material I, the modified basalt fiber final product J and the material L by a granulator to obtain PA 6-polyolefin alloy master batch M.
As a further improvement of the method, the wind power blade recovery fiber in the step S1 is a mechanical processing recovery product of the waste wind power blade, and the mechanical processing comprises one or more of a cutting step, an impact step, a tearing step, an extrusion step, a hammering step, a grinding step and a sieving step.
As a further improvement of the method, the wind power blade recovery fiber in the step S1 comprises 60-90 parts by weight of glass fiber and 10-40 parts by weight of cured epoxy resin powder, and the epoxy resin powder is irregularly distributed and attached to the surface of the glass fiber.
As a further improvement of the above method, the silane coupling agent in the step S2 is one or more of silane coupling agents having an amino functional group or a vinyl functional group.
As a further improvement of the above method, the silane coupling agent is KH550 silane coupling agent and/or KH151 silane coupling agent.
As a further improvement of the method, when the type of the modified primary product E in the step S8 is a staple fiber, treating the modified primary product E with a low-temperature plasma processor through powder to obtain a modified intermediate product G; when the type of the modified primary product E is continuous fibers, the modified primary product E is treated by a low-temperature plasma surface treatment machine or a corona machine to obtain a modified intermediate product G.
As a further improvement of the above method, the mass ratio of DCP contained in the solution H of step S9 to the mass ratio of the material F is 1:1000 to 1: in the range of 100; the mass ratio of DCP contained in the solution H of the step S9 to the modified intermediate product G is 1:1000 to 1: in the range of 100.
As a further improvement of the above method, the mass ratio of DCP contained in the solution K of step S11 to the mass ratio of the material L is 1:1000 to 1: in the range of 100; the mass ratio of the MAH contained in the solution K in the step S11 to the mass ratio of the material L is 1:200 to 1:20 range; the polyolefin is at least one of PE and PP.
As a further improvement of the above method, in the step S13, the granulator has a main machine barrel, the main machine barrel has a main feeding port thereon, the granulator further has a side feeding machine and a die, one or more barrel sections are arranged between the main feeding port of the main machine barrel and the side feeding machine, one or more barrel sections are arranged between the side feeding machine and the die, and one or more ultrasonic devices are arranged on the barrel sections; the material I and the modified basalt fiber final product J are fed by the side feeder; when the modified primary product E is a short fiber, uniformly mixing a modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and a material I accounting for 10-30% of the mass fraction, and then placing the mixture into a side feeding machine; when the type of the modified primary product E is continuous fibers, the modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and the material I accounting for 10-30% of the mass fraction are respectively placed in two side feeders; and (3) placing a material L accounting for 40% -80% of the total mass fraction of the PA 6-polyolefin alloy master batch M into the main feeding port of the granulator, and carrying out reaction extrusion modification by the granulator to obtain the PA 6-polyolefin alloy master batch M.
As a further improvement of the above method, the granulator in step S13 has a main machine barrel, the main machine barrel has a main feeding port thereon, a plurality of barrel sections are arranged between the main feeding port and the die, and one or more ultrasonic devices are arranged on the barrel sections between the main feeding port and the die; uniformly mixing a material I accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M, a modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and a material L accounting for 40-80% of the total mass fraction of the PA 6-polyolefin alloy master batch M, and carrying out reaction extrusion modification by a granulator to obtain the PA 6-polyolefin alloy master batch M.
The beneficial effects of the invention are as follows:
1. in the recovery process of the waste wind power blade, two recovery materials of recovered fibers and recovered resin are mainly produced. However, the industrialization and high-value utilization of the recycled materials are difficult, and the mechanism of difficult recycling is not fully disclosed and disclosed by related academic research, but the invention creates a novel PA 6-polyolefin alloy master batch preparation process for fully playing the reinforcing role of the recycled fibers, and explores a better fiber dispersion technology to ensure that glass fibers and basalt fibers can fully interpenetrate with PA6 and polyolefin, thereby improving the reinforcing effect. Based on the research of the inventor, a new material formula system is developed, the proportion and compatibility of materials are optimized, the materials are better fused together, and complementary advantages are exerted.
2. In the curing process of the epoxy resin, a large number of active groups such as hydroxyl groups, epoxy groups and the like participate in the reaction, so that the active groups of the cured epoxy resin are fewer. In order to realize good interface bonding between the cured epoxy resin and the polyolefin, the invention can add a large number of active groups such as hydroxyl groups, carbonyl groups, carboxyl groups and the like on the surface of the cured epoxy resin attached to the recycled fiber by a method of carrying out low-temperature plasma treatment on the recycled fiber. The active groups can be subjected to chemical reaction or hydrogen bonding with a silane coupling agent and maleic anhydride grafted polyolefin, and meanwhile, the surface of the cured epoxy resin can be etched to form grooves, so that the specific surface area is increased, and the adhesive force is further improved.
3. In the pelletization process, the movement of the material is exacerbated by the use of ultrasonic vibration, thereby increasing the chance of microcontact. The reaction probability of active groups is increased, so that the reaction is more complete, and the interface compatibility is better. And the ultrasonic vibration is beneficial to the dispersion of the recycled fibers and avoids the aggregation of the recycled fibers.
4. In the invention, after the recovered fibers and basalt fibers of the waste wind power blades are treated by KH550 and/or KH151 coupling agents, the coupling agents can generate silanol in the hydrolysis process and then react with hydroxyl groups on the surfaces of glass fibers, basalt fibers, PA6 and cured epoxy resin of the recovered fibers to form silica-alumina covalent bonds. By such treatment, the interfacial bond between glass fiber, basalt fiber, PA6 and cured epoxy resin can be improved on the one hand; on the other hand, amino groups in the KH550 silane coupling agent can react with maleic anhydride groups on polyolefin molecular chains, and vinyl groups in the KH151 coupling agent can carry out free radical polymerization reaction with polyolefin molecular chains under the action of DCP, and the reactions can further improve the interface combination among glass fibers, basalt fibers, PA6, cured epoxy resin and PE, so that the effect of alloy master batch on improving the performance of the composite material is improved.
5. After the silane coupling agent treatment, most of the hydroxyl groups of the epoxy resin on the recycled fiber have reacted with the silane coupling agent. In order to further improve the interfacial properties of the material, the present invention provides a plurality of steps of low temperature plasma treatment. The treatment can introduce more hydroxyl, carboxyl and other active groups on the surfaces of the epoxy resin and the basalt fiber, so that the probability and the chance of chemical reaction with maleic anhydride grafted polyolefin are increased. By the treatment method, the chemical reaction between the recycled fiber and the basalt fiber and the PA6 and the polyolefin can be more sufficient, the chemical interaction probability between the recycled fiber and the basalt fiber and the polymer matrix is further increased, the interface bonding capacity is enhanced, and the bonding strength and the stability of the interface are improved.
6. In order to ensure that the vinyl groups in KH151 react rapidly with the polyolefin, the present invention fully considers the premature depletion of DCP in material I due to the in situ grafting reaction. By adding a proper amount of DCP into the material F and the modified intermediate product G to generate more free radicals so as to ensure that vinyl groups in KH151 are effectively combined with polyolefin, the reaction efficiency can be improved and the interface combination of the products can be increased by the action.
7. The invention grafts maleic anhydride group on the polyolefin surface through the in-situ grafting reaction of DCP and MAH.
8. It is generally considered that the ultrasonic wave has no obvious influence on the preparation process of the composite material, but the ultrasonic device arranged between the main feeding port of the granulator and the side feeding machine can play a role in improving the chemical reaction process of the polyolefin, and the free radical content is increased under the vibration effect of the ultrasonic wave, so that the movement of polyolefin molecular chains is promoted. Thus, more Maleic Anhydride (MAH) can be successfully grafted onto the polyolefin molecular chain under the influence of the present invention, thereby improving the in-situ grafting rate.
9. According to the invention, an ultrasonic device is arranged between the side feeder and the die of the granulator, the free radical content is increased by ultrasonic vibration, the movement of polyolefin molecular chains is accelerated, more covalent bonds are formed between the vinyl functional groups on the KH151 coupling agent and the polyolefin, the reaction probability of the amino functional groups of KH550 and the maleic anhydride groups on the in-situ grafted polyolefin is increased, more amide covalent bonds are formed, and the reaction contact points of epoxy resin, glass fiber, basalt fiber, PA6 and polyolefin molecular chains are greatly increased, so that the interface compatibility of the components is greatly improved. In addition, the ultrasonic vibration is beneficial to the dispersion of the final products J of the glass fibers and the modified basalt fibers, and the probability of aggregation of the final products J of the glass fibers and the modified basalt fibers is reduced, so that the function of the fiber reinforced thermoplastic resin can be exerted.
In conclusion, active groups in the wind power blade recovery fiber are greatly increased through modification treatment of low-temperature plasma and silane coupling agent, and the mutual interfacial compatibility of glass fiber, cured epoxy resin, basalt fiber, PA6 and polyolefin in the wind power blade recovery fiber is greatly improved through in-situ grafting modification and ultrasonic vibration, so that the dispersibility of the recovery fiber and basalt fiber in PA 6-polyolefin alloy is improved, the wind power blade recovery fiber and basalt fiber reinforced PA 6-polyolefin alloy master batch are prepared, and the recovered waste wind power blade can be utilized in a high value.
Drawings
FIG. 1 is a schematic flow chart of the method for preparing PA 6-polyolefin alloy master batch by using wind power blade recycled fibers.
Detailed Description
In order to more clearly describe the technical solution in the embodiments of the present invention, the following description will simply describe the embodiments. It is apparent that only some embodiments, but not all embodiments, of the present invention have been described, and that those skilled in the art may obtain other designs from the flow diagrams without the exercise of inventive faculty.
A method for preparing PA 6-polyolefin alloy master batch by wind power blade recycled fiber comprises the following steps of S1: low temperature plasma modification; s2: preparing a solution; s3: soaking and standing; s4: drying the materials; s5: pretreatment and ageing; s6: drying; s7: plasma treatment; s8: plasma treatment or corona modification; s9: dissolving DCP; s10: mixing and stirring uniformly; s11: dissolving DCP and MAH in an acetone solution; s12: spraying and stirring the solution uniformly; s13: granulating.
As a further improvement of the above method, the step S1: modifying the wind power blade recycled fiber by a low-temperature plasma treatment process to obtain a material A; s2: preparing absolute ethyl alcohol and distilled water into a solution B, and adding a silane coupling agent into the solution B to prepare a solution C; s3: placing the material A in the solution C, soaking the material A in the solution C, and performing a storage process treatment; s4: the material treated in the step S3 is further placed in drying equipment for drying to obtain a material D; s5: placing basalt fibers in the solution C, soaking the basalt fibers in the solution C, and performing a ageing process; s6: the material treated in the step S5 is further placed in drying equipment for drying to obtain a modified primary product E; s7: carrying out low-temperature plasma treatment process modification on the material D to obtain a material F; s8: modifying the modified primary product E by using a low-temperature plasma processor or a corona machine through powder to obtain a modified intermediate product G; s9: dissolving DCP in an acetone solution to obtain a solution H; s10: spraying the solution H into the material F, and uniformly stirring to obtain a material I; spraying the solution H into the modified intermediate product G, and uniformly stirring to obtain a modified basalt fiber final product J; s11: dissolving DCP and MAH in an acetone solution to obtain a solution K; s12: spraying the solution K into PA6 and polyolefin, and uniformly stirring to obtain a material L; s13: granulating the material I, the modified basalt fiber final product J and the material L by a granulator to obtain PA 6-polyolefin alloy master batch M. The beneficial effects of this embodiment are: active groups in the wind power blade recovery fiber are greatly increased through modification treatment of low-temperature plasma and silane coupling agent, and through in-situ grafting modification and ultrasonic vibration, the mutual interfacial compatibility of glass fiber, cured epoxy resin, basalt fiber, PA6 and polyolefin in the wind power blade recovery fiber is greatly improved, and the dispersibility of the recovery fiber and basalt fiber in PA 6/polyolefin alloy is improved, so that the wind power blade recovery fiber/basalt fiber reinforced PA 6/polyolefin alloy master batch is prepared, and the recovered waste wind power blade can be utilized in a high value.
As a further improvement of the method, the wind power blade recovery fiber in the step S1 is formed by cutting, crushing, grinding, screening and other mechanical processing of waste wind power blades, and mainly comprises 60-90 parts by mass of glass fiber and 10-40 parts by mass of cured epoxy resin powder, wherein the epoxy resin powder is irregularly distributed and attached to the surface of the glass fiber. The beneficial effects of this embodiment are: when the epoxy resin is cured, a large number of active groups such as hydroxyl groups, epoxy groups and the like participate in the reaction, so that the cured epoxy resin has fewer active groups. In order to enable the cured epoxy resin to form good interface combination with PA6 and polyolefin, the surface of the epoxy resin attached to the recycled fiber is increased with a large number of active groups such as hydroxyl groups by carrying out low-temperature plasma treatment on the recycled fiber, so that the epoxy resin can be subjected to chemical reaction with a silane coupling agent and maleic anhydride grafted PA 6/polyolefin alloy, and meanwhile, the surface of the epoxy resin is etched to form grooves, so that the specific surface area is increased, and the adhesive force is improved.
As a further improvement of the method, the silane coupling agent in the step S2 is selected from KH550 silane coupling agent with amino functional group and KH151 silane coupling agent with vinyl functional group. The basalt fiber types include short fibers or continuous fibers. The beneficial effects of this embodiment are: in the process of recycling the waste wind power blades, part of epoxy resin is peeled off from the surface of the glass fiber through mechanical actions such as crushing, grinding and the like, and part of epoxy resin is adhered to the surface of the glass fiber, but the mechanical actions cause severe damage to the interface between the epoxy resin and the glass fiber and more connection weaknesses. This results in increased defects and reduced mechanical properties of the composite material produced. KH550 and KH151 coupling agent are hydrolyzed into silanol, and react with glass fiber of waste wind power blade recovery fiber and hydroxyl on the surface of epoxy resin to form a silica-silica covalent bond, so that on one hand, the interface combination of glass fiber and epoxy resin can be improved, on the other hand, amino group of KH550 silane coupling agent can react with maleic anhydride group grafted on PA 6/polyolefin alloy molecular chain, vinyl group of KH151 coupling agent can react with polyolefin, so that the interface combination of glass fiber, epoxy resin, PA6 and polyolefin can be improved. The basalt fiber surface contains a large number of hydroxyl groups, and the coupling agent treatment mechanism is the same as that of the wind power blade recovery fiber.
As a further improvement of the above method, when the modified basalt fiber type in the step S8 is a staple fiber, the basalt fiber is treated with a low-temperature plasma treatment machine by powder, and when the modified basalt fiber type is a continuous fiber, the basalt fiber is treated with a low-temperature plasma surface treatment machine or a corona machine. The beneficial effects of this embodiment are: the low-temperature plasma treatment machine for powder can rotate and roll the powder, particles, short fibers and other objects, and can theoretically carry out uniform plasma treatment of 360 degrees on the objects, so that the method is suitable for basalt short fibers treatment. The low-temperature plasma surface treatment machine and the corona machine do not have the function of rotating and rolling the object, and only can treat the upper surface and the lower surface of the object, so that the method is suitable for basalt continuous fiber treatment. Through low-temperature plasma treatment or corona treatment, the basalt fiber surface is etched to form grooves, the specific surface area is increased, and the adhesive force can be improved. After the recycled fiber is treated by the silane coupling agent, most of hydroxyl groups of the epoxy resin on the recycled fiber react with the silane coupling agent. The low-temperature plasma treatment is performed again to increase active groups such as hydroxyl, carboxyl and the like on the surface of the epoxy resin, so that the probability of chemical reaction with maleic anhydride grafted PA 6/polyolefin alloy is increased.
As a further improvement of the above method, in the step S9, DCP accounts for 0.1% -1% of the mass of the material F, and DCP accounts for 0.1% -1% of the mass of the modified intermediate product G. The beneficial effects of this embodiment are: the DCP in the material L is possibly consumed prematurely because of the in-situ grafting reaction of the material L, so that the DCP is added into the material F and the modified intermediate product G to generate free radicals, thereby ensuring the chemical reaction of vinyl energy of KH151 and polyolefin.
As a further improvement of the above method, in the step S11, the DCP accounts for 0.1% -1% of the mass fraction of PA6 and the polyolefin, the MAH accounts for 0.5% -5% of the mass fraction of PA6 and the polyolefin, and the polyolefin is one or both of PE and PP. The beneficial effects of this embodiment are: through the in-situ grafting reaction of DCP and MAH, maleic anhydride groups are grafted on the surface of polyolefin, and partial maleic anhydride groups react with the terminal amino groups of PA6 to form amide covalent bonds, so that the compatibility of PA6 and polyolefin is promoted.
As a further improvement of the method, in the step S13, the granulator is a parallel twin-screw granulator, one cylinder of the main machine of the granulator is connected with one or two side feeders, one or more ultrasonic devices are arranged at each cylinder between a feeding port of the main machine of the granulator and the side feeders, and one or more ultrasonic devices are arranged at each cylinder between the side feeders and a die of the granulator. When the basalt fiber is short fiber, the modified basalt fiber final product J with the mass fraction of 10-30% and the material I with the mass fraction of 10-30% are mixed uniformly, and then put into a side feeder. When the basalt fiber is continuous fiber, the modified basalt fiber final product J with the mass fraction of 10-30% and the material I with the mass fraction of 10-30% are respectively placed in two side feeders. And (3) placing the material L with the mass fraction of 40% -80% into a main machine feeding port of a granulator, and carrying out reactive extrusion modification by the granulator to obtain the wind power blade recovery fiber/basalt fiber reinforced PA 6/polyolefin alloy master batch M. The beneficial effects of this embodiment are: an ultrasonic device is arranged between a main feeding port of the granulator and a side feeding machine, the content of free radicals is increased by ultrasonic vibration, the movement of PA6 and polyolefin molecular chains is accelerated, more MAH is grafted onto the polyolefin molecular chains, the in-situ grafting rate is increased, the reaction probability of maleic anhydride groups and terminal amino groups of PA6 is increased, and therefore the PA6 and the polyolefin have good interface compatibility. An ultrasonic device is arranged between the side feeder and the die of the granulator, the content of free radicals is increased by ultrasonic vibration, the movement of the PA 6/polyolefin alloy molecular chain is accelerated, more covalent bonds are formed between a vinyl functional group on the KH151 coupling agent and polyolefin, the probability of reaction between an amino functional group of KH550 and a maleic anhydride group on in-situ grafted polyolefin is increased, more amide covalent bonds are formed, and the reaction contact points of epoxy resin, glass fiber, basalt fiber and PA 6/polyolefin alloy molecular chain are greatly increased, so that the interfacial compatibility of the components is greatly improved. In addition, the ultrasonic vibration is beneficial to the dispersion of glass fibers and basalt fibers, and reduces the probability of aggregation of the glass fibers and the basalt fibers, so that the function of the fiber reinforced thermoplastic resin can be better played.
As a further improvement of the above method, the granulator in the step S13 is a parallel twin screw granulator, and one or more ultrasonic devices are disposed at each barrel of the granulator. Uniformly mixing 10% -30% by mass of material I, 10% -30% by mass of modified basalt fiber final product J and 40% -80% by mass of material L, and carrying out reactive extrusion modification by a granulator to obtain the wind power blade recovery fiber/basalt fiber reinforced PA 6/polyolefin alloy master batch M. The beneficial effects of this embodiment are: compared with the process with the side feeder, the process weakens the grafting rate of the maleic anhydride and the reaction probability of the terminal amino group of the PA6 and the maleic anhydride due to the in-situ grafting reaction of the maleic anhydride and the polyolefin and the chemical reaction of the amino group of the KH 550. However, the process is simpler and the quality is easier to control because of no side feeder, and the recycled fiber and basalt fiber in the PA 6/polyolefin alloy are more uniformly dispersed by the material I, the modified basalt fiber final product J and the material L through the mixing process, so that the two processes have advantages and disadvantages.
According to the invention, through modification treatment of low-temperature plasmas and silane coupling agents, active groups in the wind power blade recovery fibers and basalt fibers are greatly increased, through in-situ grafting modification and ultrasonic vibration, the mutual interfacial compatibility of glass fibers, basalt fibers, PA6, cured epoxy resin and polyolefin in the wind power blade recovery fibers is greatly improved, and the dispersibility of the recovery fibers and basalt fibers in the PA 6-polyolefin is improved, so that the wind power blade recovery fibers and basalt fiber reinforced PA 6-polyolefin alloy master batches are prepared, and the master batches are favorable for improving the mechanical properties of the composite material.
Claims (10)
1. The method for preparing the PA 6-polyolefin alloy master batch by using the wind power blade recycled fiber is characterized by comprising the following steps of:
s1: modifying the wind power blade recycled fiber by a low-temperature plasma treatment process to obtain a material A;
s2: preparing absolute ethyl alcohol and distilled water into a solution B, and adding a silane coupling agent into the solution B to prepare a solution C;
s3: placing the material A in the solution C, soaking the material A in the solution C, and performing a storage process treatment;
s4: the material treated in the step S3 is further placed in drying equipment for drying to obtain a material D;
s5: placing basalt fibers in the solution C, soaking the basalt fibers in the solution C, and performing a ageing process;
s6: the material treated in the step S5 is further placed in drying equipment for drying to obtain a modified primary product E;
s7: carrying out low-temperature plasma treatment process modification on the material D to obtain a material F;
s8: modifying the modified primary product E by using a low-temperature plasma processor or a corona machine through powder to obtain a modified intermediate product G;
s9: dissolving DCP in an acetone solution to obtain a solution H;
s10: spraying the solution H into the material F, and uniformly stirring to obtain a material I; spraying the solution H into the modified intermediate product G, and uniformly stirring to obtain a modified basalt fiber final product J;
s11: dissolving DCP and MAH in an acetone solution to obtain a solution K;
s12: spraying the solution K into PA6 and polyolefin, and uniformly stirring to obtain a material L;
s13: granulating the material I, the modified basalt fiber final product J and the material L by a granulator to obtain PA 6-polyolefin alloy master batch M.
2. The method for preparing PA 6-polyolefin alloy master batch from recycled fiber of wind power blade according to claim 1, wherein the recycled fiber of wind power blade in step S1 is a mechanically processed recycled product of waste wind power blade, and the mechanical processing comprises one or more of cutting step, impacting step, tearing step, extruding step, hammering step, grinding step and sieving step.
3. The method for preparing PA 6-polyolefin alloy master batch with wind power blade recovery fiber according to claim 1, wherein the wind power blade recovery fiber in step S1 comprises 60-90 parts by mass of glass fiber and 10-40 parts by mass of cured epoxy resin powder, and the epoxy resin powder is randomly distributed and attached to the surface of the glass fiber.
4. The method for preparing PA 6-polyolefin alloy master batch from recycled fiber of wind power blade according to claim 1, wherein the silane coupling agent in step S2 is one or more of silane coupling agents with amino functional group or vinyl functional group.
5. The method for preparing PA 6-polyolefin alloy master batch from recycled fiber of wind power blade according to claim 4, wherein the silane coupling agent is KH550 silane coupling agent and/or KH151 silane coupling agent.
6. The method for preparing PA 6-polyolefin alloy master batch by using recycled fiber of wind power blade according to claim 1, wherein when the type of the modified primary product E in the step S8 is short fiber, the modified primary product E is treated by a low-temperature plasma processor through powder to obtain a modified intermediate product G; when the type of the modified primary product E is continuous fibers, the modified primary product E is treated by a low-temperature plasma surface treatment machine or a corona machine to obtain a modified intermediate product G.
7. The method for preparing PA 6-polyolefin alloy master batch from recycled fiber of wind power blade according to any one of claims 1 to 6, wherein the mass ratio of DCP contained in solution H of step S9 to material F is 1:1000 to 1: in the range of 100; the mass ratio of DCP contained in the solution H of the step S9 to the modified intermediate product G is 1:1000 to 1: in the range of 100.
8. The method for preparing PA 6-polyolefin alloy master batch from recycled fiber of wind power blade according to any one of claims 1 to 6, wherein the mass ratio of DCP contained in solution K in step S11 to material L is 1:1000 to 1: in the range of 100; the mass ratio of the MAH contained in the solution K in the step S11 to the mass ratio of the material L is 1:200 to 1:20 range; the polyolefin is at least one of PE and PP.
9. The method for producing PA 6-polyolefin alloy master batch with wind power blade recycled fiber according to claim 6, wherein the granulator in step S13 has a main machine barrel with a main feeding port thereon, the granulator further has a side feeder and a die, one or more barrel sections are provided between the main feeding port of the main machine barrel and the side feeder, one or more barrel sections are provided between the side feeder and the die, and one or more ultrasonic devices are provided on the barrel sections; the material I and the modified basalt fiber final product J are fed by the side feeder; when the modified primary product E is a short fiber, uniformly mixing a modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and a material I accounting for 10-30% of the mass fraction, and then placing the mixture into a side feeding machine; when the type of the modified primary product E is continuous fibers, the modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and the material I accounting for 10-30% of the mass fraction are respectively placed in two side feeders; and (3) placing a material L accounting for 40% -80% of the total mass fraction of the PA 6-polyolefin alloy master batch M into the main feeding port of the granulator, and carrying out reaction extrusion modification by the granulator to obtain the PA 6-polyolefin alloy master batch M.
10. The method for producing PA 6-polyolefin alloy master batch with wind power blade recycled fiber according to any one of claims 1 to 5, wherein the granulator in step S13 has a main machine barrel with a main feeding port thereon, a plurality of barrel sections are provided between the main feeding port and the die, and one or more ultrasonic devices are provided on the barrel sections between the main feeding port and the die; uniformly mixing a material I accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M, a modified basalt fiber final product J accounting for 10-30% of the total mass fraction of the PA 6-polyolefin alloy master batch M and a material L accounting for 40-80% of the total mass fraction of the PA 6-polyolefin alloy master batch M, and carrying out reaction extrusion modification by a granulator to obtain the PA 6-polyolefin alloy master batch M.
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