CN112679908A - Prepreg toughening material, high-toughness prepreg and preparation method thereof - Google Patents
Prepreg toughening material, high-toughness prepreg and preparation method thereof Download PDFInfo
- Publication number
- CN112679908A CN112679908A CN201910987515.8A CN201910987515A CN112679908A CN 112679908 A CN112679908 A CN 112679908A CN 201910987515 A CN201910987515 A CN 201910987515A CN 112679908 A CN112679908 A CN 112679908A
- Authority
- CN
- China
- Prior art keywords
- prepreg
- epoxy resin
- toughening
- resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a prepreg toughening material, a high-toughness prepreg and a preparation method thereof, and mainly solves the problems that the viscosity of a system is increased, the process operability is poor and the carbon fiber impregnation effect is poor due to the fact that a thermoplastic resin toughening epoxy resin matrix for the prepreg is subjected to a hot melting method. The above problems are solved by means of dispensing modified clay with ultrafine particles of thermoplastic resin as toughening agent into epoxy resin and then as toughening layer. The prepreg toughening material comprises 100 parts of epoxy resin, 2-200 parts of modified clay and 2-200 parts of thermoplastic resin. The high-toughness prepreg provided by the invention can greatly reduce the system viscosity, has good manufacturability, has high compressive strength after the impact of the laminated board, and can be used for preparing various carbon fiber composite material main bearing structures and non-bearing parts.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a prepreg toughening material, a high-toughness prepreg and preparation methods thereof.
Background
The advanced resin-based composite material has the performance characteristics of high specific modulus and specific strength, fatigue resistance, corrosion resistance, strong designability and the like, is widely applied, is one of light-weight and high-performance materials which are optimized for main bearing structural members of aerospace aircrafts, is widely applied to various fields of aerospace aviation, war industry, automobile light-weight and the like, and has increasingly increased application proportion. Advanced resin-based composite materials are divided into three generations according to the toughness. Since the first generation of composite materials exhibit brittle material performance characteristics, the performance of laminates is susceptible to impact load induced damage, particularly delamination damage, and for this reason, the development of toughened epoxy resin matrices and improved fiber reinforcement means are required to improve impact resistance. The second generation composite material is toughened and modified resin-based composite material, the used matrix resin is a thermoplastic resin toughening system such as 977, 6376, 5260 and the like, and the reinforced fiber is represented by middle-mold high-strength carbon fiber in T800H of Dongli company and IM7 of Hercules company. Typical applications are boeing B777 aircraft empennage and other aircraft wings, fuselages, horizontal tails, floor beams, hatches, fairings, transmitter blades, etc. As a candidate scheme for weight reduction of the civil aircraft body structure, Boeing company provides a carbon fiber performance improvement index, and establishes a carbon fiber reinforced material, a medium-modulus high-strength yarn and a fabric standard BMS 8-17. The boeing company of 5 months in 1990 also provides a high-toughness carbon fiber epoxy prepreg standard (BMS8-276), a technical index system suitable for a composite material for a main bearing structure of a civil company is provided, a third-generation high-toughness resin-based composite material is produced at the same time, a resin-rich interlayer toughening or intercalation toughening technology is adopted, the compression strength (CAI) after impact is greatly improved, representative matrix resins are Toray 3900, Hexcel8552 and the like, and the representative Dongli high-toughness T800/3900 prepreg is mainly used for a B787 main bearing structure composite material of the boeing company.
High CAI requires the composite material to have high toughness, and the main approach to improve toughness is to perform matrix resin toughening and interlayer toughening. The thermoplastic resin is preferably used as a toughening agent for toughening the matrix resin, so that the toughness is improved and the heat resistance of the composite material is not reduced. The Hexcel company patent EP2607411 adopts polyether sulfone (PES) resin and Polyamide (PA) particles to perform composite toughening modification on an epoxy resin matrix, PES exists in the epoxy resin in a completely dissolved mode, PA particles exist in the epoxy resin in a dispersed state, and the CAI of a carbon fiber prepreg laminated board prepared by adopting the toughening resin matrix can reach 350 MPa. As the content of the thermoplastic resin is close to 30 wt%, the viscosity of the toughened resin matrix is very high, and the requirements on the mixing process of the resin matrix and the subsequent coating and presoaking processes are very high. Yixiaosu et al proposed the "ex-situ toughening" technique (CN1923506A) to solve a series of process problems caused by the direct dissolution or dispersion of high content of thermoplastic resin in the resin matrix. The dislocation toughening technology places thermoplastic resin between two carbon fiber layers impregnated by low-viscosity resin matrix in the form of film, powder and the like, and purposefully improves the interlaminar toughness of the composite material, thereby obviously improving the CAI of the composite material. Chinese patent CN104842619A provides a high-toughness multilayer structure prepreg manufacturing process, which is characterized in that one or more toughening layers are additionally arranged on the basis of a resin layer-fiber layer-resin layer three-layer structure, the toughening layers exist in the form of films, powder or fabrics and the like, and the CAI of the toughened composite material reaches 260 MPa. Although the toughening techniques described above achieve better toughening, they also present other problems, such as "ex-situ toughening" which results in a loss of tack in the prepreg.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, a prepreg laminated board has low compression strength after impact and is difficult to meet the performance requirement of a composite material, and provides a prepreg toughening material and a high-toughness prepreg obtained from the prepreg toughening material.
One of the purposes of the invention is to provide a prepreg toughening material, which comprises an epoxy resin, and modified clay and thermoplastic resin which are dispersed in the epoxy resin, wherein the prepreg toughening material comprises the following components in parts by weight:
100 parts of epoxy resin;
2-200 parts of modified clay; preferably 5-90 parts; more preferably 5 to 60 parts;
2-200 parts of thermoplastic resin; preferably 30-90 parts; more preferably 30 to 70 parts.
The epoxy resin may be any epoxy resin commonly used in the art, and is preferably at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, and glycidyl amine epoxy resin.
The thermoplastic resin is soluble in an epoxy resin, and is preferably at least one thermoplastic resin such as polyethersulfone, polyetherimide, polyetheretherketone, or polysulfone.
The modified clay is preferably physically modified, inorganic intercalated or organically modified.
The particle size of the thermoplastic resin is preferably 200 to 2000 meshes, and more preferably 200 to 600 meshes.
In the prepreg toughening material, the modified clay and the thermoplastic resin particles are dispersed in the epoxy resin and are not dissolved.
The invention can also add various auxiliary agents commonly used in the field according to the processing requirements, such as flame retardants, diluents, accelerators and the like, and the dosage of the auxiliary agents is conventional dosage or is adjusted according to the requirements of actual situations.
The invention also aims to provide a preparation method of the prepreg toughening material, which comprises the step of dispersing components including the modified clay and the thermoplastic resin particles into epoxy resin.
In the above technical solutions, the method for dispersing the modified clay and the thermoplastic resin in the epoxy resin is a method generally used in the art, and includes, but is not limited to, a mechanical force dispersion method, an ultrasonic dispersion method, and a high energy treatment method.
Preferably, the modified clay and the thermoplastic resin are dispersed in the epoxy resin at a temperature below the melting point of the thermoplastic resin to ensure that the thermoplastic resin is only dispersed and insoluble.
The invention also aims to provide a high-toughness prepreg, which comprises an epoxy resin matrix, reinforcing fibers and a toughening layer, wherein the toughening layer covers the reinforcing fibers impregnated in the epoxy resin matrix, and the raw material of the toughening layer is the prepreg toughening material.
In the technical scheme, the high-toughness prepreg comprises the following components in percentage by weight:
10-50% of epoxy resin matrix, preferably 20-35%;
40-85% of reinforcing fiber, preferably 60-75%;
2-40% of toughening layer, preferably 5-20%.
In the above technical solution, the epoxy resin in the epoxy resin matrix may be an epoxy resin generally used in the art, and is preferably at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, and glycidyl amine epoxy resin.
The composition of the resin matrix is not particularly limited, and the components and the amounts of the components are all common components and conventional amounts in the field, or are adjusted according to the requirements of actual situations.
In the above technical solution, the epoxy resin matrix may contain a curing agent, and the curing agent may be a curing agent generally used in the art, and is preferably at least one of an amine curing agent, an acid anhydride curing agent, a phenol novolac curing agent, a polyester resin curing agent, a polyurethane curing agent, a styrene-maleic anhydride copolymer resin curing agent, and a polysulfide rubber curing agent. The amount of the curing agent is the usual amount, and is calculated according to the reaction formula of the epoxy value of the epoxy resin and the curing agent, based on 100 parts by weight of the epoxy resin.
In the above technical solution, the epoxy resin matrix may also include an accelerator for accelerating the curing reaction, and the accelerator may be an accelerator commonly used in the art, including but not limited to boron-amine complex or a passivating imidazole accelerator. The amount of the accelerator is generally used, and preferably, the amount of the accelerator is 0.01 to 10 parts by weight based on 100 parts by weight of the epoxy resin.
In the above technical solution, the reinforcing fiber may be a fiber generally used in the art, and the reinforcing fiber is preferably at least one of carbon fiber, aramid fiber, glass fiber, and basalt fiber.
The reinforcing fibers may be in the form of continuous unidirectional fibers or a fabric.
The fourth purpose of the invention is to provide a preparation method of the high-toughness prepreg, which comprises the steps of impregnating the reinforcing fibers with the epoxy resin matrix, and then covering the reinforcing fibers with the toughening layer.
The impregnation method is a method generally used in the art.
The toughening layer may be applied over the reinforcing fibers as described above using methods common in the art.
In the above technical solution, the impregnation process and conditions may adopt the processes and conditions that are common in the prior art. The used equipment is also the equipment in the prepreg processing in the prior art, such as a film coating machine, a pre-dipping machine and the like.
Specifically, the preparation method of the high-toughness prepreg can comprise the following steps:
a) preparation of epoxy resin matrix: adding a curing agent under the conditions of heating, stirring and vacuumizing;
b) preparing a resin adhesive film: uniformly coating the epoxy resin matrix on the surface of release paper on a hot-melt film coating machine;
c) preparing a toughening layer: uniformly coating the epoxy resin dispersed with the modified clay and the thermoplastic resin on release paper on a hot-melt method coating machine under the condition that the temperature is lower than the melting point of the thermoplastic resin;
d) preparing a prepreg: on a pre-dipping machine provided with a plurality of groups of winding and unwinding stations, firstly, the resin adhesive film is used for dipping the reinforced fibers, then the toughening layer is covered on the reinforced fibers, and the PE film is covered and wound.
The high-toughness prepreg provided by the invention has the advantages that:
1) the modified clay and the thermoplastic resin particles are dispersed in the epoxy resin and then used as a toughening layer, and the epoxy resin matrix system has low viscosity, so that the improvement of the process operability and the carbon fiber impregnation effect are facilitated.
2) The modified clay and the thermoplastic resin particles in the toughening layer can improve the toughness of the system through synergistic effect.
The invention mainly solves the problems that the viscosity of a system is increased, the process operability is poor and the carbon fiber impregnation effect is poor due to the fact that the thermoplastic resin for the hot-melt prepreg toughens the epoxy resin matrix. The invention provides a mode of distributing modified clay and thermoplastic resin ultrafine particles as a toughening agent into epoxy resin and then serving as a toughening layer, the provided high-toughness prepreg can greatly reduce the system viscosity, has good manufacturability, has high compressive strength after the impact of a laminated board, and can be used for preparing main bearing structures and non-bearing parts of various carbon fiber composite materials.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the embodiments of the present invention are commercially available.
[ example 1 ]
Preparation of fiber areal density of 160g/m with Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 62.5 wt%
A toughening layer: 12.5 wt.%
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
bisphenol a epoxy resin: 100 portions of
4, 4' -diaminodiphenyl sulfone: 45 portions of
The mixing process comprises the following steps: adding 4, 4' -diaminodiphenyl sulfone into the epoxy resin mixture, heating to 90 ℃, and uniformly mixing.
Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a coating machine, and uniformly coating the resin matrix on release paper at a coating temperature of 90 ℃. The surface density of the resin film surface is 20g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
bisphenol a epoxy resin: 100 portions of
Polyethersulfone (400 mesh): 40 portions of
Modified clay: 10 portions of
The mixing process comprises the following steps: the modified clay and the polyether sulfone are dispersed in epoxy resin at 90 deg.c to ensure the polyether sulfone to disperse and dissolve.
Preparing a toughening layer: putting the toughening layer resin into a resin tank of a coating machine, and uniformly coating the resin on release paper at a coating temperature of 90 ℃ to obtain the surface density of 20g/m2The toughening layer of (1).
3) Prepreg preparation
And respectively placing the two rolls of resin films on an upper roll placing station and a lower roll placing station at the front end of the pre-soaking machine, and placing the toughening layer on an unreeling station in the middle of the pre-soaking machine. And the upper and lower layers of resin adhesive films finish the impregnation of the carbon fibers arranged in a single direction at the first and second heating rollers and the heating plate. And then, rolling the upper release paper, unreeling the toughening layer from the middle unreeling station to cover the surface of the prepreg, and finishing the attachment of the toughening layer to the surface of the prepreg at a third heating roller and a heating plate. And (4) winding the upper delamination type paper after cooling by the cooling plate, covering the PE film, and finally finishing winding the prepreg.
4) Laminate preparation and performance evaluation:
cutting the prepreg into proper sizes according to the requirements of GB/T21239-2007 standard, laying, placing the prepreg into an autoclave for curing in the sequence of [45/0/-45/90] S, wherein the curing process is 120 ℃/1h +180 ℃/2h, the heating rate is 2 ℃/min, and the cured laminated board is cut to obtain the test sample plate with the size of 150mm x 100mm x 5 mm. The samples were tested for post-impact compressive strength according to GB/T21239-2007 standard.
[ examples 2 to 3 ]
The prepreg process was the same as in example 1 except that the amount of modified clay added in the toughening layer was 5 parts and 180 parts, respectively.
[ examples 4 to 5 ]
The prepreg method was the same as example 1 except that the amount of polyethersulfone added in the toughening layer was 5 parts and 180 parts, respectively.
[ examples 6 to 7 ]
The prepreg process was the same as in example 1, except that the proportions of the components in the prepreg were different.
Example 6 preparation of a fiber with an areal density of 160g/m using Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 45.0 wt.%
T700 × 12k carbon fiber: 52.0 wt%
A toughening layer: 3.0 wt.%
Example 7 preparation of a fiber with an areal density of 160g/m using Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 15.0 wt.%
T700 × 12k carbon fiber: 50.0 wt%
A toughening layer: 35.0 wt.%
[ example 8 ]
Preparation of fiber areal density of 160g/m with Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 62.5 wt%
A toughening layer: 12.5 wt.%
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
4, 4' -diaminodiphenyl sulfone: 60 portions of
The mixing process comprises the following steps: adding 4, 4' -diaminodiphenyl sulfone into the epoxy resin mixture, heating to 90 ℃, and uniformly mixing.
Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a coating machine, and uniformly coating the resin matrix on release paper at a coating temperature of 90 ℃. The surface density of the resin film surface is 20g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
Polyethersulfone (400 mesh): 40 portions of
Modified clay: 10 portions of
The mixing process comprises the following steps: the modified clay and the polyether sulfone are dispersed in epoxy resin at 90 deg.c to ensure the polyether sulfone to disperse and dissolve.
Preparing a toughening layer: putting the toughening layer resin into a resin tank of a coating machine, and uniformly coating the resin on release paper at a coating temperature of 90 ℃ to obtain the surface density of 20g/m2The toughening layer of (1).
3) Prepreg preparation
And respectively placing the two rolls of resin films on an upper roll placing station and a lower roll placing station at the front end of the pre-soaking machine, and placing the toughening layer on an unreeling station in the middle of the pre-soaking machine. And the upper and lower layers of resin adhesive films finish the impregnation of the carbon fibers arranged in a single direction at the first and second heating rollers and the heating plate. And then, rolling the upper release paper, unreeling the toughening layer from the middle unreeling station to cover the surface of the prepreg, and finishing the attachment of the toughening layer to the surface of the prepreg at a third heating roller and a heating plate. And (4) winding the upper delamination type paper after cooling by the cooling plate, covering the PE film, and finally finishing winding the prepreg.
4) Laminate preparation and performance evaluation:
cutting the prepreg into proper sizes according to the requirements of GB/T21239-2007 standard, laying, placing the prepreg into an autoclave for curing in the sequence of [45/0/-45/90] S, wherein the curing process is 120 ℃/1h +180 ℃/2h, the heating rate is 2 ℃/min, and the cured laminated board is cut to obtain the test sample plate with the size of 150mm x 100mm x 5 mm. The samples were tested for post-impact compressive strength according to GB/T21239-2007 standard.
[ example 9 ]
Preparation of fiber areal density of 160g/m with Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 62.5 wt%
A toughening layer: 12.5 wt.%
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
4, 4' -diaminodiphenyl sulfone: 60 portions of
The mixing process comprises the following steps: adding 4, 4' -diaminodiphenyl sulfone into the epoxy resin mixture, heating to 90 ℃, and uniformly mixing.
Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a coating machine, and uniformly coating the resin matrix on release paper at a coating temperature of 90 ℃. The surface density of the resin film surface is 20g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
Polyetheretherketone (400 mesh): 40 portions of
Modified clay: 10 portions of
The mixing process comprises the following steps: the modified clay and the polyether-ether-ketone are dispersed in the epoxy resin at the temperature of 90 ℃ to ensure that the polyether-ether-ketone is only dispersed and not dissolved.
Preparing a toughening layer: putting the toughening layer resin into a resin tank of a coating machine, and uniformly coating the resin on release paper at a coating temperature of 90 ℃ to obtain the surface density of 20g/m2The toughening layer of (1).
3) Prepreg preparation
And respectively placing the two rolls of resin films on an upper roll placing station and a lower roll placing station at the front end of the pre-soaking machine, and placing the toughening layer on an unreeling station in the middle of the pre-soaking machine. And the upper and lower layers of resin adhesive films finish the impregnation of the carbon fibers arranged in a single direction at the first and second heating rollers and the heating plate. And then, rolling the upper release paper, unreeling the toughening layer from the middle unreeling station to cover the surface of the prepreg, and finishing the attachment of the toughening layer to the surface of the prepreg at a third heating roller and a heating plate. And (4) winding the upper delamination type paper after cooling by the cooling plate, covering the PE film, and finally finishing winding the prepreg.
4) Laminate preparation and performance evaluation:
cutting the prepreg into proper sizes according to the requirements of GB/T21239-2007 standard, laying, placing the prepreg into an autoclave for curing in the sequence of [45/0/-45/90] S, wherein the curing process is 120 ℃/1h +180 ℃/2h, the heating rate is 2 ℃/min, and the cured laminated board is cut to obtain the test sample plate with the size of 150mm x 100mm x 5 mm. The samples were tested for post-impact compressive strength according to GB/T21239-2007 standard.
[ example 10 ]
Preparation of fiber areal density of 160g/m with Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 62.5 wt%
A toughening layer: 12.5 wt.%
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
3, 3' -diaminodiphenyl sulfone: 60 portions of
The mixing process comprises the following steps: adding 3, 3' -diaminodiphenyl sulfone into the epoxy resin mixture, heating to 90 ℃, and uniformly mixing.
Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a coating machine, and uniformly coating the resin matrix on release paper at a coating temperature of 90 ℃. The surface density of the resin film surface is 20g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
Polyetherimide (400 mesh): 40 portions of
Modified clay: 10 portions of
The mixing process comprises the following steps: the modified clay and the polyether sulfone are dispersed in epoxy resin at 90 deg.c to ensure the polyether sulfone to disperse and dissolve.
Preparing a toughening layer: putting the toughening layer resin into a resin tank of a coating machine, and uniformly coating the resin on release paper at a coating temperature of 90 ℃ to obtain the surface density of 20g/m2The toughening layer of (1).
3) Prepreg preparation
And respectively placing the two rolls of resin films on an upper roll placing station and a lower roll placing station at the front end of the pre-soaking machine, and placing the toughening layer on an unreeling station in the middle of the pre-soaking machine. And the upper and lower layers of resin adhesive films finish the impregnation of the carbon fibers arranged in a single direction at the first and second heating rollers and the heating plate. And then, rolling the upper release paper, unreeling the toughening layer from the middle unreeling station to cover the surface of the prepreg, and finishing the attachment of the toughening layer to the surface of the prepreg at a third heating roller and a heating plate. And (4) winding the upper delamination type paper after cooling by the cooling plate, covering the PE film, and finally finishing winding the prepreg.
4) Laminate preparation and performance evaluation:
cutting the prepreg into proper sizes according to the requirements of GB/T21239-2007 standard, laying, placing the prepreg into an autoclave for curing in the sequence of [45/0/-45/90] S, wherein the curing process is 120 ℃/1h +180 ℃/2h, the heating rate is 2 ℃/min, and the cured laminated board is cut to obtain the test sample plate with the size of 150mm x 100mm x 5 mm. The samples were tested for post-impact compressive strength according to GB/T21239-2007 standard.
[ examples 11 to 12 ] of the present invention
The prepreg method was the same as in example 1, except that the carbon fibers used were different, i.e., Toray T300 × 12k carbon fibers and Toray T800H × 12k carbon fibers.
[ example 13 ]
Preparation of fiber areal density of 160g/m with Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 62.5 wt%
A toughening layer: 12.5 wt.%
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
4, 4' -diaminodiphenyl sulfone: 60 portions of
The mixing process comprises the following steps: adding 4, 4' -diaminodiphenyl sulfone into the epoxy resin mixture, heating to 90 ℃, and uniformly mixing.
Preparing a resin adhesive film: pouring the resin matrix into a resin tank of a coating machine, and uniformly coating the resin matrix on release paper at a coating temperature of 90 ℃. The surface density of the resin film surface is 20g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin: 30 portions of
Trifunctional epoxy resin: 30 portions of
Bisphenol a epoxy resin: 40 portions of
Polyethersulfone (2000 mesh): 40 portions of
Modified clay: 10 portions of
The mixing process comprises the following steps: the modified clay and the polyether sulfone are dispersed in epoxy resin at 90 deg.c to ensure the polyether sulfone to disperse and dissolve.
Preparing a toughening layer: putting the toughening layer resin into a resin tank of a coating machine, and uniformly coating the resin on release paper at a coating temperature of 90 ℃ to obtain the surface density of 20g/m2The toughening layer of (1).
3) Prepreg preparation
And respectively placing the two rolls of resin films on an upper roll placing station and a lower roll placing station at the front end of the pre-soaking machine, and placing the toughening layer on an unreeling station in the middle of the pre-soaking machine. And the upper and lower layers of resin adhesive films finish the impregnation of the carbon fibers arranged in a single direction at the first and second heating rollers and the heating plate. And then, rolling the upper release paper, unreeling the toughening layer from the middle unreeling station to cover the surface of the prepreg, and finishing the attachment of the toughening layer to the surface of the prepreg at a third heating roller and a heating plate. And (4) winding the upper delamination type paper after cooling by the cooling plate, covering the PE film, and finally finishing winding the prepreg.
4) Laminate preparation and performance evaluation:
cutting the prepreg into proper sizes according to the requirements of GB/T21239-2007 standard, laying, placing the prepreg into an autoclave for curing in the sequence of [45/0/-45/90] S, wherein the curing process is 120 ℃/1h +180 ℃/2h, the heating rate is 2 ℃/min, and the cured laminated board is cut to obtain the test sample plate with the size of 150mm x 100mm x 5 mm. The samples were tested for post-impact compressive strength according to GB/T21239-2007 standard.
[ COMPARATIVE EXAMPLE 1 ]
The prepreg method was the same as example 1, except that the toughening layer resin formulation was:
bisphenol a epoxy resin: 100 portions of
Polyethersulfone (400 mesh): 40 portions of
[ COMPARATIVE EXAMPLE 2 ]
The prepreg method was the same as example 1, except that the toughening layer resin formulation was:
bisphenol a epoxy resin: 100 portions of
Modified clay: 10 parts.
Table 1 below shows the results of the compression strength test after impact of the laminates of examples and comparative examples.
TABLE 1 post impact compressive Strength test results for laminates
| Compressive Strength after impact (MPa) | |
| Example 1 | 246 |
| Example 2 | 231 |
| Example 3 | 212 |
| Example 4 | 236 |
| Example 5 | 223 |
| Example 6 | 189 |
| Example 7 | 177 |
| Example 8 | 257 |
| Example 9 | 252 |
| Example 10 | 249 |
| Example 11 | 221 |
| Example 12 | 297 |
| Example 13 | 209 |
| Comparative example 1 | 225 |
| Comparative example 2 | 213 |
Claims (10)
1. A prepreg toughening material comprises an epoxy resin, and dispersed therein, a modified clay and a thermoplastic resin, in parts by weight:
100 parts of epoxy resin;
2-200 parts of modified clay; preferably 5-90 parts;
2-200 parts of thermoplastic resin; preferably 30 to 90 parts.
2. The prepreg toughening material of claim 1, wherein:
the epoxy resin is at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin and glycidyl amine epoxy resin; and/or the presence of a gas in the gas,
the thermoplastic resin is at least one of polyether sulfone, polyether imide, polyether ether ketone and polysulfone.
3. The prepreg toughening material of claim 1, wherein:
the particle size of the thermoplastic resin is 200-2000 meshes, preferably 200-600 meshes; and/or the presence of a gas in the gas,
the modified clay is physically modified, inorganic intercalated or organically modified.
4. A method of preparing a prepreg toughening material according to any one of claims 1 to 3 comprising dispersing components comprising the modified clay and thermoplastic resin particles into an epoxy resin.
5. The method for preparing the prepreg toughening material according to claim 4, wherein:
the dispersion methods include a mechanical force dispersion method, an ultrasonic dispersion method, and a high energy treatment method.
6. A high toughness prepreg comprising an epoxy resin matrix, reinforcing fibres and a toughening layer, wherein the toughening layer overlies the reinforcing fibres impregnated with the epoxy resin matrix, the toughening layer being derived from a prepreg toughening material as claimed in any one of claims 1 to 3.
7. A high tenacity prepreg according to claim 6 comprising the following components in weight percent:
10-50% of epoxy resin matrix, preferably 20-35%;
40-85% of reinforcing fiber, preferably 60-75%;
2-40% of toughening layer, preferably 5-20%.
8. A high tenacity prepreg according to claim 6 wherein:
the reinforced fiber is at least one of carbon fiber, aramid fiber, glass fiber and basalt fiber; and/or the presence of a gas in the gas,
the reinforcing fibers are continuous unidirectional fibers or fabrics.
9. A high tenacity prepreg according to claim 6 wherein:
the epoxy resin matrix contains a curing agent, and the curing agent is preferably at least one of an amine curing agent, an anhydride curing agent, a linear phenolic curing agent, a polyester resin curing agent, a polyurethane curing agent, a styrene-maleic anhydride copolymer resin curing agent and a polysulfide rubber curing agent; and/or the presence of a gas in the gas,
the epoxy resin matrix contains an accelerant, and the accelerant is preferably at least one of boron-amine complex or passivated imidazole accelerant.
10. A process for the preparation of a high tenacity prepreg according to any one of claims 6 to 9 comprising impregnating the reinforcing fibres with an epoxy resin matrix and then covering the reinforcing fibres with a toughening layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987515.8A CN112679908A (en) | 2019-10-17 | 2019-10-17 | Prepreg toughening material, high-toughness prepreg and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910987515.8A CN112679908A (en) | 2019-10-17 | 2019-10-17 | Prepreg toughening material, high-toughness prepreg and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112679908A true CN112679908A (en) | 2021-04-20 |
Family
ID=75444486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910987515.8A Pending CN112679908A (en) | 2019-10-17 | 2019-10-17 | Prepreg toughening material, high-toughness prepreg and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112679908A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114670466A (en) * | 2022-04-19 | 2022-06-28 | 中复神鹰(上海)科技有限公司 | Laminate with high post-impact compressive strength and method of making same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376737A (en) * | 2001-03-27 | 2002-10-30 | 北京航空材料研究院 | Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process |
| CN1923506A (en) * | 2006-07-19 | 2007-03-07 | 中国航空工业第一集团公司北京航空材料研究院 | Toughening composite material lamination board and method for making same |
| GB0714224D0 (en) * | 2007-07-20 | 2007-08-29 | Advanced Composites Group Ltd | Thermoset resin fibres |
| CN108137836A (en) * | 2015-09-28 | 2018-06-08 | 东丽株式会社 | The prepreg of resin combination comprising adjustable curing rate |
-
2019
- 2019-10-17 CN CN201910987515.8A patent/CN112679908A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376737A (en) * | 2001-03-27 | 2002-10-30 | 北京航空材料研究院 | Epoxy resin toughened by composite rubber/clay toughening agent and its preparing process |
| CN1923506A (en) * | 2006-07-19 | 2007-03-07 | 中国航空工业第一集团公司北京航空材料研究院 | Toughening composite material lamination board and method for making same |
| GB0714224D0 (en) * | 2007-07-20 | 2007-08-29 | Advanced Composites Group Ltd | Thermoset resin fibres |
| CN108137836A (en) * | 2015-09-28 | 2018-06-08 | 东丽株式会社 | The prepreg of resin combination comprising adjustable curing rate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114670466A (en) * | 2022-04-19 | 2022-06-28 | 中复神鹰(上海)科技有限公司 | Laminate with high post-impact compressive strength and method of making same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794979B (en) | High-compression-strength and high-tensile-ratio carbon fiber composite material and preparation method thereof | |
| US20220347940A1 (en) | Hybrid veil as interlayer in composite materials | |
| EP2799470A1 (en) | Carbon fiber base, prepreg, and carbon-fiber-reinforced composite material | |
| CN111086283B (en) | High-temperature-resistant high-toughness prepreg and preparation method thereof | |
| JP5228853B2 (en) | Epoxy resin composition, fiber reinforced composite material, and production method thereof | |
| CN111087757A (en) | High-temperature-resistant high-toughness prepreg and preparation method and application thereof | |
| CN109749363B (en) | Carbon nanotube toughened high-thermal-conductivity asphalt-based carbon fiber composite material and preparation method thereof | |
| CN111087756A (en) | High-temperature-resistant high-toughness prepreg and preparation method thereof | |
| WO2018181254A1 (en) | Prepreg and fiber reinforced composite material | |
| CN112679908A (en) | Prepreg toughening material, high-toughness prepreg and preparation method thereof | |
| JP2013159618A (en) | Epoxy resin composition, fiber reinforced composite material, and method for producing them | |
| CN112677602B (en) | Toughening material for prepreg, high-toughness composite material and preparation method thereof | |
| CN111320841B (en) | Aramid fiber/carbon nanotube composite reinforced carbon fiber resin prepreg | |
| CN110804281A (en) | Preparation method of graphene-reinforced carbon fiber epoxy prepreg | |
| Studer et al. | Local reinforcement of aerospace structures using co-curing RTM of metal foil hybrid composites | |
| CN114479358A (en) | Prepreg toughening resin, prepreg toughening layer, prepreg, preparation method and application thereof | |
| Charitidis | Criteria for the selection of carbon fiber composite materials for fighter aircraft | |
| EP4112795A1 (en) | Stitched reinforcing fiber base material, preform material, fiber reinforced composite material, and manufacturing methods for same | |
| CN209869584U (en) | Light high-strength unidirectional carbon fiber laminated board | |
| KR101884606B1 (en) | Epoxy resin composition for fiber reinforced composite with high impact resistance and high strength | |
| JP2010059300A (en) | Carbon fiber reinforced composite material and method for producing the same | |
| CN113072795A (en) | Aramid fiber/graphene composite reinforced carbon fiber resin prepreg | |
| CN110951217A (en) | Aramid fiber reinforced carbon fiber resin prepreg and preparation method thereof | |
| CN116023759A (en) | Toughened prepreg | |
| JP2006241308A (en) | Fiber-reinforced composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |