CN109517383B - Resin composite material and preparation method thereof - Google Patents
Resin composite material and preparation method thereof Download PDFInfo
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- CN109517383B CN109517383B CN201710845639.3A CN201710845639A CN109517383B CN 109517383 B CN109517383 B CN 109517383B CN 201710845639 A CN201710845639 A CN 201710845639A CN 109517383 B CN109517383 B CN 109517383B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
In order to overcome the problem that the material performance is affected due to the bonding bias of silane coupling agents in the existing resin-based composite material, the invention provides a resin composite material, which comprises a fiber material, a first silane coupling agent layer, a second silane coupling agent layer and a resin, wherein the first silane coupling agent layer covers the surface of the fiber material, the second silane coupling agent layer covers the surface, facing away from the fiber material, of the first silane coupling agent layer, and the resin covers the surface, facing away from the first silane coupling agent layer, of the second silane coupling agent layer. Meanwhile, the invention also discloses a preparation method of the resin composite material. The resin composite material provided by the invention improves the binding force between the fiber material and the resin, and enhances the comprehensive mechanical property of the composite material.
Description
Technical Field
The invention belongs to the technical field of fiber reinforced resin materials, and particularly relates to a resin composite material and a preparation method thereof.
Background
The thermoplastic resin matrix composite material is prepared by taking thermoplastic resin, a reinforced fiber material and a coupling agent as basic materials.
Generally speaking, there are two main aspects to the modification of resin-based composites: firstly, adding modification, namely adding a certain proportion of reinforcing materials such as long glass fibers or short glass fibers into a powder resin raw material, then uniformly mixing and dispersing by using high-efficiency dispersing equipment, and finally performing hot press molding or extrusion granulation and injection molding; secondly, performing composite modification, namely treating the glass fiber cloth by using a coupling agent, and then tightly pressing the glass fiber cloth and resin at high temperature and high pressure; finally, the purpose of improving the overall mechanical property of the material is achieved.
Silane coupling agents are silicon-based chemical molecules containing both inorganic and organic reactivity in the same molecule, and are generally of the typical structure:
(RO)3SiCH2CH2CH2-X
here, RO means a hydrolyzable group such as methoxy, ethoxy or acetoxy, and X is an organic functional group such as amino, methacryloxy, epoxy, or the like. Silane coupling agents act at the interface of an inorganic material (such as glass, metal or mineral) and an organic material (such as an organic polymer coating or adhesive) to bind or couple two distinct materials. The alkoxy on the silicon atom of the silane coupling agent is hydrolyzed into silanol, the silanol reacts with the metal hydroxyl on the inorganic surface to form an alkoxy structure, water is removed, and finally the surface of the inorganic material is covered by the silane coupling agent. Meanwhile, the organic group of the silane coupling agent chemically reacts with the organic functional group of the organic polymer to complete the coupling process between the inorganic material and the organic material.
Because different silane coupling agents have certain bias in the bonding strength with the fiber material and the bonding strength with the resin material, for example, part of the silane coupling agents can be better bonded with one end of the fiber material and weaker in the bonding strength with the resin material, so that the mechanical property of the resin-based composite material is influenced.
Disclosure of Invention
Aiming at the problems that the silane coupling agent in the existing resin-based composite material has bonding bias and influences the material performance, the invention provides a resin composite material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
provided is a resin composite material, which comprises a fiber material, a first silane coupling agent layer, a second silane coupling agent layer and a resin, wherein the first silane coupling agent layer, the second silane coupling agent layer and the resin are sequentially covered on the surface of the fiber material from inside to outside.
Optionally, the fiber material is a fiber woven material formed by weaving fiber bundles, and the surface of the fiber bundles is covered with the first silane coupling agent layer, the second silane coupling agent layer and the resin in sequence from inside to outside.
Optionally, the composition comprises the following components in parts by weight: 50-90 parts of fiber material, 20-90 parts of resin, 0.01-1 part of first silane coupling agent and 0.01-1 part of second silane coupling agent.
Optionally, the fiber material has a thickness of 100 to 200 μm, the first silane coupling agent layer has a thickness of 10 to 50 μm, the second silane coupling agent layer has a thickness of 10 to 50 μm, and the resin has a thickness of 10 to 30 μm.
Optionally, the bonding strength of the first silane coupling agent layer to the fiber material is greater than the bonding strength of the second silane coupling agent layer to the fiber material, and the bonding strength of the second silane coupling agent layer to the resin is greater than the bonding strength of the first silane coupling agent layer to the resin.
Optionally, the fiber material comprises one or more of glass fibers, carbon fibers, aramid fibers, and polyethylene fibers.
Optionally, the first silane coupling agent layer includes a vinyl silane oligomer.
Optionally, the second silane coupling agent comprises one or more of a silane coupling agent with an epoxy cyclohexyl group, methylpropylacyloxypropyltrimethoxysilane, and gamma-aminopropyltriethoxysilane.
Optionally, the resin is a thermoplastic resin.
Optionally, the resin comprises one or more of polypropylene, polyamide, polyphenylene sulfide, polyethylene terephthalate, polyethylene, polyetherimide, polycarbonate, polyetheretherketone, polyetherketoneketone.
Optionally, chopped fibers are wrapped in the resin, the surfaces of the chopped fibers, which are in contact with the resin, are covered with a third silane coupling agent layer, and the weight component of the chopped fibers is 10-30 parts.
The invention also provides a preparation method of the resin composite material, which comprises the following steps:
applying a first silane coupling agent to the fiber material to form a first silane coupling agent layer;
applying a second silane coupling agent on the first silane coupling agent layer to form a second silane coupling agent layer;
and impregnating the fiber material with the first silane coupling agent layer and the second silane coupling agent layer in resin, and curing to obtain the resin composite material.
Alternatively, the "applying a first silane coupling agent on the fiber material to form a first silane coupling agent layer" includes:
mixing 0.3-1.0 part by weight of a first silane coupling agent and 99-99.7 parts by weight of deionized water, hydrolyzing for 3-5 hours, wherein the pH value of the hydrolysis solution is 3-5, after the hydrolysis is completed, putting a fiber material into the hydrolysis solution of the first silane coupling agent, soaking for 3-8 minutes under the action of ultrasound, taking out the fiber material after the soaking is completed, and drying to form a first silane coupling agent layer on the fiber material.
Alternatively, the "applying a second silane coupling agent on the first silane coupling agent layer to form a second silane coupling agent layer" includes:
mixing 0.3-1.0 part by weight of a second silane coupling agent, 94-96 parts by weight of isopropanol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, after the hydrolysis is completed, putting the fiber material with the first silane coupling agent layer into a hydrolysis solution of the second silane coupling agent, soaking for 3-8 min under the action of ultrasound, taking out the fiber material after the soaking is completed, and drying to form a second silane coupling agent layer on the first silane coupling agent layer.
Alternatively, the "impregnating a fiber material with the first and second silane coupling agent layers in a resin and curing the impregnated fiber material to obtain a resin composite material" includes:
filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material with a first silane coupling agent layer and a second silane coupling agent layer on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material, carrying out hot-pressing operation, keeping the temperature and pressure at 220-300 ℃ and 1-5 MPa for 5-15 min, and cooling and curing to obtain the resin composite material.
Optionally, before the step of impregnating the fiber material with the first and second silane coupling agent layers in the resin and curing to obtain the resin composite material, the method further comprises:
mixing 0.3-1.0 part by weight of a third silane coupling agent, 94-96 parts by weight of isopropanol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, adding the chopped fibers into a hydrolysis solution of the third silane coupling agent for soaking after the hydrolysis is finished, taking out the chopped fibers, drying, forming a third silane coupling agent layer on the surfaces of the chopped fibers, adding the chopped fibers into thermoplastic resin powder, and uniformly dispersing.
Optionally, the particle size of the thermoplastic resin powder is 200-300 meshes.
According to the resin composite material provided by the invention, a modification scheme of coating a double-layer coupling agent is adopted, a first silane coupling agent layer with good wetting permeability to fiber materials is coated on the surface of the fiber materials, then a second silane coupling agent layer with a solubility parameter close to that of the resin is coated on the surface of the fiber materials, the first silane coupling agent layer and the second silane coupling agent layer generate chemical bonds through chemical reaction and are coated on the surface of the fiber materials, the fiber materials are combined through the first silane coupling agent layer, the resin is combined through the second silane coupling agent layer, meanwhile, silane in the first silane coupling agent layer and silane in the second silane coupling agent layer can be combined with each other to form a tightly-attached multi-molecular-structure siloxane layer, so that strong binding force between the fiber materials and the resin is ensured, and the comprehensive mechanical property of the composite material is enhanced.
Drawings
Fig. 1 is a schematic structural diagram of a resin composite material according to an embodiment of the present invention.
The reference numbers in the drawings of the specification are as follows:
1. fiber material; 2. a first silane coupling agent layer; 3. a second silane coupling agent layer; 4. a resin; 5. and (3) chopped fibers.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, an embodiment of the present invention discloses a resin composite material, including a fiber material 1, a first silane coupling agent layer 2, a second silane coupling agent layer 3, and a resin 4, wherein the fiber material 1 is formed by weaving a plurality of woven bundles, and the resin 4, the second silane coupling agent layer 3, and the first silane coupling agent layer 2 are sequentially coated on the surfaces of the woven bundles from outside to inside.
Specifically, the first silane coupling agent layer 2 is coated on the surface of the fiber material 1, the second silane coupling agent layer 3 is coated on the surface of the first silane coupling agent layer 2 facing away from the fiber material, and the resin 4 is coated on the surface of the second silane coupling agent layer 3 facing away from the first silane coupling agent layer 2.
In the present invention, the term "fiber material" should be understood in a broad sense, and may be a single fiber, a fiber bundle integrated by a plurality of fibers, a sponge-like structure formed by disorderly arranging fiber bundles, or a fiber woven fabric, etc., and those skilled in the art should specifically understand according to the specific application environment.
In some embodiments of the present invention, the fiber material is a fiber woven material formed by weaving fiber bundles, and the surface of the fiber bundles is covered with the first silane coupling agent layer, the second silane coupling agent layer, and the resin in this order from inside to outside.
The fiber woven material is of a porous woven structure, the first silane coupling agent layer and the second silane coupling agent layer are surface modification layers of the fiber woven material, the surface modification of the whole fiber woven material can be carried out, namely the surface modification of the fiber woven material is carried out, namely the surface modification of the inner fiber bundle of the fiber woven material and the modification of the inner fiber bundle penetration of the fiber woven material are carried out, and the resin and the fiber woven material are in a infiltration relation, namely the resin is partially immersed into the inner portion of the fiber woven material and is adhered to the fiber woven material. The fiber woven cloth can adopt 3K or 6K or 12K or 24K checkered cloth or unidirectional cloth, can be one or a plurality of combinations, 3K or 6K or 12K or 24K refers to the number of fibers in a single-bundle fiber bundle, and the unidirectional cloth is four-warp-broken satin or long-shaft satin fabric woven by coarse warp yarns and fine weft yarns, and is characterized in that the warp yarns have high strength in the 0-degree direction; the grid cloth is formed by fibers into mutually vertical grids, the direction of a longitudinal fiber bundle is a 0-degree direction, and the direction of a transverse fiber bundle is a 90-degree direction, so that the grid cloth has better tensile strength in the 0-degree direction and the 90-degree direction.
The resin composite material adopts a modification scheme of coating a double-layer coupling agent, a first silane coupling agent layer 2 with good wetting permeability to the fiber material 1 is firstly coated on the surface of the fiber material 1, then, a second silane coupling agent layer 3 with the solubility parameter similar to that of the resin 4 is covered on the surface layer of the fiber material 1, the first silane coupling agent layer 2 and the second silane coupling agent layer 3 generate chemical bonds through chemical reaction and are coated on the surface layer of the fiber material 1, the fiber material 1 is bonded with the first silane coupling agent layer 2, the resin 4 is bonded with the second silane coupling agent layer 3, meanwhile, the silanes in the first silane coupling agent layer 2 and the second silane coupling agent layer 3 can be combined with each other to form a close-contact compact multi-molecular structure siloxane layer, thereby ensuring stronger binding force between the fiber material 1 and the resin 4 and enhancing the comprehensive mechanical property of the composite material.
In some embodiments of the present invention, the resin composite comprises the following components in parts by weight: 50-90 parts of fiber material, 20-90 parts of resin, 0.01-1 part of first silane coupling agent and 0.01-1 part of second silane coupling agent.
Preferably, the mass content of the fiber material 1 accounts for 70-80% of the total mass of the resin composite material, and the mass content of the resin 4 accounts for 20-30% of the total mass of the resin composite material.
The thickness of the fiber material is 100 to 200 [ mu ] m, the thickness of the first silane coupling agent layer 2 is 10 to 50 [ mu ] m, the thickness of the second silane coupling agent layer 3 is 10 to 50 [ mu ] m, and the thickness of the resin 4 is 10 to 30 [ mu ] m.
In different embodiments, when different fiber materials 1 and different resin 4 materials are selected, a silane coupling agent having high bonding strength with the fiber materials 1 and the resin 4 materials is also selected for the first silane coupling agent layer 2 and the second silane coupling agent layer 3.
Specifically, in some embodiments of the present invention, when the selection of the material of the first silane coupling agent layer 2 and the second silane coupling agent layer 3 is performed, the preferable conditions are: the first silane coupling agent layer 2 has a higher binding ability with the fiber material 1 than the second silane coupling agent layer 3; the second silane coupling agent layer 3 has a higher binding ability with the resin 4 than the first silane coupling agent layer 2; that is, the bonding strength between the first silane coupling agent layer 2 and the fiber material 1 is higher than the bonding strength between the second silane coupling agent layer 2 and the fiber material 1, and the bonding strength between the second silane coupling agent layer 2 and the resin 4 is higher than the bonding strength between the first silane coupling agent layer 2 and the resin 4. This arrangement is effective in improving the bonding strength between the fiber material 1 and the resin 4, relative to a single silane coupling agent or non-layered mixing of different silane coupling agents.
In some embodiments of the present invention, the fiber stock 1 includes one or more of Glass Fibers (GF), Carbon Fibers (CF), aramid fibers, and polyethylene fibers. More preferably, the fiber material 1 is made of glass fiber.
The fiber material 1 often has high strength and modulus, and after the fiber material is compounded with the resin 4, when the fiber material is impacted by external force, the fiber material 1 can bear a part of stress, so that the impact strength of the resin composite material is improved.
In some embodiments of the invention, the first silane coupling agent comprises a vinyl silane oligomer, wherein the vinyl silane oligomer is selected from the group consisting of silane coupling agents of Uygur chemical designation J & Y3137.
In some embodiments of the invention, the second silane coupling agent comprises one or more of an epoxy cyclohexyl-containing silane coupling agent selected from the group consisting of jiangyi chemical brand J & Y3185, methylpropyl acyloxy propyl trimethoxy silane selected from the group consisting of shin-yi chemical brand KBM-903, and gamma-aminopropyltriethoxysilane selected from the group consisting of dow corning brand Z-6030.
In some embodiments of the present invention, the resin 4 is a thermoplastic resin.
Specifically, the resin 4 includes one or more of polypropylene (PP), Polyamide (PA), Polyphenylene Sulfide (PPs), polyethylene terephthalate (PET), Polyethylene (PC), Polyetherimide (PEI), Polycarbonate (PC), polyether ether ketone (PEEK), and polyether ketone (PEKK).
In some embodiments of the present invention, the resin 4 is wrapped with chopped fibers 5, the surfaces of the chopped fibers 5, which are in contact with the resin 4, are covered with a third silane coupling agent layer, and the weight component of the chopped fibers 5 is 10-30 parts.
The bending strength and tensile strength of the resin 4 can be further enhanced by adding chopped fibers 5 to the resin 4, wherein the chopped fibers 5 are one or more of Glass Fibers (GF), Carbon Fibers (CF), aramid fibers and polyethylene fibers.
Preferably, the third silane coupling agent layer is made of the same material as the second silane coupling agent layer 3.
Another embodiment of the present invention discloses a method for preparing the resin composite material as described above, comprising the steps of:
applying a first silane coupling agent on the fiber material 1 to form a first silane coupling agent layer 2;
applying a second silane coupling agent on the first silane coupling agent layer 2 to form a second silane coupling agent layer 3;
the fiber material 1 having the first silane coupling agent layer 2 and the second silane coupling agent layer 3 is impregnated in a resin 4, and cured to obtain a resin composite material.
The "applying the first silane coupling agent on the fiber material 1 to form the first silane coupling agent layer 2" may perform surface treatment on the fiber material 1 by a process such as dipping, spray coating, mixing, and the like.
In some embodiments of the present invention, the "applying a first silane coupling agent on the fiber material 1 to form the first silane coupling agent layer 2" includes:
mixing 0.3-1.0 part by weight of a first silane coupling agent and 99-99.7 parts by weight of deionized water, hydrolyzing for 3-5 hours, wherein the pH value of the hydrolysis solution is 3-5, after the hydrolysis is completed, putting the fiber material 1 into the hydrolysis solution of the first silane coupling agent, soaking for 3-8 minutes under the action of ultrasound, taking out the fiber material 1 after the soaking is completed, and drying to form a first silane coupling agent layer 2 on the fiber material 1.
By the impregnation, the first silane coupling agent can be brought into sufficient contact with the fiber material 1, and the first silane coupling agent can have sufficient reaction time with the fiber material 1, thereby improving the bonding effect between the first silane coupling agent layer 2 and the fiber material 1.
In some embodiments of the present invention, the "applying a second silane coupling agent on the first silane coupling agent layer 2 to form the second silane coupling agent layer 3" includes:
mixing 0.3-1.0 part by weight of a second silane coupling agent, 94-96 parts by weight of isopropyl alcohol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, after the hydrolysis is completed, putting the fiber material 1 with the first silane coupling agent layer 2 into a hydrolysis solution of the second silane coupling agent, soaking for 3-8 min under the action of ultrasound, taking out the fiber material 1 after the soaking is completed, and drying to form a second silane coupling agent layer 3 on the first silane coupling agent layer 2.
The silane groups of the first and second silane coupling agents can be bonded to each other during the impregnation process to form a tightly adhered silicone layer having a multi-molecular structure, and the first silane coupling agent layer 2 is bonded to the fiber material 1, and the second silane coupling agent layer 3 is bonded to the resin 4.
It should be noted that, in some embodiments, a portion of the second silane coupling agent may also penetrate into the first silane coupling agent and be reacted and combined with the fiber material 1.
In some embodiments of the present invention, the "impregnating the fiber material 1 with the first and second silane coupling agent layers 2 and 3 in the resin 4, and curing to obtain the resin composite material" includes:
filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material 1 with a first silane coupling agent layer 2 and a second silane coupling agent layer 3 on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material 1, carrying out hot-pressing operation, keeping the hot-pressing temperature at 220-300 ℃ and the pressure at 1-5 MPa for 5-15 min, and cooling and curing to obtain the resin composite material.
In the present embodiment, the resin 4 is a thermoplastic resin powder having a particle size of 200 to 300 mesh and sufficiently dried.
In other embodiments, the fiber material with the first and second silane coupling agent layers may be impregnated with the resin by other methods, for example, by thermocompression bonding of a thermoplastic resin film and the fiber material, by coating a liquid resin on the surface of the fiber material and then curing, or by pouring a molten resin onto the fiber material.
In some embodiments of the present invention, before "soaking the fiber material 1 with the first silane coupling agent layer 2 and the second silane coupling agent layer 3 in a resin, and obtaining a resin composite material after curing" further includes:
mixing 0.3-1.0 part by weight of a third silane coupling agent, 94-96 parts by weight of isopropanol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, adding the chopped fiber 5 into a hydrolysis solution of the third silane coupling agent for soaking after the hydrolysis is finished, taking out the chopped fiber 5, drying, forming a third silane coupling agent layer on the surface of the chopped fiber 5, adding the chopped fiber 5 into thermoplastic resin powder, and uniformly dispersing.
The third silane coupling agent can adopt the same silane coupling agent as the second silane coupling agent, and the third silane coupling agent in the second silane coupling agent layer 3 and the resin 4 forms tight combination through mutual diffusion, an interpenetrating network system, molecular winding and chemical reaction, so that the comprehensive mechanical property of the composite material is enhanced.
The present invention will be further illustrated by the following examples.
Example 1
This example is for the purpose of illustrating the resin composite material and the method of preparing the same disclosed herein.
The material composition comprises the following components in parts by weight:
the method comprises the following operation steps:
the method comprises the following steps: mixing 0.5 part of first silane coupling agent and 99.5 parts of deionized water according to the weight parts, hydrolyzing for 4 hours, wherein the pH value of a hydrolysis solution is 4, after the hydrolysis is finished, putting a fiber material into the hydrolysis solution of the first silane coupling agent, soaking for 5min under the action of ultrasound, taking out the fiber material after the soaking is finished, and drying to form a first silane coupling agent layer on the fiber material.
Step two: mixing 0.5 part by weight of a second silane coupling agent, 95 parts by weight of isopropyl alcohol, and 4.5 parts by weight of deionized water, hydrolyzing for 30 minutes, after completion of the hydrolysis, putting the fiber material with the first silane coupling agent layer into a hydrolysis solution of the second silane coupling agent, soaking for 5 minutes under the action of ultrasound, taking out the fiber material after completion of the soaking, and forming a second silane coupling agent layer on the first silane coupling agent layer after drying.
Step three: mixing 0.5 part of third silane coupling agent, 95 parts of isopropanol and 4.5 parts of deionized water in parts by weight, hydrolyzing for 30min, adding the chopped fibers into a hydrolysis solution of the third silane coupling agent for soaking after the hydrolysis is finished, taking out the chopped fibers, drying, forming a third silane coupling agent layer on the surfaces of the chopped fibers, adding the chopped fibers into thermoplastic resin powder, and uniformly dispersing.
Step four: filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material with a first silane coupling agent layer and a second silane coupling agent layer on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material, carrying out hot-pressing operation, keeping the temperature and pressure at 280 ℃ and 3MPa for 10min, and cooling and curing to obtain the resin composite material.
The resulting resin composite material is labeled S1.
Example 2
This example is for the purpose of illustrating the resin composite material and the method of preparing the same disclosed herein.
The material composition comprises the following components in parts by weight:
the procedure was the same as in example 1.
The resulting resin composite material is labeled S2.
Example 3
This example is for the purpose of illustrating the resin composite material and the method of preparing the same disclosed herein.
The material composition comprises the following components in parts by weight:
the procedure was the same as in example 1.
The resulting resin composite material is labeled S3.
Example 4
This example is for the purpose of illustrating the resin composite material and the method of preparing the same disclosed herein.
The material composition comprises the following components in parts by weight:
the method comprises the following operation steps:
the method comprises the following steps: mixing 0.5 part of first silane coupling agent and 99.5 parts of deionized water according to the weight parts, hydrolyzing for 4 hours, wherein the pH value of a hydrolysis solution is 4, after the hydrolysis is finished, putting a fiber material into the hydrolysis solution of the first silane coupling agent, soaking for 5min under the action of ultrasound, taking out the fiber material after the soaking is finished, and drying to form a first silane coupling agent layer on the fiber material.
Step two: mixing 0.5 part by weight of a second silane coupling agent, 95 parts by weight of isopropyl alcohol, and 4.5 parts by weight of deionized water, hydrolyzing for 30 minutes, after completion of the hydrolysis, putting the fiber material with the first silane coupling agent layer into a hydrolysis solution of the second silane coupling agent, soaking for 5 minutes under the action of ultrasound, taking out the fiber material after completion of the soaking, and forming a second silane coupling agent layer on the first silane coupling agent layer after drying.
Step three: filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material with a first silane coupling agent layer and a second silane coupling agent layer on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material, carrying out hot-pressing operation, keeping the temperature and pressure at 280 ℃ and 3MPa for 10min, and cooling and curing to obtain the resin composite material.
The resulting resin composite material is labeled S4.
Example 5
This example is for the purpose of illustrating the resin composite material and the method of preparing the same disclosed herein.
The material composition comprises the following components in parts by weight:
the procedure was the same as in example 1.
The resulting resin composite material is labeled S5.
Comparative example 1
This example is for comparative illustration of the resin composite material and the method of preparing the same disclosed in the present invention.
The material composition comprises the following components in parts by weight:
thermoplastic resin powder: baoli polyphenylene sulfide 0220U 35 parts
First silane coupling agent: 31370.5 portions of J & Y (build and resolute)
Fiber material: taishan fiberglass cloth 7628M 65 parts
The procedure was the same as in example 1.
The method comprises the following operation steps:
the method comprises the following steps: mixing 0.5 part of first silane coupling agent and 99.5 parts of deionized water according to the weight parts, hydrolyzing for 4 hours, wherein the pH value of a hydrolysis solution is 4, after the hydrolysis is finished, putting a fiber material into the hydrolysis solution of the first silane coupling agent, soaking for 5min under the action of ultrasound, taking out the fiber material after the soaking is finished, and drying to form a first silane coupling agent layer on the fiber material.
Step two: filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material with a first silane coupling agent layer on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material, carrying out hot-pressing operation, keeping the hot-pressing temperature at 280 ℃ and the pressure at 3MPa for 10min, and cooling and curing to obtain the resin composite material.
The resulting resin composite was labeled D1.
Performance testing
The following performance tests were performed on the prepared S1 to S5 and D1:
the resin composite materials S1-S5 and D1 are processed into standard parts according to corresponding national standards GB/T1447, GB/T1449 and GB/T1451, and main mechanical strength (including tensile strength, bending modulus and notch impact strength) is detected.
The test results obtained are filled in Table 1.
TABLE 1
The results of the comparative examples 1-5 and the comparative example 1 show that the resin composite material obtained by the technical scheme of the invention has effectively improved mechanical properties in all aspects.
The results of comparative examples 1 to 3 show that the type of the coupling agent and the length of the chopped fiber added to the resin have a significant effect on the mechanical properties of the composite material. The second silane coupling agent in example 1 has better compatibility with the first silane coupling agent and PPS resin than the second silane coupling agent in example 2, and the final material has higher strength. The chopped fibers added into the resin in the embodiment 1 are short in length, so that the tensile strength and the bending strength of the material are improved, and the chopped fibers added into the resin in the embodiment 3 are long in length, so that the impact strength is obviously improved.
Comparing the results of example 1, example 4 and example 5, it can be seen that the presence or absence of the addition of chopped fibers to the resin, and the type of resin, have a significant effect on the mechanical strength of the material. In example 5, the resin polyamide itself is slightly more flexible than polyphenylene sulfide, and thus the final composite material has improved notched impact strength although the tensile and flexural strength is slightly lower.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (13)
1. A resin composite material, comprising a fiber material, a first silane coupling agent layer, a second silane coupling agent layer, and a resin, wherein the first silane coupling agent layer, the second silane coupling agent layer, and the resin are sequentially coated on the surface of the fiber material from inside to outside;
the first silane coupling agent layer includes a vinyl silane oligomer, and the second silane coupling agent includes one or more of a silane coupling agent with an epoxy cyclohexyl group, methacryloxypropyltrimethoxysilane, and γ -aminopropyltriethoxysilane;
the resin is wrapped by chopped fibers, the surfaces of the chopped fibers, which are in contact with the resin, are covered by a third silane coupling agent layer, and the third silane coupling agent layer is made of the same material as the second silane coupling agent layer;
the bonding strength between the first silane coupling agent layer and the fiber material is greater than the bonding strength between the second silane coupling agent layer and the fiber material, and the bonding strength between the second silane coupling agent layer and the resin is greater than the bonding strength between the first silane coupling agent layer and the resin.
2. The resin composite according to claim 1, wherein the fiber material is a fiber woven cloth formed by weaving fiber bundles, and the surface of the fiber bundles is covered with the first silane coupling agent layer, the second silane coupling agent layer, and the resin in this order from inside to outside.
3. The resin composite material according to claim 1, characterized by comprising the following components in parts by weight: 50-90 parts of fiber material, 20-90 parts of resin, 0.01-1 part of a first silane coupling agent layer, 0.01-1 part of a second silane coupling agent layer and 10-30 parts of chopped fibers.
4. The resin composite material according to claim 1, wherein the fiber material has a thickness of 100 to 200 μm, the first silane coupling agent layer has a thickness of 10 to 50 μm, the second silane coupling agent layer has a thickness of 10 to 50 μm, and the resin has a thickness of 10 to 30 μm.
5. The resin composite of claim 1, wherein the fiber material comprises one or more of glass fibers, carbon fibers, aramid fibers, and polyethylene fibers.
6. The resin composite according to claim 1, wherein the resin is a thermoplastic resin.
7. The resin composite of claim 6, wherein the resin comprises one or more of polypropylene, polyamide, polyphenylene sulfide, polyethylene terephthalate, polyethylene, polyetherimide, polycarbonate, polyetheretherketone, polyetherketoneketone.
8. The method for producing a resin composite material as claimed in any one of claims 1 to 7, comprising the steps of:
applying a first silane coupling agent to the fiber material to form a first silane coupling agent layer;
applying a second silane coupling agent on the first silane coupling agent layer to form a second silane coupling agent layer;
soaking the fiber material with the first silane coupling agent layer and the second silane coupling agent layer in resin, and curing to obtain a resin composite material;
the first silane coupling agent layer includes a vinyl silane oligomer, and the second silane coupling agent includes one or more of a silane coupling agent with an epoxy cyclohexyl group, methacryloxypropyltrimethoxysilane, and γ -aminopropyltriethoxysilane;
the resin is wrapped by chopped fibers, the surfaces of the chopped fibers, which are in contact with the resin, are covered by a third silane coupling agent layer, and the third silane coupling agent layer is made of the same material as the second silane coupling agent layer;
the bonding strength between the first silane coupling agent layer and the fiber material is greater than the bonding strength between the second silane coupling agent layer and the fiber material, and the bonding strength between the second silane coupling agent layer and the resin is greater than the bonding strength between the first silane coupling agent layer and the resin.
9. The method for producing a resin composite according to claim 8, wherein the "applying a first silane coupling agent on a fiber material to form a first silane coupling agent layer" includes:
mixing 0.3-1.0 part by weight of a first silane coupling agent and 99-99.7 parts by weight of deionized water, hydrolyzing for 3-5 hours, wherein the pH value of the hydrolysis solution is 3-5, after the hydrolysis is completed, putting a fiber material into the hydrolysis solution of the first silane coupling agent, soaking for 3-8 minutes under the action of ultrasound, taking out the fiber material after the soaking is completed, and drying to form a first silane coupling agent layer on the fiber material.
10. The method for producing a resin composite material according to claim 8, wherein the "applying a second silane coupling agent on the first silane coupling agent layer to form a second silane coupling agent layer" includes:
mixing 0.3-1.0 part by weight of a second silane coupling agent, 94-96 parts by weight of isopropanol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, after the hydrolysis is completed, putting the fiber material with the first silane coupling agent layer into a hydrolysis solution of the second silane coupling agent, soaking for 3-8 min under the action of ultrasound, taking out the fiber material after the soaking is completed, and drying to form a second silane coupling agent layer on the first silane coupling agent layer.
11. The method for producing a resin composite material according to claim 8, wherein the step of impregnating a fiber material having the first silane coupling agent layer and the second silane coupling agent layer with a resin and curing the impregnated fiber material to obtain the resin composite material comprises:
filling part of thermoplastic resin powder into a hot-pressing die, placing a fiber material with a first silane coupling agent layer and a second silane coupling agent layer on the thermoplastic resin powder, filling the rest of the thermoplastic resin powder on the top of the fiber material, carrying out hot-pressing operation, keeping the temperature and pressure at 220-300 ℃ and 1-5 MPa for 5-15 min, and cooling and curing to obtain the resin composite material.
12. The method of producing a resin composite material according to claim 11, wherein the step of impregnating a fiber material having the first silane coupling agent layer and the second silane coupling agent layer with a resin and curing the impregnated fiber material to obtain the resin composite material further comprises:
mixing 0.3-1.0 part by weight of a third silane coupling agent, 94-96 parts by weight of isopropanol and 3-7 parts by weight of deionized water, hydrolyzing for 25-40 min, adding the chopped fibers into a hydrolysis solution of the third silane coupling agent for soaking after the hydrolysis is finished, taking out the chopped fibers, drying, forming a third silane coupling agent layer on the surfaces of the chopped fibers, adding the chopped fibers into thermoplastic resin powder, and uniformly dispersing.
13. The method for producing a resin composite material according to claim 11, wherein the particle size of the thermoplastic resin powder is 200 to 300 mesh.
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