WO2021000727A1 - 芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法 - Google Patents

芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法 Download PDF

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WO2021000727A1
WO2021000727A1 PCT/CN2020/096445 CN2020096445W WO2021000727A1 WO 2021000727 A1 WO2021000727 A1 WO 2021000727A1 CN 2020096445 W CN2020096445 W CN 2020096445W WO 2021000727 A1 WO2021000727 A1 WO 2021000727A1
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Prior art keywords
aramid
epoxy resin
glue
present
fiber
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PCT/CN2020/096445
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English (en)
French (fr)
Inventor
邓海
董雪妍
金晓明
金晶
刘涛
Original Assignee
中车长春轨道客车股份有限公司
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Application filed by 中车长春轨道客车股份有限公司 filed Critical 中车长春轨道客车股份有限公司
Priority to EP20835004.1A priority Critical patent/EP3957781A4/en
Priority to SG11202112868TA priority patent/SG11202112868TA/en
Publication of WO2021000727A1 publication Critical patent/WO2021000727A1/zh

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Definitions

  • the invention belongs to the technical field of aramid epoxy resin adhesives, and specifically relates to an aramid 1313 mesh fiber and a preparation method thereof, an aramid epoxy resin adhesive and a preparation method thereof, and particularly relates to an aramid 1313 mesh fiber and a preparation method thereof Preparation method, room temperature curing aramid flame-retardant epoxy resin structural adhesive series and preparation method thereof, aramid paper honeycomb composite parts.
  • Adhesive refers to a natural or synthetic, organic or inorganic substance that can connect two or more parts or materials together through the adhesion and cohesion of the interface. Collectively referred to as glue Adhesive, also called adhesive, is customarily referred to as glue for short. In short, an adhesive is a substance that binds the adherends together through adhesion. Gluing (bonding, bonding, gluing, gluing) refers to the technology of connecting the surfaces of homogeneous or heterogeneous objects with adhesives, which can be applied to the connection of different materials, different thicknesses, ultra-thin specifications and complex components . Adhesive has the fastest development in the near-generation and has a wide range of applications.
  • thermosetting glue is a kind of glue that is widely used in industry, mainly including epoxy resin, phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, silicone resin, furan resin, unsaturated polyester, acrylic resin , Polyimide, polybenzimidazole, phenolic-polyvinyl acetal, phenolic-polyamide, phenolic-epoxy resin, epoxy-polyamide, etc.
  • the bonding and curing of thermosetting adhesives often require heating, which brings great inconvenience to its application and limits its further application.
  • aramid paper honeycomb in aviation materials has low density and high Strength, no thermal expansion and contraction, no metal fatigue, flame retardant, non-toxic, low temperature resistance and other advantages, and the development of domestic high-speed rail, the same batch of aramid paper honeycomb core parts applied to high-speed rail vehicle interior materials.
  • the technical problem to be solved by the present invention is to provide an aramid 1313 mesh fiber and a preparation method thereof, an aramid epoxy resin adhesive and a preparation method thereof, especially an aramid flame-retardant epoxy resin cured at room temperature Resin structural adhesive series.
  • the aramid flame-retardant epoxy resin structural adhesive series provided by the present invention has good bonding performance, and can also be used for edge sealing and molding, thereby meeting various needs.
  • the present invention provides an aramid 1313 mesh fiber, wherein the aramid 1313 fiber is a flocculent fiber cluster aramid 1313 fiber;
  • Aramid 1313 fiber filaments are interwoven to form a three-dimensional network structure.
  • the fineness of the aramid 1313 mesh fiber is 1 to 2D;
  • the aramid 1313 mesh fiber has a microscopic three-dimensional network structure formed by mutual cross-linking of filaments, strips and membranes;
  • the diameter of the wire is 10-500nm
  • the diameter of the strip is 0.5-20 ⁇ m
  • the diameter of the film is 5-50 ⁇ m.
  • the present invention provides a method for preparing aramid 1313 mesh fiber, including the following steps:
  • the coagulation liquid includes a dimethylacetamide solution
  • the sprayed flow rate of the aramid 1313 slurry is less than or equal to 1000 mL/min;
  • the mass ratio of the aramid 1313 slurry to the coagulation liquid is 1: (2-20);
  • the solidification and sedimentation time is 5-40 min;
  • the temperature of the hot air drying is 60-85°C.
  • the invention provides an aramid epoxy resin adhesive, which is calculated as a percentage of the mass of raw materials, and includes:
  • the epoxy resin includes flame-retardant epoxy resin
  • the length of the aramid 1313 mesh fiber is 1-7mm;
  • the aspect ratio of the aramid 1313 mesh fiber is (50 ⁇ 1000):1;
  • the silica includes fumed silica powder
  • the foamed filler includes hollow glass beads and/or nano hollow floating powder
  • the aramid epoxy resin glue includes one or more of aramid epoxy resin edge banding glue, aramid epoxy resin filling glue and aramid epoxy resin molding glue;
  • the silica is each selected from 3.5 to 5.7 parts by weight based on the mass percentage of raw materials;
  • the silica is 5.7 to 7.5 parts by weight based on the mass percentage of the raw material.
  • the particle size of the silica is 12 nm to 6 ⁇ m;
  • the density of the aramid epoxy resin edge sealant is 0.6-1.0 g/cm 3 ;
  • the aramid epoxy resin edge sealing glue is used for edge sealing of lightweight honeycomb composite materials
  • the density of the aramid epoxy resin filler is 1.4-1.6 g/cm 3 ;
  • the aramid epoxy resin filler is used to bond hardware on the resin composite material
  • the density of the aramid epoxy resin molding glue is 0.9-1.6 g/cm 3 ;
  • the aramid epoxy resin molding glue becomes dough-like before curing
  • the aramid epoxy resin molding glue is used for molding on the resin composite material.
  • the present invention provides a method for preparing the aramid epoxy resin adhesive according to any one of the above technical solutions, including the following steps:
  • a foamed filler is further included;
  • the mixing time is 10-30 min;
  • the aramid epoxy resin adhesive needs to be added with a curing aid before use;
  • the curing aids include modified amine curing agents, accelerators and coupling agents;
  • the mass ratio of the aramid epoxy resin adhesive to the curing aid is 4:1;
  • the open time of the aramid epoxy resin adhesive is 30-40 minutes.
  • the invention also provides an aramid paper honeycomb composite article, which includes a prepreg cured sheet, an aramid paper honeycomb core and Hanikon glue;
  • the aramid paper honeycomb core is compounded between the cured prepreg sheets to form a sandwich structure
  • the Hanacon glue includes Hanacon adhesive glue
  • the Hanacon adhesive is bonded between the aramid paper honeycomb core and the prepreg cured sheet;
  • the Hanikang glue is the aramid epoxy resin glue according to any one of the above technical solutions or the aramid epoxy resin glue prepared by the preparation method according to any one of the above technical solutions.
  • the Hanikon glue also includes Hanikon edge banding glue
  • the Hanikang edge banding glue is used as the edge banding of the aramid paper honeycomb composite product.
  • the prepreg cured sheet includes glass fiber and/or carbon fiber prepreg cured sheet;
  • the Hanikang glue can also be filled and embedded in any position of the aramid paper honeycomb composite part;
  • the aramid paper honeycomb composite article also includes hardware.
  • the arbitrary position includes a position requiring later machining or manual processing
  • the processing method includes one or more of size positioning, edge trimming, hole opening and grooving;
  • the hardware is set at the place where the Hanikang glue is filled with pre-buried or post-buried;
  • the hardware can also be used in conjunction with the Hanikang glue when installed.
  • the prepreg cured sheet includes a double-layer prepreg cured sheet and/or a multilayer prepreg cured sheet;
  • the thickness of the double-layer prepreg cured sheet is 0.3 to 0.36 mm;
  • the thickness of the multilayer cured prepreg sheet is greater than or equal to 0.45 mm;
  • the resin content of the cured prepreg sheet is 35%-65%;
  • the volatile content of the cured prepreg sheet is less than or equal to 8%.
  • the shape of the aramid paper honeycomb core includes one or more of a regular hexagonal honeycomb core, a polygonal honeycomb core, a corrugated honeycomb core, and an overstretched honeycomb core;
  • the cell size of the aramid paper honeycomb core is 1.83 ⁇ 3.67mm;
  • the density of the aramid paper honeycomb core is 32 ⁇ 120kg/m 3 ;
  • the height of the aramid paper honeycomb core is 1 to 860 mm.
  • the invention also provides a method for preparing the aramid paper honeycomb composite article, which includes the following steps:
  • the aramid paper honeycomb is used as the core material, and the cured prepreg sheet is used as the surface material.
  • the adhesive is used for bonding with Hanikon adhesive. After the mold is closed and pressurized and cured, the edge is sealed with Hanikon edge sealing adhesive to obtain Aramid paper honeycomb composite parts.
  • the temperature of the clamping and pressure curing is 25-60°C;
  • the initial curing time of the clamping and pressure curing is 3 to 48 hours;
  • the complete curing time of the clamping and pressure curing is 1-7 days;
  • the pressure of the clamping and pressure curing is 0.1-0.3 MPa
  • the prepreg cured sheet is obtained by curing glass fiber and/or carbon fiber prepreg through heat and pressure;
  • the heat and pressure curing temperature is 120-150°C;
  • the heat and pressure curing time is 25 to 330 minutes;
  • the heat and pressure curing pressure is 0.1-0.3 MPa.
  • the pre-treatment step is further included before the bonding
  • the pretreatment includes one or more of cutting, sanding, degreasing and dust removal;
  • the dosage of the Hanacon adhesive is 300-350 g/m2;
  • the bonding After the bonding, it also includes a filling and embedding step;
  • the edge sealing Before and/or after the edge sealing, it also includes a machining step;
  • a post-processing step is also included.
  • the filling and embedding step is specifically:
  • the machining steps are specifically:
  • the post-treatment step includes one or more of spray painting, film sticking and fireproof board sticking.
  • the present invention also provides the aramid paper honeycomb composite article according to any one of the above technical solutions or the aramid paper honeycomb composite article prepared by the preparation method according to any one of the above technical solutions for use in rail transit. Application of high-quality flame-retardant board furniture.
  • the present invention provides an aramid 1313 mesh fiber.
  • the aramid 1313 fiber is a flocculent aramid 1313 fiber; the aramid 1313 fiber filaments are interwoven to form a three-dimensional network structure.
  • the present invention often requires heating for the bonding and curing of the existing thermosetting adhesive, which brings great inconvenience to its application and limits the drawbacks of its further application.
  • the process In combination with the current existing production process of aramid honeycomb composite parts, the process has high energy consumption, high equipment cost, low production efficiency, high temperature hot press is required, and it is difficult to achieve large-scale low-cost production, resulting in expensive products , Especially there are still big limitations in custom processing.
  • the present invention creatively obtains an aramid 1313 mesh fiber.
  • the aramid 1313 fiber has a flocculent fiber cluster shape, and the aramid 1313 fiber filaments are interwoven to form a three-dimensional network structure.
  • it is used in epoxy resin glue to obtain an aramid epoxy resin glue.
  • Aramid 1313 mesh fiber is added to the epoxy resin glue, similar to the principle of cement and steel reinforcement, so that the epoxy resin glue is cured After that, it has better bonding properties such as better compression resistance, shear resistance, crack resistance, and low temperature resistance.
  • the aramid epoxy resin adhesive is a series of flame-retardant epoxy resin structural adhesives.
  • Aramid epoxy resin adhesive can be cured at room temperature and has good performance. It can meet the relevant standards of aramid paper honeycomb composite parts, thereby solving the cumbersome process of preparing aramid honeycomb composite parts. Defects such as high cost.
  • the invention also designs a process for the aramid paper honeycomb composite part and its normal temperature preparation method.
  • the aramid epoxy resin glue is used to paste the aramid paper honeycomb core between the cured prepreg sheets to form a sandwich structure to obtain an aramid paper honeycomb composite article.
  • the aramid paper honeycomb composite article provided by the present invention adopts a prepreg cured sheet prepared in advance and an aramid epoxy resin glue, and can be compounded at room temperature in the final compounding process, reducing production time and equipment investment. This eliminates the need for large-scale equipment such as hot presses, large vacuum tanks, and high-temperature ovens when processing finished parts, thereby reducing production costs and realizing the industrial production of large quantities of aramid paper honeycomb composite panels.
  • the prepared aramid paper honeycomb composite article effectively maintains the rigidity, flatness and strength of the aramid paper honeycomb core, and has good flame retardancy, heat preservation and mechanical properties.
  • the preparation method of the aramid 1313 mesh fiber provided by the invention has simple process and mild conditions, and is more suitable for large-scale production and promotion.
  • the aramid epoxy resin adhesive provided by the present invention has a colloidal Shore hardness of 85-95D after being fully cured, and the compressive strength of the cured rubber block is greater than or equal to 55-65MPa; the tensile force of the 10mm deep M6 screw is greater than or equal to 2000N; The strength (60°C for 3 days, 25°C for 7 days at room temperature) is greater than or equal to 10-15MPa, with good low temperature performance, and low temperature resistance reaches -55°C.
  • the prepared aramid paper honeycomb composite parts also have good comprehensive properties, with tensile properties of 1.70-2.40MPa; flat compression properties of 2.0-3.6MPa; shear properties of 0.60-1.30MPa; roller peel strength of 45 ⁇ 70N*mm/mm; the bending stiffness is 6.0*10 7 ⁇ 11.0*10 7 N ⁇ mm 2 .
  • Figure 1 is an appearance view of the aramid 1313 mesh fiber prepared by the present invention
  • Figure 2 is a scanning electron micrograph of the aramid 1313 mesh fiber prepared by the present invention.
  • the purity of all raw materials of the present invention is not particularly limited.
  • the present invention preferably adopts analytical purity or conventional purity requirements in the field of aramid epoxy resin preparation.
  • the present invention provides an aramid 1313 mesh fiber, wherein the aramid 1313 fiber is a flocculent fiber cluster aramid 1313 fiber;
  • Aramid 1313 fiber filaments are interwoven to form a three-dimensional network structure.
  • aramid 1313 has no special restrictions on the definition of aramid 1313.
  • the definition and concept of aramid 1313 well known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the aramid 1313 mesh fiber of the present invention has a floc-like fiber cluster or a macroscopic morphology similar to a cotton-like fiber cluster, and the aramid 1313 fiber filaments are interwoven to form a 3D three-dimensional space network structure.
  • the present invention has no special restrictions on the characteristic parameters of the aramid 1313 mesh fiber. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures that the aramid 1313 mesh fiber It can better improve the performance of aramid epoxy resin adhesive and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the fineness of the aramid 1313 mesh fiber is preferably 1 to 2D, more preferably It is 1.2 to 1.8D, more preferably 1.4 to 1.6D.
  • the present invention has no special restrictions on the microstructure of the aramid 1313 mesh fiber. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures that the aramid 1313 mesh fiber It can better improve the performance of aramid epoxy resin adhesive, and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the aramid 1313 mesh fiber particularly preferably has filaments and strips. The microscopic three-dimensional network structure formed by cross-linking between the shape and the film.
  • the filaments, strips and membranes are all composed of aramid 1313, aramid 1313 filaments have a thin filament shape, and the aramid 1313 strips can be strips after crimping the aramid 1313 film, or The aramid 1313 filaments are twisted together to form a strip, while the aramid 1313 film has the typical two-dimensional characteristics of the film, with a larger sheet diameter and a thinner thickness.
  • the present invention does not specifically limit the microstructure parameters of the aramid 1313 mesh fiber. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures that the aramid 1313 mesh
  • the performance of the fiber can better improve the performance of the aramid epoxy resin adhesive and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the diameter of the filament is preferably 10-500nm, more preferably 50-400nm, It is more preferably 100 to 300 nm, and more preferably 150 to 200 nm.
  • the diameter of the bar is preferably 0.5 to 20 ⁇ m, more preferably 3 to 18 ⁇ m, more preferably 5 to 15 ⁇ m, and more preferably 8 to 12 ⁇ m.
  • the diameter of the film is preferably 5 to 50 ⁇ m, more preferably 15 to 40 ⁇ m, and even more preferably 25 to 30 ⁇ m.
  • the present invention also provides a method for preparing aramid 1313 mesh fiber, which includes the following steps:
  • the present invention can correspond to the parameters, selection and structure in the above-mentioned preparation method, and the corresponding optimization principle, and the parameters, selection and structure relationship in the aforementioned aramid 1313 mesh fiber, and the corresponding optimization principle. Go into details one by one.
  • the polymerized aramid 1313 slurry is sprayed into the coagulation liquid, and coagulation and sedimentation are carried out under stirring conditions to obtain a wet fiber mass.
  • the present invention has no special restrictions on the polymerization method and process.
  • the conventional polymerization method and process for preparing aramid 1313 well known to those skilled in the art can be used according to actual production conditions, product requirements and quality requirements. Selection and adjustment.
  • the present invention has no special restrictions on the injection method and parameters of the aramid 1313 slurry. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention guarantees that the aramid 1313 mesh
  • the performance of the fiber-like fiber can better improve the performance of the aramid epoxy resin adhesive and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the injection method is preferably high-pressure spray formed by a platinum nozzle. .
  • the sprayed flow rate of the aramid 1313 slurry of the present invention is preferably less than or equal to 1000 mL/min, more preferably less than or equal to 800 mL/min, more preferably less than or equal to 500 mL/min, and can be 1 to 1000 mL/min, and can be 300 to 800 mL/min. min, can be 500-600mL/min.
  • the present invention has no special restrictions on the selection of the coagulation liquid. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the performance of aramid 1313 mesh fibers.
  • the coagulation liquid that is, the precipitating agent, preferably includes dimethylacetamide (DMAc) solution, more preferably It is a dimethylacetamide solution with a mass content of 45% to 55% (wherein, the mass content can also be 47% to 53%, or 49% to 51%).
  • DMAc dimethylacetamide
  • the dimethylacetamide solution of the present invention can be specifically 45%-55% dimethylacetamide, 0-1% polar solvent (such as lithium chloride) and 44%-54% water.
  • the polar solvent can also be 0.2% to 0.8%, or 0.4% to 0.6%; water can also be 46% to 52%, or 48% to 50%.
  • the present invention does not specifically limit the amount of the coagulation liquid. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid 1313 mesh fiber.
  • the mass ratio of the aramid 1313 slurry to the coagulation liquid is preferably 1: (2-20), more Preferably it is 1: (5-18), more preferably 1: (7-15), and more preferably 1: (10-13).
  • the present invention has no special restrictions on the state of coagulation and sedimentation. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid 1313 mesh fibers. It can improve the performance of aramid epoxy resin adhesive and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the coagulation sedimentation that is, sedimentation, is the result of the aramid slurry being coagulated into fibrous filaments.
  • the state preferably means that the aramid 1313 slurry has been coagulated into an aramid 1313 fiber shape after spinning.
  • the present invention has no special restrictions on the specific parameters of coagulation and precipitation. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the performance of aramid 1313 mesh fibers. Better improve the performance of the aramid epoxy resin adhesive and meet the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the solidification and sedimentation time that is, the stirring time or the time in the coagulation liquid, is preferably 5 ⁇ 40 min, more preferably 10 to 35 min, more preferably 15 to 30 min, more preferably 20 to 25 min.
  • the present invention has no special restrictions on the specific parameters of the hot air drying. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid 1313 mesh fiber.
  • the hot air drying temperature is preferably 60-85°C, more preferably 65-80°C, more preferably It is 70 ⁇ 75°C.
  • the aramid slurry after the polymerization reaction is sprayed into the coagulation bath through the platinum nozzle high pressure spray, and under the condition of stirring, the wet flocculent fiber cluster is formed on the stirring device or the rod medium, and then The obtained wet fiber mass is dried and fluffed through a large-scale hot-air drying device, and then the aramid 1313 mesh fiber is obtained in which the fiber filaments are interwoven to form a three-dimensional network structure.
  • the invention also provides an aramid epoxy resin adhesive, which is calculated as a percentage of the mass of the raw material, and includes:
  • the present invention does not specifically limit the specific selection of the epoxy resin. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid epoxy resin adhesive.
  • the epoxy resin preferably includes a flame-retardant epoxy resin.
  • the present invention does not have special restrictions on the amount of epoxy resin added. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid epoxy resin adhesive.
  • the epoxy resin is preferably added in an amount of 90 to 94 parts by weight, more preferably 90.5 to 93.5 parts by weight, more preferably 91 to 93 parts by weight, and more Preferably it is 91.5-92.5 parts by weight.
  • the present invention has no special restrictions on the specific selection of the silica. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid epoxy resin adhesive.
  • the silica preferably includes fumed silica powder.
  • the particle size of the silica is preferably 12 nm to 6 ⁇ m, more preferably 50 nm to 1 ⁇ m, more preferably 100 to 800 nm, more preferably 150 to 600 nm, and more preferably 200 to 400 nm.
  • the present invention does not have special restrictions on the amount of silica added. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid epoxy resin adhesive.
  • the added amount of silica is preferably 3.5 to 7.5 parts by weight, more preferably 4 to 7 parts by weight, more preferably 4.5 to 6.5 parts by weight, and more Preferably it is 5-6 weight parts.
  • the present invention does not specifically limit the specific selection of the foamed filler. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid epoxy resin adhesive.
  • the foamed filler preferably includes hollow glass beads, more preferably single-density hollow glass beads or hollow glass beads with different densities.
  • the foamed filler of the present invention is preferably used to adjust the density of the aramid epoxy resin glue.
  • the present invention has no special restrictions on the amount of foam filler added. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid epoxy resin adhesive.
  • the added amount of the foamed filler is preferably 0-10 parts by weight, more preferably 2-8 parts by weight, more preferably 4-6 parts by weight .
  • the present invention has no special restrictions on the specific parameters of the aramid 1313 mesh fiber. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures that the aramid epoxy resin adhesive
  • the performance of the aramid paper honeycomb composite product meets the processing requirements and quality requirements of the aramid paper honeycomb composite product.
  • the length of the aramid 1313 mesh fiber is preferably 1-7 mm, more preferably 2-6 mm, and more preferably 3-5 mm.
  • the aspect ratio of the aramid 1313 mesh fiber is preferably (50-1000):1, more preferably (250-800):1, and more preferably (450-600):1.
  • the present invention has no special restrictions on the amount of aramid 1313 mesh fiber added. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the performance of the aramid paper honeycomb composite product meets the processing requirements and quality requirements of the aramid paper honeycomb composite product.
  • the added amount of the aramid 1313 mesh fiber is preferably 0.3 to 0.5 parts by weight, more preferably 0.32 to 0.48 parts by weight, and more preferably 0.35 ⁇ 0.45 parts by weight, more preferably 0.38 to 0.42 parts by weight.
  • the aramid epoxy resin adhesive in order to complete and refine the technical solution, to ensure the performance of the aramid epoxy resin adhesive, it not only meets the processing requirements and quality requirements of the aramid paper honeycomb composite parts, but also further meets the various requirements of the composite parts
  • the types of the aramid epoxy resin adhesive preferably include one or more of aramid epoxy resin edge sealant, aramid epoxy resin filler and aramid epoxy resin molding adhesive, and more preferably include aramid Epoxy resin edge banding glue, aramid epoxy resin filling glue and aramid epoxy resin molding glue.
  • the present invention has no special restrictions on the composition of the aramid epoxy resin edge sealant. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the performance of the glue satisfies the various processing requirements and high quality requirements of composite parts.
  • the amount of silica added is preferably 3.5-5.7 by weight based on the mass percentage of raw materials. Parts, more preferably 3.8 to 5.5 parts by weight, more preferably 4.0 to 5.3 parts by weight, still more preferably 4.2 to 5.0 parts by weight.
  • the aramid epoxy resin edge banding glue of the present invention preferably controls the density, and the density of the aramid epoxy resin edge banding glue is preferably 0.6 to 1.0 g/cm 3 , more preferably 0.65 to 0.95 g/cm 3 , More preferably 0.7 to 0.9 g/cm 3 , more preferably 0.75 to 0.85 g/cm 3 .
  • the aramid epoxy resin edge sealing glue of the present invention is preferably used for edge sealing of lightweight honeycomb composite materials.
  • the present invention has no special restrictions on the composition of the aramid epoxy resin filler. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the performance of the composite parts meets the various processing requirements and high quality requirements of composite parts.
  • the added amount of silica is preferably 3.5 to 5.7 parts by weight based on the mass percentage of the raw material , More preferably 3.8 to 5.5 parts by weight, more preferably 4.0 to 5.3 parts by weight, still more preferably 4.2 to 5.0 parts by weight.
  • the aramid epoxy resin filler of the present invention preferably controls the density.
  • the density of the aramid epoxy resin filler is preferably 1.4 to 1.6 g/cm 3 , more preferably 1.42 to 1.58 g/cm 3 , and more It is preferably 1.45 to 1.55 g/cm 3 , more preferably 1.48 to 1.53 g/cm 3 .
  • the aramid epoxy resin filler of the present invention is preferably used for bonding hardware on resin composite materials.
  • the present invention has no special restrictions on the composition of the aramid epoxy resin molding adhesive. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures that the aramid epoxy resin adhesive
  • the performance of the composite parts meets the various processing requirements and high quality requirements.
  • the aramid epoxy resin molding glue preferably controls the amount of silica added.
  • the amount of silica added is calculated by the mass percentage of the raw material. The amount is preferably 5.7 to 7.5 parts by weight, more preferably 6.0 to 7.3 parts by weight, more preferably 6.2 to 7.0 parts by weight, and more preferably 6.4 to 6.8 parts by weight.
  • the density of the aramid epoxy resin filler of the present invention is preferably 0.9 to 1.6 g/cm 3 , more preferably 1.0 to 1.5 g/cm 3 , more preferably 1.1 to 1.4 g/cm 3 , and more preferably 1.2 to 1.3g/cm 3 .
  • the aramid epoxy resin molding glue of the present invention preferably has a dough-like morphology before curing; the aramid epoxy resin molding glue is preferably used for molding on resin composite materials.
  • the present invention also provides a method for preparing the aramid epoxy resin adhesive according to any one of the above technical solutions, including the following steps:
  • the specific preferred options of the raw materials, the preferred values of the added parts and the specific preferred options of the components in the aforementioned aramid epoxy resin adhesive, and the number of added parts are all the same, so I won’t repeat them here.
  • Step a) preferably further includes foamed fillers, that is, the raw materials are preferably aramid 1313 mesh fibers, epoxy resin, foamed fillers and silica.
  • the step a) may specifically be:
  • the present invention has no special restrictions on the specific parameters of the mixing. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid epoxy resin adhesive and meets the According to the processing requirements and quality requirements of the fiber-paper honeycomb composite article, the mixing time is preferably 10-30 min, more preferably 12-28 min, more preferably 15-25 min, and more preferably 18-22 min.
  • the aramid epoxy resin adhesive needs to be added with a curing aid before being used.
  • the present invention has no special restrictions on the specific selection and proportion of the curing aids. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the performance meets the processing requirements and quality requirements of the aramid paper honeycomb composite article.
  • the curing aid preferably includes a modified amine curing agent, an accelerator and a coupling agent.
  • the mass ratio of the aramid epoxy resin adhesive to the curing aid is preferably 4:1.
  • the present invention is a complete and detailed technical solution to ensure the performance of the aramid epoxy resin adhesive, and is more conducive to actual use when meeting the processing requirements and quality requirements of aramid paper honeycomb composite parts.
  • the open time of the glue is preferably 30-40 min, more preferably 32-38 min, more preferably 34-36 min.
  • the open time is the gluing time after mixing the A and B components of the aramid epoxy resin glue, including the mixing and gluing time. In the present invention, after the open time, the colloid gradually becomes viscous and hardens.
  • the invention also provides an aramid paper honeycomb composite article, which includes a prepreg cured sheet, an aramid paper honeycomb core and Hanikon glue;
  • the aramid paper honeycomb core is compounded between the cured prepreg sheets to form a sandwich structure
  • the Hanacon glue includes Hanacon adhesive glue
  • the Hanacon adhesive is bonded between the aramid paper honeycomb core and the prepreg cured sheet;
  • the Hanikang glue is the aramid epoxy resin glue according to any one of the above technical solutions or the aramid epoxy resin glue prepared by the preparation method according to any one of the above technical solutions.
  • the present invention does not have any special restrictions on the definition of the cured prepreg sheet.
  • the definition of the cured prepreg sheet is well known to those skilled in the art, and those skilled in the art can follow the actual production situation, product requirements and quality requirements.
  • the present invention is to ensure the performance of the aramid paper honeycomb composite part, meet the processing requirements, and facilitate mass production.
  • the prepreg cured sheet preferably refers to a sheet after the prepreg is cured by heat and pressure, preferably Prepreg resin cured sheet.
  • the present invention has no special restrictions on the selection of the prepreg cured sheet. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the quality of aramid paper honeycomb composite parts.
  • the prepreg cured sheet preferably includes glass fiber and/or carbon fiber prepreg cured sheet, more preferably glass fiber or carbon fiber prepreg cured sheet, that is, glass fiber resin prepreg Material curing sheet or carbon fiber resin prepreg curing sheet.
  • the present invention has no special restrictions on the structure of the prepreg cured sheet. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention guarantees the quality of aramid paper honeycomb composite parts.
  • the prepreg cured sheet preferably includes a double-layer prepreg cured sheet and/or a multilayer prepreg cured sheet.
  • the thickness of the double-layer prepreg cured sheet is preferably 0.3 to 0.36 mm, more preferably 0.31 to 0.35 mm, and more preferably 0.32 to 0.34 mm.
  • the thickness of the multilayer cured prepreg sheet is preferably greater than or equal to 0.45 mm, more preferably greater than or equal to 0.65 mm, more preferably greater than or equal to 0.85 mm.
  • the present invention has no special restrictions on the parameters of the prepreg cured sheet. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid paper honeycomb composite parts. Performance, meet processing requirements, and facilitate mass production.
  • the resin content of the cured prepreg is preferably 35%-65%, more preferably 40%-60%, and more preferably 45%-55%.
  • the volatile content of the cured prepreg sheet is preferably 8% or less, more preferably 6% or less, and more preferably 4% or less.
  • the present invention has no special restrictions on the aramid paper honeycomb core, and only a honeycomb core made of aramid paper known to those skilled in the art can be selected and adjusted according to actual production conditions, product requirements and quality requirements.
  • the material of the aramid honeycomb core of the present invention is preferably aramid paper;
  • the honeycomb core is preferably one of regular hexagonal honeycomb cores, polygonal honeycomb cores, corrugated honeycomb cores and overstretched honeycomb cores.
  • the present invention has no special restrictions on the parameters of the aramid paper honeycomb core. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements. Performance, meet processing requirements, and facilitate mass production.
  • the cell size of the aramid paper honeycomb core is preferably 1.83 to 3.67 mm, more preferably 2.03 to 3.37 mm, more preferably 2.33 to 3.17 mm, more preferably 2.63 to 3.17 mm.
  • the height of the aramid paper honeycomb core is preferably 1 to 860 mm, more preferably 50 to 600 mm, more preferably 100 to 500 mm, and more preferably 200 to 400 mm.
  • the density of the aramid paper honeycomb core is preferably 32 to 120 kg/m 3 , more preferably 40 to 110 kg/m 3 , more preferably 50 to 100 kg/m 3 , more preferably 60 to 90 kg/m 3 , more preferably It is 70 ⁇ 80kg/m 3 .
  • the present invention does not have any special restrictions on the Hanikon glue.
  • the Hanikon glue that is well known to those skilled in the art can be used, and it can be prepared by itself or purchased commercially. Those skilled in the art can according to actual production conditions, product requirements and The quality requirements are selected and adjusted.
  • the Hanacon adhesive preferably includes Hanacon adhesive, that is, aramid epoxy resin filler .
  • the Hanecon adhesive glue may specifically be Hanecon CP2016 glue.
  • the aramid paper honeycomb core is compounded between the cured prepreg sheets, that is, the upper and lower surfaces of the aramid paper honeycomb core are compounded with the prepreg cured sheets to form a sandwich-like sandwich structure.
  • the present invention has no special restrictions on the composite method. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid paper honeycomb composite parts and satisfies processing requirements. It is required to facilitate mass production, and the composite is preferably adhesive. That is, the Hanikon adhesive is bonded between the aramid paper honeycomb core and the prepreg cured sheet.
  • the present invention has no special restrictions on the selection of the Hanikon glue. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid paper honeycomb composite parts.
  • the Hanikon glue preferably further includes Hanikon edge banding glue, that is, aramid epoxy resin edge banding glue.
  • the Hanecon edge banding glue may specifically be Hanecon CP2015 glue.
  • the Hanikon edge banding glue is used as the edge banding of the aramid paper honeycomb composite product, that is, the Hanikon edge banding glue is arranged around the sandwich structure to form an edge banding.
  • the present invention does not specifically limit the amount of the Hanikon edge banding glue.
  • Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the quality of aramid paper honeycomb composite parts. Performance, meeting processing requirements, and conducive to mass production, the edge sealing thickness of the Hanikon edge banding glue is preferably 1-8mm, more preferably 2-6mm, more preferably 3-4mm, and more preferably 3.3-3.6mm.
  • the Hanikang glue can preferably be filled and embedded in the aramid paper honeycomb composite Any position of the part.
  • the Hanikon glue that is filled and embedded in any position of the aramid paper honeycomb composite article is specifically preferably Hanikon adhesive glue or Hanikon filling molding glue, more preferably Hanikon filling molding glue.
  • the present invention does not have any special restrictions on the Hanikon glue.
  • the Hanikon glue that is well known to those skilled in the art can be used, and it can be prepared by itself or purchased commercially. Those skilled in the art can according to actual production conditions, product requirements and Quality requirements are selected and adjusted.
  • the Hanacon glue preferably includes Hanacon filling molding glue, that is, aramid epoxy resin molding glue .
  • the Hanecon filling molding glue may specifically be Hanecon CP2017 glue.
  • the arbitrary position preferably includes a position requiring later machining or manual processing. That is to say, if you need to perform machining or manual processing on the aramid paper honeycomb composite part in the future, you can fill the parts that need to be machined or manually processed according to the process drawings with Hanikon adhesive or filling molding glue for pre-embedding.
  • the processing method of the present invention preferably includes one or more of size positioning, edge trimming, opening and slotting, and more preferably multiple of size positioning, edge trimming, opening and slotting.
  • the present invention further completes and refines the structure of the aramid paper honeycomb composite article, meets various needs, satisfies the processing requirements, and facilitates mass production.
  • the aramid paper honeycomb composite article preferably further includes hardware.
  • the present invention does not have any special restrictions on the arrangement of the hardware. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of aramid paper honeycomb composite parts.
  • the hardware is preferably arranged at the place where the embedded Hanikon glue (specifically, Hanikon adhesive glue or Hanikon filling molding glue) is filled.
  • the hardware can preferably also be used in conjunction with the Hanikang glue when it is installed.
  • the Hanikon glue used in combination in the present invention is specifically preferably Hanikon adhesive glue or Hanikon filling molding glue.
  • the molding can be filled with Hanikang glue, and the hardware can be embedded.
  • the aramid paper honeycomb composite part with Hanikon edge-sealing glue is finally obtained.
  • the invention also provides a method for preparing the aramid paper honeycomb composite article, which includes the following steps:
  • the aramid paper honeycomb is used as the core material, and the cured prepreg sheet is used as the surface material.
  • the adhesive is used for bonding with Hanikon adhesive. After the mold is closed and pressurized and cured, the edge is sealed with Hanikon edge sealing adhesive to obtain Aramid paper honeycomb composite parts.
  • the parameters, selection and structural relationship of the required materials in the above-mentioned aramid paper honeycomb composite article, and the corresponding optimization principle, and the parameters, selection and structural relationship in the aforementioned aramid paper honeycomb composite article, and the corresponding optimization The principles can be corresponded, so I won’t repeat them here.
  • the present invention does not specifically limit the source of the prepreg cured sheet. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the quality of aramid paper honeycomb composite parts. Performance, meeting processing requirements, and facilitating mass production, the prepreg cured sheet is particularly preferably obtained from glass fiber and/or carbon fiber prepreg after heat and pressure curing. Specifically:
  • Coat the contact surface between the prepreg and the mold with a release agent lay two or more layers of prepreg in the mold evenly, close the mold and put it into the hot press.
  • the present invention has no special restrictions on the process parameters in the above steps. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the process parameters in the above steps of the present invention are based on the material and number of layers of the prepreg. And product requirements for selection and adjustment.
  • the present invention does not particularly limit the parameters of the heat and pressure curing. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the performance of aramid paper honeycomb composite parts.
  • the temperature of the heat and pressure curing is preferably 120-150°C, more preferably 125-145°C, and more preferably 130-140°C.
  • the pressure of the thermo-pressurization curing of the present invention is preferably 0.1 to 0.3 MPa, more preferably 0.12 to 0.28 MPa, more preferably 0.15 to 0.25 MPa, and more preferably 0.18 to 0.22 MPa.
  • the heat and pressure curing time of the present invention is preferably 25 to 330 minutes, more preferably 60 to 300 minutes, more preferably 120 to 240 minutes, and more preferably 150 to 210 minutes.
  • the prepreg cured sheet is prepared separately, so that the prepreg can get rid of multiple restrictions such as refrigerated storage and short product shelf life.
  • the prepreg can be cured in batches, so that the hot press is no longer needed in the processing of finished parts. , Thereby reducing production costs and achieving mass production.
  • the present invention has no special restrictions on the bonding process. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention guarantees the performance of the aramid paper honeycomb composite parts and meets Processing requirements are conducive to mass production, and the bonding process preferably refers to the bonding standard DIN6701.
  • the present invention ensures the performance of the aramid paper honeycomb composite part, meets the processing requirements, and facilitates mass production, especially the above-mentioned bonding process is refined, and the pretreatment step is preferably included before the bonding .
  • the pretreatment preferably includes one or more of cutting, sanding, oil removal and dust removal, and more preferably cutting, sanding, oil removal and dust removal.
  • the prepreg cured sheet should be polished on both sides (if there is a prepreg splicing seam that needs to be polished smooth), use acetone or alcohol solvent to scrub to remove oil and dust.
  • the present invention does not have special restrictions on the bonding parameters. Those skilled in the art can select and adjust according to actual production conditions, product requirements and quality requirements.
  • the present invention ensures the performance of the aramid paper honeycomb composite parts and meets Processing requirements are conducive to mass production.
  • the dosage of the Hanikon adhesive for bonding is preferably 300-350 g/m2, more preferably 310-340 g/m2, more preferably 320-330 g/m2 .
  • the present invention has no special restrictions on the parameters of the clamping and pressurizing and curing. Those skilled in the art can select and adjust according to the actual production situation, product requirements and quality requirements.
  • the present invention is to ensure the performance of the aramid paper honeycomb composite parts. The performance meets the processing requirements and is conducive to mass production.
  • the pressure of the clamping and pressure curing is preferably 0.1 to 0.3 MPa, more preferably 0.12 to 0.28 MPa, more preferably 0.15 to 0.25 MPa, and more preferably 0.18 to 0.22 MPa.
  • the temperature of the clamping and pressure curing is preferably 25 to 60°C, more preferably 30 to 55°C, more preferably 35 to 50°C, and more preferably 40 to 45°C.
  • the time of clamping and pressing and curing includes two concepts: preliminary curing time and/or complete curing time.
  • the initial curing time of the clamping and pressure curing is preferably 3 to 48 hours, more preferably 12 to 36 hours, and more preferably 18 to 30 hours.
  • the complete curing time of the clamping and pressure curing is preferably 1 to 7 days, more preferably 2 to 6 days, and more preferably 3 to 5 days.
  • the initial curing time of the mold clamping and pressure curing is preferably 24 hours or more, more preferably 36 hours or more, and more preferably Equal to 48 hours.
  • the initial curing time of the mold clamping and pressure curing is preferably 3 hours or more, more preferably 5 hours or more, and more preferably 8 hours or more.
  • the complete curing time of the mold clamping and pressure curing is preferably 7 days or more, more preferably 9 days or more, and more preferably 12 days or more. day.
  • the complete curing time of the mold clamping pressure curing is preferably 1 day or more, more preferably 2 days or more, and more preferably 3 days or more.
  • the present invention does not specifically limit the amount of the Hanikon edge banding glue. Those skilled in the art can make selections and adjustments according to actual production conditions, product requirements and quality requirements.
  • the present invention is to ensure the quality of aramid paper honeycomb composite parts. Performance meets processing requirements and is conducive to mass production.
  • the amount of the Hanikon edge banding glue is preferably related to the thickness of the edge banding of the composite part.
  • the edge sealing thickness of the Hanecon edge sealing glue is preferably 1-8 mm, more preferably 2-6 mm, more preferably 3-4 mm, and more preferably 3.3-3.6 mm.
  • the invention preferably further includes a pretreatment step after bonding.
  • the filling and embedding step is specifically preferably:
  • the parts that need to be drilled, grooved, etc. are filled with Hanikon adhesive for pre-embedding.
  • the invention preferably further includes a machining step before and/or after the edge sealing.
  • the machining step is specifically preferably:
  • the parts After demolding, the parts are processed for size positioning, edge trimming, hole drilling, grooving, and hardware is installed or installed with the use of Hanikon adhesive.
  • the present invention preferably further includes a post-processing step before obtaining the aramid paper honeycomb composite article.
  • the post-treatment step preferably includes one or more of spray painting, film sticking and fireproofing board (preferably a thermosetting resin impregnated paper high-pressure laminate).
  • the specific preparation process of the above aramid paper honeycomb composite article may include the following steps:
  • Step 1 Put the double (multi-layer) glass fiber or carbon fiber prepreg into the hot press for curing to form a prepreg cured sheet;
  • Step 2 Cut the aramid paper honeycomb sheet and the prepreg cured sheet, and leave the corresponding size margin.
  • the prepreg cured sheet should be polished on both sides (if there is a prepreg splicing seam, it needs to be polished smoothly), and wiped with acetone or alcohol solvent to remove oil and dust
  • Step 3 Confirm the mixing ratio of Hanikon adhesive glue, strictly weigh the A and B components, and fully stir and mix the glue. After the A and B components are mixed, the appropriate operation time is about 30 minutes, and the gel hardens over time.
  • Step 4 According to the process drawings, fill the parts that need to be drilled, grooved, etc. to be machined with Hanikon adhesive for pre-embedding.
  • Step 5 For each layer, apply the Hanikon adhesive at an amount of 300-350g/m 2. After closing the mold, the flat part is pressurized by 0.1 ⁇ 0.2 MPa, and the arc part is pressurized by 0.2 ⁇ 0.3 MPa. Pressure curing (at least 24 hours at 25°C, and initial curing at 60°C for at least 3 hours).
  • Step 6 After demolding, the parts are processed for size positioning, edge trimming, opening, digging, filling and bonding with Hanikon adhesive (if necessary), and aramid paper honeycomb composite after edge sealing with Hanikon structural adhesive Parts.
  • Hanikon adhesive if necessary
  • aramid paper honeycomb composite after edge sealing with Hanikon structural adhesive Parts.
  • Step 7 The aramid paper honeycomb composite article obtained in step 6 is coated, filmed or pasted with a fireproof board (thermosetting resin impregnated paper high-pressure laminate) to obtain a light weight suitable for use in the interior decoration of Chinese standard EMUs. Quantify partition cabinet panels.
  • a fireproof board thermosetting resin impregnated paper high-pressure laminate
  • the present invention also provides the aramid paper honeycomb composite article according to any one of the above technical solutions or the aramid paper honeycomb composite article prepared by the preparation method of any one of the above technical solutions in terms of lightweight panel furniture application.
  • the present invention has no special restrictions on the specific selection of the lightweight panel furniture.
  • the concept of panel furniture in a broad sense that is well known to those skilled in the art can be used. Those skilled in the art can choose according to the use situation, environmental requirements and performance requirements.
  • the lightweight panel furniture of the present invention is more preferably a lightweight panel furniture on a sports carrier, and specifically can be high-speed rail train interiors, partitions, cabinets, etc.
  • the above steps of the present invention provide an aramid paper honeycomb and its normal temperature preparation method and application.
  • the aramid paper honeycomb core is pasted between the cured prepreg sheets by using the Hanikon adhesive glue to form a sandwich structure, and then the aramid paper honeycomb composite part is edge-sealed by using the Hanikon edge sealing glue to obtain Aramid paper honeycomb composite part is a kind of aramid paper honeycomb composite part that can be cured at room temperature.
  • the aramid paper honeycomb composite article provided by the present invention adopts the prepreg cured sheet prepared in advance and the Hanikon glue, and can be composited at room temperature in the final composite process, reducing production time and equipment investment, and making the finished product When processing parts, it is no longer necessary to occupy large equipment such as hot presses, large vacuum tanks, and high temperature ovens, thereby reducing production costs and realizing the industrial production of large quantities of aramid paper honeycomb composite panels.
  • the use of Hanikon glue for edge sealing can directly produce batches of panels, and the comprehensive use of Hanikon glue for bonding, edge sealing and landfilling can produce various batches of panels.
  • Hanikang glue can also be used for edge banding and post-processing to obtain customized finished plates. This is also conducive to batch industrial production and solves the limitations of customized processing.
  • the prepreg cured sheet is prepared separately in advance, which also frees the prepreg from multiple restrictions such as refrigerated storage and short product shelf life, and can be cured in batches.
  • the normal temperature preparation method provided by the present invention has simple process and mild conditions, and is more suitable for large-scale production and promotion, and the prepared aramid paper honeycomb composite article effectively maintains the rigidity, flatness and strength of the aramid paper honeycomb core, and has Good flame retardancy, heat preservation and mechanical properties.
  • the above steps of the present invention provide an aramid 1313 mesh fiber and a preparation method thereof, a normal temperature curing aramid flame-retardant epoxy resin structural adhesive series and a preparation method thereof, and an aramid paper honeycomb composite article.
  • the present invention adopts a specific aramid 1313 mesh fiber, which has a floc-like fiber cluster morphology, and the aramid 1313 fiber filaments are interwoven to form a three-dimensional network structure.
  • it is used in epoxy resin glue to obtain an aramid epoxy resin glue.
  • Aramid 1313 mesh fiber is added to the epoxy resin glue, similar to the principle of cement and steel reinforcement, so that the epoxy resin glue is cured After that, it has better bonding properties such as better compression resistance, shear resistance, crack resistance, and low temperature resistance.
  • the aramid epoxy resin adhesive is a series of flame-retardant epoxy resin structural adhesives. It not only has good bonding performance, but also can be used for edge banding and molding by adjusting the components and physical parameters, thereby satisfying multiple requirements. Demand.
  • Aramid epoxy resin adhesive can be cured at room temperature and has good performance. It can meet the relevant standards of aramid paper honeycomb composite parts, thereby solving the cumbersome process of preparing aramid honeycomb composite parts. Defects such as high cost.
  • the invention also provides an aramid paper honeycomb composite article process and a normal temperature preparation method thereof.
  • the aramid epoxy resin glue is used to paste the aramid paper honeycomb core between the cured prepreg sheets to form a sandwich structure to obtain an aramid paper honeycomb composite article.
  • the aramid paper honeycomb composite article provided by the present invention adopts a prepreg cured sheet prepared in advance and an aramid epoxy resin glue, and can be compounded at room temperature in the final compounding process, reducing production time and equipment investment. This eliminates the need for large-scale equipment such as hot presses, large vacuum tanks, and high-temperature ovens when processing finished parts, thereby reducing production costs and realizing the industrial production of large quantities of aramid paper honeycomb composite panels.
  • the prepared aramid paper honeycomb composite article effectively maintains the rigidity, flatness and strength of the aramid paper honeycomb core, and has good flame retardancy, heat preservation and mechanical properties.
  • the preparation method of the aramid 1313 mesh fiber, the flame-retardant epoxy resin structural glue and the aramid paper honeycomb composite article provided by the invention has simple process and mild conditions, and is more suitable for large-scale production and promotion.
  • the aramid epoxy resin adhesive provided by the present invention has a colloidal Shore hardness of 85-95D after being fully cured, and the compressive strength of the cured rubber block is greater than or equal to 55-65MPa; the tensile force of the 10mm deep M6 screw is greater than or equal to 2000N; The strength (60°C for 3 days, 25°C for 7 days at normal temperature) is greater than or equal to 10-15MPa; it has good low temperature performance, and the low temperature resistance reaches -55°C.
  • the prepared aramid paper honeycomb composite parts also have good comprehensive properties, with tensile properties of 1.70-2.40MPa; flat compression properties of 2.0-3.6MPa; shear properties of 0.60-1.30MPa; roller peel strength of 45 ⁇ 70N*mm/mm; the bending stiffness is 6.0*10 7 ⁇ 11.0*10 7 N ⁇ mm 2 .
  • the polymerized aramid 1313 slurry is sprayed into the coagulation liquid through a platinum nozzle to form a high-pressure spray.
  • the coagulation liquid is a precipitating agent, which is a 50% dimethylacetamide (DMAc) solution and 50% ionized water.
  • the mixed liquid, the flow rate of aramid 1313 slurry sprayed into is 500mL/min. Stir while spraying, and synchronously add the coagulation liquid into the sedimentation tank at a flow of 3000 mL/min. After 30 minutes of coagulation and sedimentation of the aramid 1313 slurry, a wet fiber mass is obtained.
  • the aramid 1313 mesh fiber prepared in Example 1 of the present invention was tested.
  • the aramid 1313 mesh fiber prepared in Example 1 of the present invention was characterized.
  • Fig. 1 is an appearance diagram of the aramid 1313 mesh fiber prepared by the present invention.
  • the aramid 1313 mesh fiber prepared by the present invention has a flocculent fiber cluster, or a macroscopic morphology of a cotton-like fiber cluster, and the aramid 1313 fiber filaments are interwoven to form a 3D three-dimensional space. grid.
  • the aramid 1313 mesh fiber prepared by the present invention has a microscopic three-dimensional network structure formed by mutual cross-linking of filaments, strips and membranes.
  • the mixing time is 30 min.
  • the mass ratio of the A-component aramid epoxy resin adhesive to the B-component curing aid is preferably 4:1.
  • the A and B components were stirred and mixed at a mass ratio of 4:1 for 10 minutes to make a test sample.
  • Table 2 is the performance data of the aramid epoxy resin edge sealant prepared in Example 2 of the present invention.
  • Hardness of fully cured colloid Shaw ⁇ 85D Compressive strength of cured rubber block ⁇ 55MPa Density of fully cured colloid 1.0 g/cm 3 Shear strength (MPa) ⁇ 10MPa (3 days at 60°C, 7 days at 25°C normal temperature)
  • the mixing time is 30 min.
  • the mass ratio of the A-component aramid epoxy resin adhesive to the B-component curing aid is preferably 4:1.
  • the A and B components were stirred and mixed at a mass ratio of 4:1 for 10 minutes to make a test sample.
  • Hardness of fully cured colloid Shaw ⁇ 92D Compressive strength of cured rubber block ⁇ 63MPa Density of fully cured colloid ⁇ 1.5g/cm 3 Shear strength (MPa) ⁇ 15MPa (3 days at 60°C, 7 days at 25°C normal temperature)
  • the A-component aramid epoxy resin adhesive After purchasing 92% of the A-component epoxy resin, 0.5% of the aramid 1313 mesh fiber, and 7.5% of the silica, the A-component aramid epoxy resin adhesive is obtained.
  • the mixing time is 30 min.
  • the mass ratio of the A-component aramid epoxy resin adhesive to the B-component curing aid is preferably 4:1.
  • the A and B components were stirred and mixed at a mass ratio of 4:1 for 10 minutes to make a test sample.
  • Hardness of fully cured colloid Shaw ⁇ 90D Compressive strength of cured rubber block ⁇ 60MPa Density of fully cured colloid ⁇ 1.6g/cm 3 Shear strength (MPa) ⁇ 13MPa (3 days at 60°C, 7 days at 25°C normal temperature)
  • Wipe and clean the mold with solvent and check the flatness of the mold Coat the contact surface between the prepreg and the mold with 55NC release agent, lay two or more layers of glass fiber phenolic prepreg in the mold evenly, and place the mold in the hot press. Raise the temperature from 20°C to 80°C and keep the temperature for 40 minutes, the heating rate is 1°C/min, the pressure is 0.1MPa; then the temperature is raised to 120°C and the temperature is kept for 60 minutes, the heating rate is 2°C/min, and the pressure is 0.2MPa; The temperature rise rate is 2°C/min and the pressure is 0.3 MPa to 150°C and heat preservation for 20 min. After cooling, it is taken out of the mold to prepare a qualified glass fiber phenolic prepreg cured sheet.
  • Table 5 is the performance data of the glass fiber phenolic prepreg cured sheet prepared in Example 5 of the present invention.
  • the glued surfaces of the two prepreg cured sheets are smoothed with sandpaper, then dusted and wiped with acetone solvent.
  • Coat the Hanikon adhesive CP2016 uniformly according to the glue amount of 330 g/m2, and glue it on the upper and lower sides of the aramid honeycomb to form a sandwich structure.
  • Example 5 of the present invention The performance of the aramid honeycomb composite part prepared in Example 5 of the present invention was tested.
  • PS The test standard stipulates that 5 samples are tested simultaneously to obtain the average value.
  • Wipe and clean the mold with solvent and check the flatness of the mold Coat the contact surface between the prepreg and the mold with 55NC release agent, lay two or more layers of glass fiber phenolic prepreg in the mold evenly, and place the mold in the hot press. The temperature was raised from 60°C to 145°C and kept for 30 minutes, the heating rate was 3°C/min, and the pressure was 0.25MPa. After cooling to 60°C, it was taken out of the mold to prepare a qualified fast-curing glass fiber phenolic prepreg. sheet.
  • Table 8 is the performance data of the glass fiber phenolic prepreg cured sheet prepared in Example 6 of the present invention.
  • the glued surfaces of the two prepreg cured sheets are smoothed with sandpaper, then dusted and wiped with acetone solvent.
  • Coat the Hanikon adhesive CP2016 uniformly according to the glue amount of 330 g/m2, and glue it on the upper and lower sides of the aramid honeycomb to form a sandwich structure.
  • Table 9 is the roll peel test performance data of the aramid honeycomb composite prepared in Example 6 of the present invention.
  • PS The test standard stipulates that 5 samples are tested simultaneously to obtain the average value.
  • Wipe and clean the mold with solvent and check the flatness of the mold Coat the contact surface between the prepreg and the mold with 55NC release agent, lay two or more layers of glass fiber phenolic prepreg in the mold evenly, and place the mold in the hot press. Raise the temperature from 20°C to 80°C and keep the temperature for 40 minutes, the heating rate is 1°C/min, the pressure is 0.1MPa; then the temperature is raised to 120°C and the temperature is kept for 60 minutes, the heating rate is 2°C/min, and the pressure is 0.2MPa; The temperature rise rate is 2°C/min and the pressure is 0.3 MPa to 150°C and heat preservation for 20 min. After cooling, it is taken out of the mold to prepare a qualified glass fiber phenolic prepreg cured sheet.
  • Table 11 is the performance data of the glass fiber phenolic prepreg cured sheet prepared in Example 7 of the present invention.
  • the glued surfaces of the two prepreg cured sheets are smoothed with sandpaper, then dusted and wiped with acetone solvent.
  • Example 7 of the present invention The performance of the aramid honeycomb composite part prepared in Example 7 of the present invention was tested.
  • PS The test standard stipulates that 5 samples are tested simultaneously to obtain the average value.
  • the aramid 1313 mesh fiber provided by the present invention and its preparation method, the series of aramid flame-retardant epoxy resin structural adhesives cured at room temperature and its preparation method, and the aramid paper honeycomb composite article have been introduced in detail above. Specific examples are used to illustrate the principle and implementation of the present invention. The description of the above examples is only used to help understand the method and core ideas of the present invention, including the best way, and also make anyone skilled in the art convinced can practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

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Abstract

提供芳纶1313网状纤维,芳纶1313纤维为絮状纤维团状芳纶1313纤维,芳纶1313纤维丝之间交织形成立体网状结构。芳纶1313网状纤维用于环氧树脂胶中得到芳纶环氧树脂胶,该芳纶环氧树脂胶用于制备芳纶纸蜂窝复合制件。

Description

[根据细则37.2由ISA制定的发明名称] 芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法
本申请要求于2019年07月02日提交中国专利局、申请号为201910591470.2、发明名称为“一种芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
技术领域
本发明属于芳纶环氧树脂胶技术领域,具体涉及一种芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法,特别涉及一种芳纶1313网状纤维及其制备方法、常温固化的芳纶阻燃环氧树脂结构胶系列及其制备方法、芳纶纸蜂窝复合制件。
背景技术
胶黏剂是指通过界面的黏附和内聚等作用,能使两种或两种以上的制件或材料连接在一起的天然的或合成的、有机的或无机的一类物质,统称为胶黏剂,又叫黏合剂,习惯上简称为胶。简而言之,胶黏剂就是通过黏合作用,能使被黏物结合在一起的物质。胶接(粘合、粘接、胶结、胶粘)是指同质或异质物体表面用胶黏剂连接在一起的技术,可以适用于不同材质、不同厚度、超薄规格和复杂构件的连接。胶接近代发展最快,应用行业极广。胶黏剂的分类方法很多,按应用方法可分为热固型、热熔型、室温固化型、压敏型等。其中,热固型胶是工业上应用较多的一类胶,主要包括环氧树脂、酚醛树脂、脲醛树脂、三聚氰-甲醛树脂、有机硅树脂、呋喃树脂、不饱和聚酯、丙烯酸树脂、聚酰亚胺、聚苯并咪唑、酚醛-聚乙烯醇缩醛、酚醛-聚酰胺、酚醛-环氧树脂、环氧-聚酰胺等类别。但是热固型胶的粘接固化,往往都需要进行加热,这为其应用带来了极大的不便,限制了其进一步的应用。
在当今高速和高效的社会,需要更加便捷快速的交通发展,各种运动载体(交通工具)为了节能环保和高速化纷纷进行轻量化设计,航空材料中的芳纶纸蜂窝,具有低密度、高强度、无热胀冷缩、无金属疲劳、阻燃、无毒、耐低温等优点,而国内的高铁发展,同样将芳纶纸蜂窝芯制件批量化应用到了高铁车辆内饰材料上。
然而,在这一航空转民用的过程中,目前最普遍的芳纶蜂窝复合制件的生产工艺在制作上,是钢模热压、真空罐热压、真空袋热复等等,不仅能耗大,设备成本高,而且生产效率低,需要高温热压机、大型真空罐、高温烘箱等大型设备,难以达到大批量低成本的生产,导致产品昂贵,特别是在定制加工上还存在很大的局限性,大大限制了芳纶纸蜂窝复合制件的发展和广泛应用。
因此,如何找到一种适宜的树脂胶及其生产方法,能够在常温下进行固化,同时具有较好的性能,能够解决目前芳纶蜂窝复合制件存在的上述缺陷,满足芳纶纸蜂窝复合制件的相关标准,已成为行业内各生产厂家亟待解决的问题之一。
发明内容
有鉴于此,本发明要解决的技术问题在于提供一种芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法,特别是一种常温固化的芳纶阻燃环氧树脂结构胶系列。本发明提供的芳纶阻燃环氧树脂结构胶系列,具有较好的粘接性能,而且还能够用于封边和塑型,进而满足多方面的需求。
本发明提供了一种芳纶1313网状纤维,所述芳纶1313纤维为絮状纤维团状芳纶1313纤维;
芳纶1313纤维丝之间交织形成立体网状结构。
优选的,所述芳纶1313网状纤维的细度为1~2D;
所述芳纶1313网状纤维在微观上,具有丝状、条状和膜状相互交联形成的微观立体网状结构;
所述丝的直径为10~500nm;
所述条的直径为0.5~20μm;
所述膜的直径为5~50μm。
本发明提供了一种芳纶1313网状纤维的制备方法,包括以下步骤:
1)将聚合后的芳纶1313浆料喷入凝固液中,在搅拌的条件下进行凝固沉析,得到湿纤维团;
2)将上述步骤得到的湿纤维团经过热风干燥后,得到蓬松的芳纶1313网状纤维。
优选的,所述凝固液包括二甲基乙酰胺溶液;
所述芳纶1313浆料喷入的流量小于等于1000mL/min;
所述芳纶1313浆料与凝固液的质量比为1:(2~20);
所述凝固沉析的时间为5~40min;
所述热风干燥的温度为60~85℃。
本发明提供了一种芳纶环氧树脂胶,按原料质量百分比计,包括:
Figure PCTCN2020096445-appb-000001
优选的,所述环氧树脂包括阻燃环氧树脂;
所述芳纶1313网状纤维的长度为1~7mm;
所述芳纶1313网状纤维的长宽比为(50~1000):1;
所述二氧化硅包括气相二氧化硅粉;
所述发泡填充料包括空心玻璃微珠和/或纳米空心漂浮粉;
所述芳纶环氧树脂胶包括芳纶环氧树脂封边胶、芳纶环氧树脂填充胶和芳纶环氧树脂成型胶中的一种或多种;
所述芳纶环氧树脂封边胶和芳纶环氧树脂填充胶中,按原料质量百分比计,所述二氧化硅各自选自3.5~5.7重量份;
所述芳纶环氧树脂成型胶中,按原料质量百分比计,所述二氧化硅为5.7~7.5重量份。
优选的,所述二氧化硅的粒径为12nm~6μm;
所述芳纶环氧树脂封边胶的密度为0.6~1.0g/cm 3
所述芳纶环氧树脂封边胶用于轻质蜂窝复合材料封边;
所述芳纶环氧树脂填充胶的密度为1.4~1.6g/cm 3
所述芳纶环氧树脂填充胶用于在树脂复合材料上粘接五金件;
所述芳纶环氧树脂成型胶的密度为0.9~1.6g/cm 3
所述芳纶环氧树脂成型胶在固化前成面团状;
所述芳纶环氧树脂成型胶用于在树脂复合材料上进行造型。
本发明提供了一种如上述技术方案任意一项所述的芳纶环氧树脂胶的制 备方法,包括以下步骤:
a)将芳纶1313网状纤维、环氧树脂和二氧化硅进行混合后,得到芳纶环氧树脂胶。
优选的,所述步骤a)中,还包括发泡填充料;
所述混合的时间为10~30min;
所述芳纶环氧树脂胶在使用前,还需加入固化助剂;
所述固化助剂包括改性胺类固化剂、促进剂和偶联剂;
所述芳纶环氧树脂胶与固化助剂的质量比为4:1;
所述芳纶环氧树脂胶的开放时间为30~40min。
本发明还提供了一种芳纶纸蜂窝复合制件,包括预浸料固化片、芳纶纸蜂窝芯以及哈尼康胶;
所述芳纶纸蜂窝芯复合在所述预浸料固化片之间,形成夹层结构;
所述哈尼康胶包括哈尼康粘接胶;
所述哈尼康粘接胶粘接在所述芳纶纸蜂窝芯和所述预浸料固化片之间;
所述哈尼康胶为上述技术方案任意一项所述的芳纶环氧树脂胶或上述技术方案任意一项所述的制备方法所制备的芳纶环氧树脂胶。
优选的,所述哈尼康胶还包括哈尼康封边胶;
所述哈尼康封边胶作为所述芳纶纸蜂窝复合制件的封边。
所述预浸料固化片包括玻纤和/或碳纤预浸料固化片;
所述哈尼康胶还可以填充预埋在所述芳纶纸蜂窝复合制件的任意位置;
所述芳纶纸蜂窝复合制件还包括五金件。
优选的,所述任意位置包括需要后期进行机加工或手工加工的位置;
所述加工的方式包括尺寸定位、切边、开孔和挖槽中的一种或多种;
所述五金件设置在填充预埋或后埋的哈尼康胶处;
所述五金件在设置时还可以与所述哈尼康胶配合使用。
优选的,所述预浸料固化片包括双层预浸料固化片和/或多层预浸料固化片;
所述双层预浸料固化片的厚度为0.3~0.36mm;
所述多层预浸料固化片的厚度大于等于0.45mm;
所述预浸料固化片的树脂含量为35%~65%;
所述预浸料固化片的挥发分含量小于等于8%。
优选的,所述芳纶纸蜂窝芯形状包括正六边形蜂窝芯、多边形蜂窝芯、波纹形蜂窝芯和过拉伸形蜂窝芯中的一种或多种;
所述芳纶纸蜂窝芯的孔格尺寸为1.83~3.67mm;
所述芳纶纸蜂窝芯的密度为32~120kg/m 3
所述芳纶纸蜂窝芯的高度为1~860mm。
本发明还提供了一种芳纶纸蜂窝复合制件的制备方法,包括以下步骤:
A)将芳纶纸蜂窝作为芯材,预浸料固化片作为面材,通过哈尼康粘接胶进行粘接,合模加压固化后,再采用哈尼康封边胶进行封边后,得到芳纶纸蜂窝复合制件。
优选的,所述合模加压固化的温度为25~60℃;
所述合模加压固化的初步固化时间为3~48小时;
所述合模加压固化的完全固化时间为1~7天;
所述合模加压固化的压力为0.1~0.3MPa;
所述预浸料固化片由玻纤和/或碳纤预浸料经过热加压固化后得到;
所述热加压固化的温度为120~150℃;
所述热加压固化的时间为25~330分钟;
所述热加压固化的压力为0.1~0.3MPa。
优选的,所述粘接前还包括预处理步骤;
所述预处理包括裁剪、打磨、去油和除尘中的一种或多种;
所述哈尼康粘接胶的用量为300~350克/平方米;
所述粘接后还包括填充预埋步骤;
所述封边前和/或封边后,还包括机加工步骤;
在得到所述芳纶纸蜂窝复合制件之前还包括后处理步骤。
优选的,所述填充预埋步骤具体为:
在需要后期进行机加工或手工加工的位置,填充哈尼康粘接胶进行预埋;
所述机加工步骤具体为:
对制件的填充预埋位置进行尺寸定位、切边、开孔和挖槽中的一步或多步 后,加装五金件或在哈尼康粘接胶的配合使用下加装五金件;
所述后处理步骤包括喷漆涂装、贴膜和贴防火板中的一种或多种。
本发明还提供了上述技术方案任意一项所述的芳纶纸蜂窝复合制件或上述技术方案任意一项所述的制备方法所制备的芳纶纸蜂窝复合制件在轨道交通轻量化、轻质阻燃板材家具方面的应用。
本发明提供了一种芳纶1313网状纤维,所述芳纶1313纤维为絮状纤维团状芳纶1313纤维;芳纶1313纤维丝之间交织形成立体网状结构。与现有技术相比,本发明针对现有热固型胶的粘接固化,往往都需要进行加热,这为其应用带来了极大的不便,限制了其进一步的应用的弊端。更结合目前现有的芳纶蜂窝复合制件生产工艺,在工艺过程上存在能耗大,设备成本高,生产效率低,需要高温热压机,难以达到大批量低成本的生产,导致产品昂贵,特别是在定制加工上还存在很大的局限性的问题。
本发明创造性的得到了一种芳纶1313网状纤维,该芳纶1313纤维具有絮状纤维团状的形貌,而且芳纶1313纤维丝之间交织形成立体网状结构。本发明又将其用于环氧树脂胶中,得到了一种芳纶环氧树脂胶,在环氧树脂胶中加入芳纶1313网状纤维,类似水泥加钢筋原理,使得环氧树脂胶固化后具有更好抗压、抗剪、防开裂、耐低温等较好的粘接性能。该芳纶环氧树脂胶是一种阻燃环氧树脂结构胶系列,不仅具有较好的粘接性能,而且通过调整组分和物理参数,还能够用于封边和塑型,进而满足多方面的需求。芳纶环氧树脂胶能够在常温下进行固化,同时具有较好的性能,能够满足芳纶纸蜂窝复合制件的相关标准,从而解决了目前制备芳纶蜂窝复合制件存在的过程繁琐,生产成本高等缺陷。
本发明还设计了一种芳纶纸蜂窝复合制件工艺及其常温制备方法。本发明利用上述芳纶环氧树脂胶,将芳纶纸蜂窝芯粘贴在预浸料固化片之间,形成夹层结构,得到了芳纶纸蜂窝复合制件。本发明提供的芳纶纸蜂窝复合制件,采用先期制备好的预浸料固化片结合芳纶环氧树脂胶,能够在最后的复合工序中使用常温进行复合,减少了生产时间和设备投入,使得在成品件加工时,不再需要占用热压机、大型真空罐、高温烘箱等大型设备,从而降低生产成本,实现大批量芳纶纸蜂窝复合板的工业化生产。而且制备的芳纶纸蜂窝复合制件有 效的保持了芳纶纸蜂窝芯的刚性、平整度及强度,具有较好的阻燃性、保温性以及力学性能。本发明提供的芳纶1313网状纤维的制备方法工艺简单,条件温和,更加适于规模化生产与推广。
实验结果表明,本发明提供的芳纶环氧树脂胶,完全固化后胶体邵氏硬度为85~95D,固化胶块的压缩强度大于等于55~65MPa;10mm深M6螺钉拉力大于等于2000N;剪切强度(60℃保温3天,25℃常温7天)大于等于10~15MPa,具有较好的低温性能,耐低温达到-55℃。而且制备的芳纶纸蜂窝复合制件同样具有较好的综合性能,拉伸性能为1.70~2.40MPa;平压性能为2.0~3.6MPa;剪切性能为0.60~1.30MPa;滚筒剥离强度为45~70N*mm/mm;弯曲刚度为6.0*10 7~11.0*10 7N·mm 2
附图说明
图1为本发明制备的芳纶1313网状纤维的外观图;
图2为本发明制备的芳纶1313网状纤维的扫描电镜图。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为了进一步说明本发明的特征和优点,而不是对发明权利要求的限制。
本发明所有原料,对其来源没有特别限制,在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
本发明所有原料,对其纯度没有特别限制,本发明优选采用分析纯或芳纶环氧树脂胶制备领域常规的纯度要求。
本发明所有原料,其牌号和简称均属于本领域常规牌号和简称,每个牌号和简称在其相关用途的领域内均是清楚明确的,本领域技术人员根据牌号、简称以及相应的用途,能够从市售中购买得到或常规方法制备得到。
本发明提供了一种芳纶1313网状纤维,所述芳纶1313纤维为絮状纤维团状芳纶1313纤维;
芳纶1313纤维丝之间交织形成立体网状结构。
本发明对所述芳纶1313的定义没有特别限制,以本领域技术人员熟知的芳纶1313的定义和概念即可,本领域技术人员可以根据实际生产情况、产品 要求和质量要求进行选择和调整,可以是一种聚酰胺纤维,可称为聚间苯二甲酰间苯二胺纤维。
本发明所述芳纶1313网状纤维,具有絮状纤维团状,或类似棉絮状的纤维团的宏观形貌,而且芳纶1313纤维丝之间交织形成3D立体空间的网状结构。
本发明原则上对所述芳纶1313网状纤维的特征参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述芳纶1313网状纤维的细度优选为1~2D,更优选为1.2~1.8D,更优选为1.4~1.6D。
本发明原则上对所述芳纶1313网状纤维的微观结构没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,在微观上,所述芳纶1313网状纤维特别优选具有丝状、条状和膜状相互交联形成的微观立体网状结构。在本发明中,丝状、条状和膜状,其组成上均是芳纶1313,芳纶1313丝具有细丝状,芳纶1313条可以是芳纶1313膜卷曲后成为条状,也可以是芳纶1313丝缠绕在一起形成条状,而芳纶1313膜则具有膜的典型类二维性征,较大的片径和较薄的厚度。
本发明原则上对所述芳纶1313网状纤维的微观结构参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述丝的直径优选为10~500nm,更优选为50~400nm,更优选为100~300nm,更优选为150~200nm。所述条的直径优选为0.5~20μm,更优选为3~18μm,更优选为5~15μm,更优选为8~12μm。所述膜的直径优选为5~50μm,更优选为15~40μm,更优选为25~30μm。
本发明还提供了一种芳纶1313网状纤维的制备方法,包括以下步骤:
1)将聚合后的芳纶1313浆料喷入凝固液中,在搅拌的条件下进行凝固沉 析,得到湿纤维团;
2)将上述步骤得到的湿纤维团经过热风干燥后,得到蓬松的芳纶1313网状纤维。
本发明对上述制备方法中的参数、选择和结构,以及相应的优选原则,与前述芳纶1313网状纤维中参数、选择和结构关系,以及相应的优选原则均可以进行对应,在此不再一一赘述。
本发明首先将聚合后的芳纶1313浆料喷入凝固液中,在搅拌的条件下进行凝固沉析,得到湿纤维团。
本发明对所述聚合的方式和过程没有特别限制,以本领域技术人员熟知的常规制备芳纶1313的聚合方式和过程即可,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整。
本发明原则上对所述芳纶1313浆料喷入的方式和参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述喷入的方式优选为通过白金喷头形成高压喷雾进行喷入。本发明所述芳纶1313浆料喷入的流量优选小于等于1000mL/min,更优选小于等于800mL/min,更优选小于等于500mL/min,可以为1~1000mL/min,可以为300~800mL/min,可以为500~600mL/min。
本发明原则上对所述凝固液的选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述凝固液,即沉析剂,优选包括二甲基乙酰胺(DMAc)溶液,更优选为质量含量为45%~55%的二甲基乙酰胺溶液(其中,质量含量还可以为47%~53%,或49%~51%)。本发明所述二甲基乙酰胺溶液具体可以为45%~55%的二甲基乙酰胺、0~1%的极性溶剂(如氯化锂)和44%~54%的水。其中,极性溶剂也可以为0.2%~0.8%,或者为0.4%~0.6%;水也可以为46%~52%,或者为48%~50%。
本发明原则上对所述凝固液的用量没有特别限制,本领域技术人员可以根 据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述芳纶1313浆料与凝固液的质量比优选为1:(2~20),更优选为1:(5~18),更优选为1:(7~15),更优选为1:(10~13)。
本发明原则上对所述凝固沉析的状态没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述凝固沉析,即沉析,是芳纶浆料凝固后沉析成纤维丝的状态,优选是指芳纶1313浆料经喷丝后已凝固成芳纶1313纤维状。
本发明原则上对所述凝固沉析的具体参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述凝固沉析的时间,即搅拌的时间或在凝固液中时间,优选为5~40min,更优选为10~35min,更优选为15~30min,更优选为20~25min。
本发明随后将上述步骤得到的湿纤维团经过热风干燥后,得到蓬松的芳纶1313网状纤维。
本发明原则上对所述热风干燥的具体参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶1313网状纤维的性能,更好的提高芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述热风干燥的温度优选为60~85℃,更优选为65~80℃,更优选为70~75℃。
本发明经过上述步骤,将聚合反应后的芳纶浆料通过白金喷头高压喷雾状打入凝固浴中,在搅拌的条件下,在搅拌装置或棍棒介质上,形成湿的絮状纤维团,然后将得到的湿纤维团,通过大型的热风烘干设备,进行干燥蓬松后,得到纤维丝交织形成立体网状结构的芳纶1313网状纤维。
本发明还提供了一种芳纶环氧树脂胶,按原料质量百分比计,包括:
Figure PCTCN2020096445-appb-000002
Figure PCTCN2020096445-appb-000003
本发明原则上对所述环氧树脂的具体选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述环氧树脂优选包括阻燃环氧树脂。
本发明原则上对所述环氧树脂的加入量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述环氧树脂的加入量优选为90~94重量份,更优选为90.5~93.5重量份,更优选为91~93重量份,更优选为91.5~92.5重量份。
本发明原则上对所述二氧化硅的具体选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述二氧化硅优选包括气相二氧化硅粉。所述二氧化硅的粒径优选为12nm~6μm,更优选为50nm~1μm,更优选为100~800nm,更优选为150~600nm,更优选为200~400nm。
本发明原则上对所述二氧化硅的加入量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述二氧化硅的加入量优选为3.5~7.5重量份,更优选为4~7重量份,更优选为4.5~6.5重量份,更优选为5~6重量份。
本发明原则上对所述发泡填充料的具体选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述发泡填充料优选包括空心玻璃微珠,更优选为单一密度的空心玻璃微珠或不同密度的空心玻璃微珠。本发明所述发泡填充料优选用于调节芳纶环氧树脂胶的密度。
本发明原则上对所述发泡填充料的加入量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述发泡填充料的加入量优选为0~10重量份,更优选为2~8重量份,更优选为4~6重量份。
本发明原则上对所述芳纶1313网状纤维的具体参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述芳纶1313网状纤维的长度优选为1~7mm,更优选为2~6mm,更优选为3~5mm。所述芳纶1313网状纤维的长宽比优选为(50~1000):1,更优选为(250~800):1,更优选为(450~600):1。
本发明原则上对所述芳纶1313网状纤维的加入量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述芳纶1313网状纤维的加入量优选为0.3~0.5重量份,更优选为0.32~0.48重量份,更优选为0.35~0.45重量份,更优选为0.38~0.42重量份。
在本发明中,为完整和细化技术方案,保证芳纶环氧树脂胶的性能,不仅满足芳纶纸蜂窝复合制件的加工要求和质量要求,而且进一步满足复合制件的多方面的需求,所述芳纶环氧树脂胶的种类优选包括芳纶环氧树脂封边胶、芳纶环氧树脂填充胶和芳纶环氧树脂成型胶中的一种或多种,更优选包括芳纶环氧树脂封边胶、芳纶环氧树脂填充胶和芳纶环氧树脂成型胶。
本发明原则上对所述芳纶环氧树脂封边胶的组成没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足复合制件多方面的加工要求和高质量要求,所述芳纶环氧树脂封边胶中,按原料质量百分比计,所述二氧化硅的加入量优选为3.5~5.7重量份,更优选为3.8~5.5重量份,更优选为4.0~5.3重量份,更优选为4.2~5.0重量份。
本发明所述芳纶环氧树脂封边胶优选对密度进行控制,所述芳纶环氧树脂封边胶的密度优选为0.6~1.0g/cm 3,更优选为0.65~0.95g/cm 3,更优选为 0.7~0.9g/cm 3,更优选为0.75~0.85g/cm 3。本发明所述芳纶环氧树脂封边胶优选用于轻质蜂窝复合材料封边。
本发明原则上对所述芳纶环氧树脂填充胶的组成没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足复合制件多方面的加工要求和高质量要求,所述芳纶环氧树脂封边胶中,按原料质量百分比计,所述二氧化硅的加入量优选为3.5~5.7重量份,更优选为3.8~5.5重量份,更优选为4.0~5.3重量份,更优选为4.2~5.0重量份。
本发明所述芳纶环氧树脂填充胶优选对密度进行控制,所述芳纶环氧树脂填充胶的密度优选为1.4~1.6g/cm 3,更优选为1.42~1.58g/cm 3,更优选为1.45~1.55g/cm 3,更优选为1.48~1.53g/cm 3。本发明所述芳纶环氧树脂填充胶优选用于在树脂复合材料上粘接五金件。
本发明原则上对所述芳纶环氧树脂成型胶的组成没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足复合制件多方面的加工要求和高质量要求,所述芳纶环氧树脂成型胶优选对二氧化硅的加入量进行控制,按原料质量百分比计,所述二氧化硅的加入量优选为5.7~7.5重量份,更优选为6.0~7.3重量份,更优选为6.2~7.0重量份,更优选为6.4~6.8重量份。
本发明所述芳纶环氧树脂填充胶的密度优选为0.9~1.6g/cm 3,更优选为1.0~1.5g/cm 3,更优选为1.1~1.4g/cm 3,更优选为1.2~1.3g/cm 3。本发明所述芳纶环氧树脂成型胶优选在固化前,具有面团状的形貌;所述芳纶环氧树脂成型胶优选用于在树脂复合材料上进行造型。
本发明还提供了一种如上述技术方案任意一项所述的芳纶环氧树脂胶的制备方法,包括以下步骤:
a)将芳纶1313网状纤维、环氧树脂和二氧化硅进行混合后,得到芳纶环氧树脂胶。
本发明所述芳纶环氧树脂胶的制备方法中,所述原料的具体优选方案,以及加入份数的优选数值与前述芳纶环氧树脂胶中组分的具体优选方案,以及加入份数的优选数值均一致,在此不再一一赘述。
本发明为完整和细化技术方案,保证芳纶环氧树脂胶的性能,不仅满足芳纶纸蜂窝复合制件的加工要求和质量要求,而且进一步满足复合制件的多方面的需求,所述步骤a)中优选还包括发泡填充料,即所述原料优选为芳纶1313网状纤维、环氧树脂、发泡填充料和二氧化硅。具体的,所述步骤a)具体可以为:
将芳纶1313网状纤维、环氧树脂、发泡填充料和二氧化硅进行混合后,得到芳纶环氧树脂胶。
本发明原则上对所述混合的具体参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述混合的时间优选为10~30min,更优选为12~28min,更优选为15~25min,更优选为18~22min。
在本发明中,为完整和细化技术方案,保证芳纶环氧树脂胶的性能,不仅满足芳纶纸蜂窝复合制件的加工要求和质量要求,而且进一步满足复合制件的多方面的需求,所述芳纶环氧树脂胶在使用前,还需加入固化助剂。本发明原则上对所述固化助剂的具体选择和比例没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶环氧树脂胶的性能,满足芳纶纸蜂窝复合制件的加工要求和质量要求,所述固化助剂优选包括改性胺类固化剂、促进剂和偶联剂。所述芳纶环氧树脂胶与固化助剂的质量比优选为4:1。
本发明为完整和细化技术方案,保证芳纶环氧树脂胶的性能,在满足芳纶纸蜂窝复合制件的加工要求和质量要求时,更有利于实际使用,所述芳纶环氧树脂胶的开放时间优选为30~40min,更优选为32~38min,更优选为34~36min。所述开放时间,即芳纶环氧树脂胶A、B组分混合后涂胶时间,包括混合和涂胶的时间。在本发明中,开放时间过后,胶体开始逐步粘稠硬化。
本发明还提供了一种芳纶纸蜂窝复合制件,包括预浸料固化片、芳纶纸蜂窝芯以及哈尼康胶;
所述芳纶纸蜂窝芯复合在所述预浸料固化片之间,形成夹层结构;
所述哈尼康胶包括哈尼康粘接胶;
所述哈尼康粘接胶粘接在所述芳纶纸蜂窝芯和所述预浸料固化片之间;
所述哈尼康胶为上述技术方案任意一项所述的芳纶环氧树脂胶或上述技术方案任意一项所述的制备方法所制备的芳纶环氧树脂胶。
本发明原则上对所述预浸料固化片的定义没有特别限制,以本领域技术人员熟知的预浸料固化片的定义即可,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述预浸料固化片优选是指预浸料热压固化后的片材,优选为预浸料树脂固化片。
本发明原则上对所述预浸料固化片的选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述预浸料固化片优选包括玻纤和/或碳纤预浸料固化片,更优选为玻纤或碳纤预浸料固化片,即玻纤树脂预浸料固化片或碳纤树脂预浸料固化片。
本发明原则上对所述预浸料固化片的结构没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述预浸料固化片优选包括双层预浸料固化片和/或多层预浸料固化片。具体的,所述双层预浸料固化片的厚度优选为0.3~0.36mm,更优选为0.31~0.35mm,更优选为0.32~0.34mm。所述多层预浸料固化片的厚度优选大于等于0.45mm,更优选大于等于0.65mm,更优选大于等于0.85mm。
本发明原则上对所述预浸料固化片的参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述预浸料固化片的树脂含量优选为35%~65%,更优选为40%~60%,更优选为45%~55%。所述预浸料固化片的挥发分含量优选小于等于8%,更优选小于等于6%,更优选小于等于4%。
本发明对所述芳纶纸蜂窝芯没有特别限制,以本领域技术人员熟知的芳纶纸制作的蜂窝芯即可,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明所述芳纶蜂窝芯的材质优选为芳纶纸;所述的 蜂窝芯优选为正六边形蜂窝芯、多边形蜂窝芯、波纹形蜂窝芯和过拉伸形蜂窝芯中的一种或多种,更优选为正六边形蜂窝芯、多边形蜂窝芯、波纹形蜂窝芯或过拉伸形蜂窝芯,更优选为正六边形蜂窝芯。
本发明原则上对所述芳纶纸蜂窝芯的参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述芳纶纸蜂窝芯的孔格尺寸优选为1.83~3.67mm,更优选为2.03~3.37mm,更优选为2.33~3.17mm,更优选为2.63~3.17mm。所述芳纶纸蜂窝芯的高度优选为1~860mm,更优选为50~600mm,更优选为100~500mm,更优选为200~400mm。所述芳纶纸蜂窝芯的密度优选为32~120kg/m 3,更优选为40~110kg/m 3,更优选为50~100kg/m 3,更优选为60~90kg/m 3,更优选为70~80kg/m 3
本发明原则上对所述哈尼康胶没有特别限制,以本领域技术人员熟知的哈尼康胶即可,可以自行制备或市售购买即可,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述哈尼康胶优选包括哈尼康粘接胶,即芳纶环氧树脂填充胶。所述哈尼康粘接胶具体可以为哈尼康CP2016胶。
在本发明中,芳纶纸蜂窝芯复合在所述预浸料固化片之间,即芳纶纸蜂窝芯的上面和下面均复合有预浸料固化片,形成三明治似的夹层结构。本发明原则上对所述复合的方式没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述复合优选为粘接。即所述哈尼康粘接胶粘接在所述芳纶纸蜂窝芯和所述预浸料固化片之间。
本发明原则上对所述哈尼康胶的选择没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述哈尼康胶优选还包括哈尼康封边胶,即芳纶环氧树脂封边胶。所述哈尼康封边胶具体可以为哈尼康CP2015胶。
在本发明中,哈尼康封边胶作为所述芳纶纸蜂窝复合制件的封边,即将哈 尼康封边胶设置在夹层结构的四周,形成封边。本发明原则上对所述哈尼康封边胶的用量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述哈尼康封边胶的封边厚度优选为1~8mm,更优选为2~6mm,更优选为3~4mm,更优选为3.3~3.6mm。
本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,更为进一步便于后续的加工定制,所述哈尼康胶优选还可以填充预埋在所述芳纶纸蜂窝复合制件的任意位置。所述填充预埋在所述芳纶纸蜂窝复合制件的任意位置的哈尼康胶具体优选为哈尼康粘接胶或哈尼康填充成型胶,更优选为哈尼康填充成型胶。
本发明原则上对所述哈尼康胶没有特别限制,以本领域技术人员熟知的哈尼康胶即可,可以自行制备或市售购买即可,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述哈尼康胶优选包括哈尼康填充成型胶,即芳纶环氧树脂成型胶。所述哈尼康填充成型胶具体可以为哈尼康CP2017胶。
在本发明中,所述任意位置优选包括需要后期进行机加工或手工加工的位置。即后续如果需要在芳纶纸蜂窝复合制件上进行机加工或手工加工时,可预先根据工艺图纸在需要进行机加工或手工加工的部位填充哈尼康粘接胶或填充成型胶进行预埋。本发明所述加工的方式优选包括尺寸定位、切边、开孔和挖槽中的一种或多种,更优选为尺寸定位、切边、开孔和挖槽中的多种。
本发明为进一步完整和细化芳纶纸蜂窝复合制件的结构,满足多方面的需求,满足加工要求,利于批量生产,所述芳纶纸蜂窝复合制件优选还包括五金件。本发明原则上对所述五金件的设置方式没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述五金件优选设置在填充预埋的哈尼康胶(具体优选为哈尼康粘接胶或哈尼康填充成型胶)处。
进一步的,所述五金件在设置时优选还可以与所述哈尼康胶配合使用。本发明所述配合使用的哈尼康胶具体优选为哈尼康粘接胶或哈尼康填充成型胶。 所述即芳纶纸蜂窝复合制件,按图纸要求进行机加工或手工加工时,如尺寸定位、切边、开孔、挖槽等,可以用哈尼康胶填充造型,埋置五金件,两者配合使用,最后得到具有哈尼康封边胶封边的芳纶纸蜂窝复合制件。
本发明还提供了一种芳纶纸蜂窝复合制件的制备方法,包括以下步骤:
A)将芳纶纸蜂窝作为芯材,预浸料固化片作为面材,通过哈尼康粘接胶进行粘接,合模加压固化后,再采用哈尼康封边胶进行封边后,得到芳纶纸蜂窝复合制件。
本发明对上述芳纶纸蜂窝复合制件中所需材料的参数、选择和结构关系,以及相应的优选原则,与前述芳纶纸蜂窝复合制件中参数、选择和结构关系,以及相应的优选原则均可以进行对应,在此不再一一赘述。
本发明原则上对所述预浸料固化片的来源没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述预浸料固化片特别优选由玻纤和/或碳纤预浸料经过热加压固化后得到。具体可以为:
将双(多层)层玻纤或碳纤预浸料放入热压机,进行固化处理,形成预浸料固化片。
更具体的步骤可以为:
用溶剂擦拭清理模具,并检查模具的平整性。在预浸料与模具的接触面上涂上脱模剂,将2层或多层预浸料平整的铺设在模具内,合模放入热压机。首先进行在第一压力下进行第一次升温保温,然后在第二压力下进行第二次升温保温,最后在第三压力下进行第三次升温保温后,待冷却后从模具中取出,从而制备出预浸料固化片。
本发明对上述步骤中的过程参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明上述步骤中的过程参数依据预浸料的材质、层数以及产品要求进行选择和调整。
本发明原则上对所述热加压固化的参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述热加压固化的温度优选为120~150℃,更优选为125~145℃,更优选为130~140℃。本发明 所述热加压固化的压力优选为0.1~0.3MPa,更优选为0.12~0.28MPa,更优选为0.15~0.25MPa,更优选为0.18~0.22MPa。本发明所述热加压固化的时间优选为25~330分钟,更优选为60~300分钟,更优选为120~240分钟,更优选为150~210分钟。
本发明先行单独制备了预浸料固化片,使得预浸料摆脱了必须冷藏储备、产品保质期短等多重限制,可以批量化固化预浸料,使得在成品件加工时不再需要占用热压机,从而降低生产成本,实现批量生产。
本发明原则上对所述粘接的过程没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述粘接的过程优选参照粘接标准DIN6701。
本发明为了进一步细化和完整制备过程,保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,特别是细化上述粘接过程,所述粘接前优选还包括预处理步骤。所述预处理优选包括裁剪、打磨、去油和除尘中的一种或多种,更优选为裁剪、打磨、去油和除尘。
上述粘接的具体步骤可以为以下步骤:
裁剪芳纶纸蜂窝片、预浸料固化片,均需留有相应尺寸余量。按粘接标准DIN6701要求双面打磨预浸料固化片(如有预浸料的拼接缝需打磨平整),用丙酮或酒精溶剂擦洗去油除尘。
上述粘接的具体步骤可以为以下步骤:
确认哈尼康粘接胶混胶配比,严格称重A、B组分,充分搅拌混胶。A、B组分混合后,合适的操作时间在30分钟左右,超时胶体硬化。
本发明原则上对所述粘接的参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述粘接用哈尼康粘接胶的用量优选为300~350克/平方米,更优选为310~340克/平方米,更优选为320~330克/平方米。
本发明原则上对所述合模加压固化的参数没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证 芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述合模加压固化的压力优选为0.1~0.3MPa,更优选为0.12~0.28MPa,更优选为0.15~0.25MPa,更优选为0.18~0.22MPa。所述合模加压固化的温度优选为25~60℃,更优选为30~55℃,更优选为35~50℃,更优选为40~45℃。所述合模加压固化的时间包括初步固化时间和/或完全固化时间两种概念。其中,所述合模加压固化的初步固化时间优选为3~48小时,更优选为12~36小时,更优选为18~30小时。所述合模加压固化的完全固化时间优选为1~7天,更优选为2~6天,更优选为3~5天。在本发明中,所述合模加压固化的温度为25~35℃的常温时,所述合模加压固化的初步固化时间优选大于等于24小时,更优选大于等于36小时,更优选大于等于48小时。所述合模加压固化的温度为50~60℃的高温时,所述合模加压固化的初步固化时间优选大于等于3小时,更优选大于等于5小时,更优选大于等于8小时。同样的,所述合模加压固化的温度为25~35℃的常温时,所述合模加压固化的完全固化时间优选大于等于7天,更优选大于等于9天,更优选大于等于12天。所述合模加压固化的温度为50~60℃的高温时,所述合模加压固化的完全固化时间优选大于等于1天,更优选大于等于2天,更优选大于等于3天。
本发明原则上对所述哈尼康封边胶的用量没有特别限制,本领域技术人员可以根据实际生产情况、产品要求和质量要求进行选择和调整,本发明为保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述哈尼康封边胶的用量优选与复合制件封边的厚度相关联。所述哈尼康封边胶的封边厚度优选为1~8mm,更优选为2~6mm,更优选为3~4mm,更优选为3.3~3.6mm。
本发明为了进一步细化和完整制备过程,保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,所述粘接后优选还包括预处理步骤。所述填充预埋步骤具体优选为:
在需要后期进行机加工或手工加工的位置,填充哈尼康胶进行预埋。
更具体可以为:
根据工艺图纸在需要开孔、挖槽等复合后进行机加工的部位填充哈尼康粘接胶进行预埋。
本发明为了进一步细化和完整制备过程,保证芳纶纸蜂窝复合制件的性 能,满足加工要求,利于批量生产,所述封边前和/或封边后优选还包括机加工步骤。所述机加工步骤具体优选为:
对制件的填充预埋位置进行尺寸定位、切边、开孔和挖槽中的一步或多步后,加装五金件或在哈尼康胶的配合使用下加装五金件。
更具体可以为:
脱模后制件后加工尺寸定位、切边、开孔、挖槽,加装五金件或在哈尼康粘接胶的配合使用下加装五金件。
本发明为了进一步细化和完整制备过程,保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,在得到芳纶纸蜂窝复合制件之前优选还包括后处理步骤。所述后处理步骤优选括喷漆涂装、贴膜和贴防火板(优选为热固性树脂浸渍纸高压层积板)中的一种或多种。
本发明为了进一步细化和完整制备过程,保证芳纶纸蜂窝复合制件的性能,满足加工要求,利于批量生产,上述芳纶纸蜂窝复合制件的具体制备过程可以为以下步骤:
步骤1:将双(多层)层玻纤或碳纤预浸料放入热压机,进行固化处理,形成预浸料固化片;
步骤2:裁剪芳纶纸蜂窝片、预浸料固化片,均需留有相应尺寸余量。按粘接标准DIN6701要求双面打磨预浸料固化片(如有预浸料的拼接缝需打磨平整),用丙酮或酒精溶剂擦洗去油除尘
步骤3:确认哈尼康粘接胶混胶配比,严格称重A、B组分,充分搅拌混胶。A、B组分混合后,合适的操作时间在30分钟左右,超时胶体硬化。
步骤4:根据工艺图纸在需要开孔、挖槽等复合后进行机加工的部位填充哈尼康粘接胶进行预埋。
步骤5:每层按300~350g/m 2用量涂刷哈尼康粘接胶,合模后平板件加压0.1~0.2MPa,弧形件加压0.2~0.3MPa。加压固化(25℃以上需24小时以上,60℃左右3小时以上达到初步固化)。
步骤6:脱模后制件后加工尺寸定位、切边、开孔、挖槽,用哈尼康粘接胶填充粘接(若需),用哈尼康结构胶封边后得到芳纶纸蜂窝复合制件。
步骤7:将步骤6得到的芳纶纸蜂窝复合制件经过涂装、贴膜或贴上防火 板(热固性树脂浸渍纸高压层积板),得到适用于中国标准动车组车内装饰中使用的轻量化间壁橱柜板材。
本发明还提供了上述技术方案任意一项所述的芳纶纸蜂窝复合制件或上述技术方案任意一项所述的制备方法所制备的芳纶纸蜂窝复合制件在轻量化板材家具方面的应用。
本发明原则上对所述轻量化板材家具的具体选择没有特别限制,以本领域技术人员熟知的广义上的板材家具概念即可,本领域技术人员可以根据使用情况、环境要求和性能要求进行选择和调整,本发明所述轻量化板材家具更优选为运动载体上的轻量化板材家具,具体可以为高铁列车内饰、间壁和橱柜等等。
本发明上述步骤提供了一种芳纶纸蜂窝及其常温制备方法、应用。本发明利用哈尼康粘接胶,将芳纶纸蜂窝芯粘贴在预浸料固化片之间,形成夹层结构,再采用哈尼康封边胶对芳纶纸蜂窝复合制件进行封边,得到了芳纶纸蜂窝复合制件,是一种可常温固化的芳纶纸蜂窝复合制件。本发明提供的芳纶纸蜂窝复合制件,采用先期制备好的预浸料固化片结合哈尼康胶,能够在最后的复合工序中使用常温进行复合,减少了生产时间和设备投入,使得在成品件加工时,不再需要占用热压机、大型真空罐、高温烘箱等大型设备,从而降低生产成本,实现大批量芳纶纸蜂窝复合板的工业化生产。而且进一步采用哈尼康胶进行封边,可以直接生产批量的板材,综合采用哈尼康胶进行粘接、封边和填埋,则可以生产各种批量的板材。同时后期定制加工和客户自行加工时,同样可以采用哈尼康胶进行封边和后期处理,得到定制的成品板材,这也有利于批量的工业化生产,同时解决了定制加工上存在的局限性。此外,预浸料固化片先行单独制备,也使得预浸料摆脱了必须冷藏储备、产品保质期短等多重限制,可以批量化固化预浸料。
本发明提供的常温制备方法工艺简单,条件温和,更加适于规模化生产与推广,而且制备的芳纶纸蜂窝复合制件有效的保持了芳纶纸蜂窝芯的刚性、平整度及强度,具有较好的阻燃性、保温性以及力学性能。
本发明上述步骤提供了一种芳纶1313网状纤维及其制备方法、常温固化的芳纶阻燃环氧树脂结构胶系列及其制备方法、芳纶纸蜂窝复合制件。本发明采用特定的芳纶1313网状纤维,该芳纶1313纤维具有絮状纤维团状的形貌, 而且芳纶1313纤维丝之间交织形成立体网状结构。本发明又将其用于环氧树脂胶中,得到了一种芳纶环氧树脂胶,在环氧树脂胶中加入芳纶1313网状纤维,类似水泥加钢筋原理,使得环氧树脂胶固化后具有更好抗压、抗剪、防开裂、耐低温等较好的粘接性能。该芳纶环氧树脂胶是一种阻燃环氧树脂结构胶系列,不仅具有较好的粘接性能,而且通过调整组分和物理参数,还能够用于封边和塑型,进而满足多方面的需求。芳纶环氧树脂胶能够在常温下进行固化,同时具有较好的性能,能够满足芳纶纸蜂窝复合制件的相关标准,从而解决了目前制备芳纶蜂窝复合制件存在的过程繁琐,生产成本高等缺陷。
本发明还提供了一种芳纶纸蜂窝复合制件工艺及其常温制备方法。本发明利用上述芳纶环氧树脂胶,将芳纶纸蜂窝芯粘贴在预浸料固化片之间,形成夹层结构,得到了芳纶纸蜂窝复合制件。本发明提供的芳纶纸蜂窝复合制件,采用先期制备好的预浸料固化片结合芳纶环氧树脂胶,能够在最后的复合工序中使用常温进行复合,减少了生产时间和设备投入,使得在成品件加工时,不再需要占用热压机、大型真空罐、高温烘箱等大型设备,从而降低生产成本,实现大批量芳纶纸蜂窝复合板的工业化生产。而且制备的芳纶纸蜂窝复合制件有效的保持了芳纶纸蜂窝芯的刚性、平整度及强度,具有较好的阻燃性、保温性以及力学性能。本发明提供的芳纶1313网状纤维、阻燃环氧树脂结构胶和芳纶纸蜂窝复合制件的制备方法工艺简单,条件温和,更加适于规模化生产与推广。
实验结果表明,本发明提供的芳纶环氧树脂胶,完全固化后胶体邵氏硬度为85~95D,固化胶块的压缩强度大于等于55~65MPa;10mm深M6螺钉拉力大于等于2000N;剪切强度(60℃保温3天,25℃常温7天)大于等于10~15MPa;具有较好的低温性能,耐低温达到-55℃。而且制备的芳纶纸蜂窝复合制件同样具有较好的综合性能,拉伸性能为1.70~2.40MPa;平压性能为2.0~3.6MPa;剪切性能为0.60~1.30MPa;滚筒剥离强度为45~70N*mm/mm;弯曲刚度为6.0*10 7~11.0*10 7N·mm 2
为了进一步说明本发明,以下结合实施例对本发明提供的一种芳纶1313网状纤维及其制备方法、芳纶环氧树脂胶及其制备方法进行了详细描述,但是 应当理解,这些实施例是在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制,本发明的保护范围也不限于下述的实施例。
实施例中所述材料均由市售购得,其牌号与厂家与说明书中所述的牌号与厂家相一致。
实施例1
1)将聚合后的芳纶1313浆料通过白金喷头形成高压喷雾喷入凝固液中,凝固液即沉析剂,为50%二甲基乙酰胺(DMAc)溶液,加50%的离子水的混合液,芳纶1313浆料喷入的流量500mL/min。喷入的同时进行搅拌,并以3000mL/min流量同步补充加入凝固液进沉析池中,芳纶1313浆料经过30分钟凝固沉析后,得到湿纤维团。
2)将湿纤维团送入干燥机经过60℃、30分钟热风干燥后,得到蓬松的芳纶1313网状纤维。
对本发明实施例1制备的芳纶1313网状纤维进行检测。
参见表1,表1为本发明制备的芳纶1313网状纤维的性能数据。
表1
Figure PCTCN2020096445-appb-000004
对本发明实施例1制备的芳纶1313网状纤维进行表征。
参见图1,图1为本发明制备的芳纶1313网状纤维的外观图。
由图1可以看出,本发明制备的芳纶1313网状纤维具有絮状纤维团状,或类似棉絮状的纤维团的宏观形貌,而且芳纶1313纤维丝之间交织形成3D立体空间的网状结构。
参见图2,图2为本发明制备的芳纶1313网状纤维的扫描电镜图。
由图2可以看出,本发明制备的芳纶1313网状纤维在微观上,具有丝状、条状和膜状相互交联形成的微观立体网状结构。
实施例2(配制哈尼康CP2015)
a)购置A组分环氧树脂90%、芳纶1313网状纤维0.5%、二氧化硅4.5%、发泡填充料5.0%进行混合后,得到A组分芳纶环氧树脂胶。
搅拌混合的时间为30min。
b)购置B组分环氧树脂(固化剂)。
A组分芳纶环氧树脂胶与B组分固化助剂的质量比优选为4:1。
将A、B组分按4:1质量比搅拌混合10min,制作检测样块。
对本发明实施例2制备的样块进行性能检测。
参见表2,表2为本发明实施例2制备的芳纶环氧树脂封边胶的性能数据。
表2 芳纶环氧树脂封边胶(哈尼康CP2015)样块检测数据
完全固化胶体硬度 邵氏:≥85D
固化胶块压缩强度 ≥55MPa
完全固化胶体密度 1.0克/cm 3
剪切强度(MPa) ≥10MPa(60℃保温3天,25℃常温7天)
实施例3(配制哈尼康CP2016)
a)购置A组分环氧树脂94%、芳纶1313网状纤维0.3%、二氧化硅5.7%进行混合后,得到A组分芳纶环氧树脂胶。
搅拌混合的时间为30min。
b)购置B组分环氧树脂(固化剂)。
A组分芳纶环氧树脂胶与B组分固化助剂的质量比优选为4:1。
将A、B组分按4:1质量比搅拌混合10min,制作检测样块。
对本发明实施例3制备的样块进行性能检测。
参见表3,表3为本发明实施例3制备的芳纶环氧树脂填充胶的性能数据。
表3 芳纶环氧树脂填充胶(哈尼康CP2016)样块检测数据
完全固化胶体硬度 邵氏:≥92D
固化胶块压缩强度 ≥63MPa
完全固化胶体密度 ≦1.5克/cm 3
剪切强度(MPa) ≥15MPa(60℃保温3天,25℃常温7天)
实施例4(配制哈尼康CP2017)
a)购置A组分环氧树脂92%、芳纶1313网状纤维0.5%、二氧化硅7.5%进行混合后,得到A组分芳纶环氧树脂胶。
搅拌混合的时间为30min。
b)购置B组分环氧树脂(固化剂)。
A组分芳纶环氧树脂胶与B组分固化助剂的质量比优选为4:1。
将A、B组分按4:1质量比搅拌混合10min,制作检测样块。
对本发明实施例4制备的样块进行性能检测。
参见表4,表4为本发明实施例4制备的芳纶环氧树脂成型胶的性能数据。
表4 芳纶环氧树脂成型胶(哈尼康CP2017)样块检测数据
完全固化胶体硬度 邵氏:≥90D
固化胶块压缩强度 ≥60MPa
完全固化胶体密度 ≦1.6克/cm 3
剪切强度(MPa) ≥13MPa(60℃保温3天,25℃常温7天)
实施例5
预浸料固化片的制备:
用溶剂擦拭清理模具,并检查模具的平整性。在预浸料与模具的接触面上涂上55NC脱模剂,将2层或多层玻纤酚醛预浸料平整的铺设在模具内,合模放入热压机。温度由20℃升至80℃并保温40min,升温速率为1℃/min,压强为0.1MPa;然后将升温至120℃并保温60min,升温速率为2℃/min,压强为0.2MPa;最后升温至150℃并保温20min升温速率为2℃/min,压强为0.3MPa,待冷却后从模具中取出,从而制备出合格的玻纤酚醛预浸料固化片。
对本发明实施例5制备的玻纤酚醛预浸料固化片进行性能检测。
参见表5,表5为本发明实施例5制备的玻纤酚醛预浸料固化片的性能数据。
表5
Figure PCTCN2020096445-appb-000005
芳纶蜂窝复合件的制备:
将两片预浸料固化片涂胶面用砂纸打磨平整,然后除尘并用丙酮溶剂擦净。按330克/平方米用胶量均匀涂上哈尼康粘接胶CP2016,黏合在芳纶蜂窝上下两面,成夹心结构。放入压机,在常温25℃左右加压0.2MPa,经过24小时后达到初步固化(可流转后道工序再加工),或者放入压机,在恒温60℃左右加压0.2MPa,经过3小时后达到初步固化(可流转后道工序再加工)。
将蜂窝预浸料复合件(板)按图纸尺寸用圆盘推锯或五轴加工中心切边,再用哈尼康封边胶CP2015封边胶加工封边,等待固化后再上五轴加工中心精准切边开孔,用哈尼康粘接胶CP2016填埋螺套或五金件。哈尼康固化不需加压,固化时间温度:常温25℃左右经过24小时后或恒温60℃左右经过3小时后达到初步固化。
对本发明实施例5制备的芳纶蜂窝复合件进行性能检测。
参见表6,表6为本发明实施例5制备的芳纶蜂窝复合件的滚筒剥离试验 性能数据。
表6
Figure PCTCN2020096445-appb-000006
PS:测试标准规定同时测试5件样品取得平均值。
参见表7,表7为本发明实施例5制备的芳纶蜂窝复合件的性能数据。
表7
Figure PCTCN2020096445-appb-000007
实施例6
快固预浸料固化片的制备:
用溶剂擦拭清理模具,并检查模具的平整性。在预浸料与模具的接触面上涂上55NC脱模剂,将2层或多层玻纤酚醛预浸料平整的铺设在模具内,合模放入热压机。温度由60℃升至145℃并保温30min,升温速率为3℃/min,压强为0.25MPa,待冷却至60℃后从模具中取出,从而制备出合格的快固玻纤酚醛预浸料固化片。
对本发明实施例6制备的玻纤酚醛预浸料固化片进行性能检测。
参见表8,表8为本发明实施例6制备的玻纤酚醛预浸料固化片的性能数据。
表8
Figure PCTCN2020096445-appb-000008
芳纶蜂窝复合件的制备:
将两片预浸料固化片涂胶面用砂纸打磨平整,然后除尘并用丙酮溶剂擦净。按330克/平方米用胶量均匀涂上哈尼康粘接胶CP2016,黏合在芳纶蜂窝 上下两面,成夹心结构。放入压机,在常温25℃左右加压0.2MPa,经过24小时后达到初步固化(可流转后道工序再加工),或者放入压机,在恒温60℃左右加压0.2MPa,经过3小时后达到初步固化(可流转后道工序再加工)。
将蜂窝预浸料复合件(板)按图纸尺寸用圆盘推锯或五轴加工中心切边,再用哈尼康封边胶CP2015封边胶加工封边,等待固化后再上五轴加工中心精准切边开孔,用哈尼康粘接胶CP2016填埋螺套或五金件。哈尼康固化不需加压,固化时间温度:常温25℃左右经过24小时后或恒温60℃左右经过3小时后达到初步固化。
对本发明实施例6制备的芳纶蜂窝复合件进行性能检测。
参见表9,表9为本发明实施例6制备的芳纶蜂窝复合件的滚筒剥离试验性能数据。
表9
Figure PCTCN2020096445-appb-000009
PS:测试标准规定同时测试5件样品取得平均值。
参见表10,表10为本发明实施例6制备的芳纶蜂窝复合件的性能数据。
表10
Figure PCTCN2020096445-appb-000010
实施例7
预浸料固化片的制备:
用溶剂擦拭清理模具,并检查模具的平整性。在预浸料与模具的接触面上涂上55NC脱模剂,将2层或多层玻纤酚醛预浸料平整的铺设在模具内,合模放入热压机。温度由20℃升至80℃并保温40min,升温速率为1℃/min,压强为0.1MPa;然后将升温至120℃并保温60min,升温速率为2℃/min,压强为0.2MPa;最后升温至150℃并保温20min升温速率为2℃/min,压强为0.3MPa,待冷却后从模具中取出,从而制备出合格的玻纤酚醛预浸料固化片。
对本发明实施例7制备的玻纤酚醛预浸料固化片进行性能检测。
参见表11,表11为本发明实施例7制备的玻纤酚醛预浸料固化片的性能数据。
表11
Figure PCTCN2020096445-appb-000011
Figure PCTCN2020096445-appb-000012
加温固化芳纶蜂窝复合件的制备:
将两片预浸料固化片涂胶面用砂纸打磨平整,然后除尘并用丙酮溶剂擦净。按330克/平方米用胶量均匀涂上哈尼康粘接胶CP2016,黏合在芳纶蜂窝上下两面,成夹心结构。放入压机,在恒温60℃左右加压0.2MPa,经过3小时后达到初步固化(可流转后道工序再加工)。
将蜂窝预浸料复合件(板)按图纸尺寸用圆盘推锯或五轴加工中心切边,再用哈尼康封边胶CP2015封边胶加工封边,等待固化后再上五轴加工中心精准切边开孔,用哈尼康粘接胶CP2016填埋螺套或五金件。哈尼康固化不需加压,固化时间温度:常温25℃左右经过24小时后或恒温60℃左右经过3小时后达到初步固化。
对本发明实施例7制备的芳纶蜂窝复合件进行性能检测。
参见表12,表12为本发明实施例7制备的芳纶蜂窝复合件的滚筒剥离试验性能数据。
表12
Figure PCTCN2020096445-appb-000013
Figure PCTCN2020096445-appb-000014
PS:测试标准规定同时测试5件样品取得平均值。
参见表13,表13为本发明实施例7制备的芳纶蜂窝复合件的性能数据。
表13
Figure PCTCN2020096445-appb-000015
以上对本发明提供的一种芳纶1313网状纤维及其制备方法、常温固化的芳纶阻燃环氧树脂结构胶系列及其制备方法、芳纶纸蜂窝复合制件进行了详细的介绍,本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想,包括最佳方式,并且也使得本领域的任何技术人员都能够实践本发明,包括制造和使用任何装置或系统,和实施任何结合的方法。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定,并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素,或者如果它们 包括与权利要求的文字表述无实质差异的等同结构要素,那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种芳纶1313网状纤维,其特征在于,所述芳纶1313纤维为絮状纤维团状芳纶1313纤维;
    芳纶1313纤维丝之间交织形成立体网状结构。
  2. 根据权利要求1所述的芳纶1313网状纤维,其特征在于,所述芳纶1313网状纤维的细度为1~2D;
    所述芳纶1313网状纤维在微观上,具有丝状、条状和膜状相互交联形成的微观立体网状结构;
    所述丝的直径为10~500nm;
    所述条的直径为0.5~20μm;
    所述膜的直径为5~50μm。
  3. 一种芳纶1313网状纤维的制备方法,其特征在于,包括以下步骤:
    1)将聚合后的芳纶1313浆料喷入凝固液中,在搅拌的条件下进行凝固沉析,得到湿纤维团;
    2)将上述步骤得到的湿纤维团经过热风干燥后,得到蓬松的芳纶1313网状纤维。
  4. 根据权利要求3所述的制备方法,其特征在于,所述凝固液包括二甲基乙酰胺溶液;
    所述芳纶1313浆料喷入的流量小于等于1000mL/min;
    所述芳纶1313浆料与凝固液的质量比为1:(2~20);
    所述凝固沉析的时间为5~40min;
    所述热风干燥的温度为60~85℃。
  5. 一种芳纶环氧树脂胶,其特征在于,按原料质量百分比计,包括:
    Figure PCTCN2020096445-appb-100001
  6. 根据权利要求5所述的芳纶环氧树脂胶,其特征在于,所述环氧树脂 包括阻燃环氧树脂;
    所述芳纶1313网状纤维的长度为1~7mm;
    所述芳纶1313网状纤维的长宽比为(50~1000):1;
    所述二氧化硅包括气相二氧化硅粉;
    所述发泡填充料包括空心玻璃微珠;
    所述芳纶环氧树脂胶包括芳纶环氧树脂封边胶、芳纶环氧树脂填充胶和芳纶环氧树脂成型胶中的一种或多种;
    所述芳纶环氧树脂封边胶和芳纶环氧树脂填充胶中,按原料质量百分比计,所述二氧化硅各自选自3.5~5.7重量份;
    所述芳纶环氧树脂成型胶中,按原料质量百分比计,所述二氧化硅为5.7~7.5重量份。
  7. 根据权利要求6所述的芳纶环氧树脂胶,其特征在于,所述二氧化硅的粒径为12nm~6μm;
    所述芳纶环氧树脂封边胶的密度为0.6~1.0g/cm 3
    所述芳纶环氧树脂封边胶用于轻质蜂窝复合材料封边;
    所述芳纶环氧树脂填充胶的密度为1.4~1.6g/cm 3
    所述芳纶环氧树脂填充胶用于在树脂复合材料上粘接五金件;
    所述芳纶环氧树脂成型胶的密度为0.9~1.6g/cm 3
    所述芳纶环氧树脂成型胶在固化前成面团状;
    所述芳纶环氧树脂成型胶用于在树脂复合材料上进行造型。
  8. 一种如权利要求5~7任意一项所述的芳纶环氧树脂胶的制备方法,其特征在于,包括以下步骤:
    a)将芳纶1313网状纤维、环氧树脂和二氧化硅进行混合后,得到芳纶环氧树脂胶。
  9. 根据权利要求8所述的制备方法,其特征在于,所述步骤a)中,还包括发泡填充料;
    所述混合的时间为10~30min;
    所述芳纶环氧树脂胶在使用前,还需加入固化助剂;
    所述固化助剂包括改性胺类固化剂、促进剂和偶联剂;
    所述芳纶环氧树脂胶与固化助剂的质量比为4:1;
    所述芳纶环氧树脂胶的开放时间为30~40min。
  10. 一种芳纶纸蜂窝复合制件,其特征在于,包括预浸料固化片、芳纶纸蜂窝芯以及哈尼康胶;
    所述芳纶纸蜂窝芯复合在所述预浸料固化片之间,形成夹层结构;
    所述哈尼康胶包括哈尼康粘接胶;
    所述哈尼康粘接胶粘接在所述芳纶纸蜂窝芯和所述预浸料固化片之间;
    所述哈尼康胶为权利要求5~7任意一项所述的芳纶环氧树脂胶或权利要求8~9任意一项所述的制备方法所制备的芳纶环氧树脂胶。
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