CN111086283B - High-temperature-resistant high-toughness prepreg and preparation method thereof - Google Patents

High-temperature-resistant high-toughness prepreg and preparation method thereof Download PDF

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Publication number
CN111086283B
CN111086283B CN201811235197.1A CN201811235197A CN111086283B CN 111086283 B CN111086283 B CN 111086283B CN 201811235197 A CN201811235197 A CN 201811235197A CN 111086283 B CN111086283 B CN 111086283B
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epoxy resin
resin
prepreg
thermoplastic resin
toughening layer
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CN111086283A (en
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余荣禄
张藕生
唐建华
杨文刚
王芳
姚斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/40—Weight reduction

Abstract

The invention relates to a high-temperature-resistant high-toughness prepreg and a preparation method thereof, which mainly solve the problems of poor process operability and poor carbon fiber impregnation effect of a thermoplastic resin toughened epoxy resin matrix for the prepreg by a hot melting method, and the high-temperature-resistant high-toughness prepreg comprises the following components by 100 percent of total mass: epoxy resin matrix: 22-35%; reinforcing fibers: 50-70%; a toughening layer: 8-15%; characterized in that the epoxy resin matrix consists of at least one of the combinations comprising epoxy resin, soluble thermoplastic resin and curing agent; the toughening layer is composed of at least one of the combination of epoxy resin, soluble thermoplastic resin and insoluble thermoplastic resin, and the toughening layer is positioned on one side of the reinforced fiber layer with the epoxy resin matrix, so that the problem is solved well, and the method can be used for preparing various carbon fiber composite material main load-bearing structural members.

Description

High-temperature-resistant high-toughness prepreg and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-temperature-resistant high-toughness prepreg and a preparation method thereof.
Background
The advanced resin-based composite material taking high-performance fibers such as carbon fibers, aramid fibers and the like as reinforcing materials is a light high-strength structural material preferred for a bearing structural member, is widely applied to the fields of aerospace, military industry, light weight of automobiles and the like, and has increasingly increased application proportion. One of the main performance indexes of the advanced resin-based composite material for the main load-bearing structural member is the compression strength after impact (CAI) which is used for representing the low-speed impact damage resistance of the composite material. BMS8-276 standard proposed by Boeing requires that the CAI of the composite material for the main bearing structure of the civil should reach 310 MPa. Therefore, improving the CAI of composite materials has been a research focus in this field.
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 (CN200610099381.9) 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 technology achieves better toughening effect, other problems are brought to the same time, such as loss of interlayer rigidity and viscosity of the prepreg caused by 'off-site toughening', reduction of volume content of reinforced fibers caused by a multi-layer toughening structure, and further influence on mechanical strength of the composite material.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the viscosity of a thermoplastic resin toughened resin matrix is high, the preparation difficulty is high, the impregnation effect is poor, the compression strength of a prepreg laminated board after impact is low, and the performance requirement of a main bearing structural member is difficult to meet.
The second technical problem to be solved by the present invention is to provide a method for preparing a high temperature resistant and high toughness prepreg corresponding to the first technical problem.
The third technical problem to be solved by the present invention is to provide an application of the high temperature resistant and high toughness prepreg corresponding to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a high-temperature-resistant high-toughness prepreg comprises the following components by the total mass of 100 percent:
epoxy resin matrix: 22-35%;
reinforcing fibers: 50-70%;
toughening layer: 8-15%;
the epoxy resin matrix is composed of at least one of a combination containing an epoxy resin, a soluble thermoplastic resin and a curing agent; the toughening layer is composed of at least one of the combination of epoxy resin, soluble thermoplastic resin and insoluble thermoplastic resin, and is positioned on one side of the reinforced fiber layer with the epoxy resin matrix.
In the above technical solution, the epoxy resin in the epoxy resin matrix and the epoxy resin in the toughening layer are the same or different, and are independently selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, and glycidyl amine epoxy resin.
In the above technical scheme, the curing agent is at least one of diaminodiphenyl sulfone or derivatives and isomers thereof, such as substituents containing alkyl, halogen and the like on a benzene ring.
In the technical scheme, the soluble thermoplastic resin is one or more than two of polyether sulfone, polyetherimide, polyether ether ketone, polysulfone and other thermoplastic resins.
In the above technical solution, the insoluble thermoplastic resin is polyamide; the particle size D90 of the polyamide is preferably not more than 10 μm.
In the technical scheme, the epoxy resin matrix further comprises a latent accelerator; the latent accelerator is preferably a boron-amine complex or a passivated imidazole.
In the technical scheme, the high-temperature-resistant high-toughness prepreg comprises, by mass, 100 parts of epoxy resin, 0-15 parts of soluble thermoplastic resin and 22-55 parts of curing agent; the toughening layer contains 100 parts of epoxy resin, 0-25 parts of soluble thermoplastic resin and 0-25 parts of insoluble thermoplastic resin.
In the technical scheme, the reinforcing fiber is at least one of carbon fiber, aramid fiber, glass fiber, basalt fiber and the like; the reinforcing fiber is in the form of continuous unidirectional fiber or fabric;
in order to solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a high temperature resistant and high toughness prepreg according to any one of the above technical solutions to solve the technical problems, comprising the steps of:
a) preparation of epoxy resin matrix: dissolving a required amount of soluble thermoplastic resin in epoxy resin, cooling, and adding a curing agent to obtain an epoxy resin matrix;
b) preparing a resin adhesive film: uniformly coating an epoxy resin matrix on the surface of release paper on a hot-melt film coating machine to obtain a resin film;
c) preparing a toughening layer: dissolving soluble thermoplastic resin in epoxy resin to obtain uniform and transparent melt, cooling to below 120 ℃, adding insoluble thermoplastic resin powder, stirring uniformly, and uniformly coating the mixture on release paper on a hot-melt film coating machine;
d) preparing a prepreg: on a pre-dipping machine provided with a plurality of groups of winding and unwinding stations, firstly, dipping the reinforced fibers by the resin adhesive film, and then covering the reinforced fiber layer with the toughening layer to obtain the high-temperature-resistant high-toughness prepreg.
In the technical scheme, in the step d), the toughening layer is covered on the reinforcing fiber layer, preferably the PE film is covered, and then the prepreg is rolled to obtain the high-temperature-resistant high-toughness prepreg.
In order to solve the second technical problem, the invention adopts the following technical scheme: use of a high temperature resistant, high tenacity prepreg according to any of the above solutions to one of the above problems.
In the above technical scheme, the application is not particularly limited, and a person skilled in the art can apply the prepreg of the present invention according to the existing process technology, for example, the prepreg is applied to a light high-strength structural material and widely applied to many fields such as aerospace, military industry, automobile weight reduction, etc.
The invention also comprises the application of the prepreg prepared by the technical scheme.
The high-temperature-resistant high-toughness prepreg and the preparation method thereof have the advantages that:
1) the resin matrix only contains a proper amount of or is not added with a thermoplastic resin toughening agent, and other toughening agents cover the surface of the prepreg in a toughening layer form, so that the resin matrix is ensured to have a good impregnation effect on the reinforced fibers;
2) except that the toughening layer does not contain a curing agent, the components of the toughening layer and the resin matrix are the same, but the content of the thermoplastic resin is higher, and under the action of heating, pressurizing and concentration difference, mutual diffusion of the components occurs between the toughening layer and the resin matrix, so that a good interface effect is ensured between the toughening layer and the fiber layer impregnated by the resin matrix.
3) Most of the thermoplastic resin is limited in an interlayer area through the toughening layer, so that the interlayer toughness and CAI of the composite material are improved.
By adopting the technical scheme of the invention, the prepared high-temperature-resistant high-toughness prepreg realizes good impregnation of the reinforcing fibers, obviously improves the compression strength of the laminated board after impact, and obtains better technical effects.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Preparation of fiber with areal density of 125g/m by Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
thermoplastic resin toughening epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 65 wt.%
A toughening layer: 10% by weight
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 16.5 portions
4, 4' -diaminodiphenyl sulfone: 49 parts by weight of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to 80 ℃ after PES is completely dissolved, adding 4, 4' -diaminodiphenyl sulfone powder, and uniformly mixing.
Preparing a resin adhesive film: and 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 gel film surface is 24g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 17.6 parts
Polyamide 12 particles (Orgasol 2001 UD): 21.3 parts of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to below 120 ℃ after PES is completely dissolved, adding the Orgasol2001, uniformly stirring, discharging, and cooling to room temperature.
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 130 ℃ to obtain the surface density of 19.2g/m2The toughening layer.
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. The temperatures of the first heating roller, the second heating roller, the third heating roller and the heating plate of the pre-soaking machine are all 110 ℃.
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 panels were tested for post impact compressive strength according to the standard.
[ examples 2 to 3 ]
The difference from example 1 is that examples 2 and 3 respectively replace the thermoplastic resin with polyetherimide (Ultem1010, Sabic) and polyetheretherketone (VICTREX 90P).
[ examples 4 to 6 ]
The difference from the embodiment 1 is that the carbon fibers in the embodiments 4 to 6 are respectively replaced by Shanghai petrochemical SCF 35S-12k, Toray T800S-24k and Toray T800H-12 k.
[ example 7 ]
Preparation of a fiber with an areal density of 150g/m using Toray T800s X24 k carbon fiber2The prepreg of (a), which consists of:
thermoplastic resin toughening epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 65 wt.%
A toughening layer: 10% by weight
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 40 portions of
5, 5-dimethyl hydantoin epoxy (MHR-070, Hubei stannate corporation): 30 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 19.8 parts of
3, 3' -diaminodiphenyl sulfone: 45.6 parts
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MHR-070 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to 80 ℃ after PES is completely dissolved, adding 4, 4' -diaminodiphenyl sulfone powder, and uniformly mixing.
Preparing a resin adhesive film: and 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 gel film surface is 28.5g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 40 portions of
5, 5-dimethyl hydantoin epoxy resin (MHR-070, Hubei stanna corporation): 30 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 17.6 parts
Polyamide 12 particles (Orgasol 2001 UD): 19.4 parts of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MHR-070 and CYD128 epoxy resin, stirring and heating to 180 ℃ under the protection of nitrogen, cooling to below 120 ℃ after PES is completely dissolved, adding the Orgasol2001, uniformly stirring, discharging, and cooling to room temperature.
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 130 ℃ to obtain the surface density of 23.8g/m2The toughening layer of (1).
The prepreg and laminate preparation process was the same as in example 1.
[ example 8 ]
Preparation of a fiber with an areal density of 150g/m using Toray T800S X24 k carbon fiber2The prepreg of (a), which consists of:
thermoplastic resin toughening epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 65 wt.%
A toughening layer: 10% by weight
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
trifunctional epoxy resin (MY0510, Huntsman corporation): 30 portions of
5, 5-dimethyl hydantoin epoxy resin (MHR-070, Hubei stanna corporation): 30 portions of
Bisphenol F epoxy resin (DER 354, DOW): 40 portions of
Polyethersulfone (5003P, sumitomo, japan): 25.7 parts of
4, 4' -diaminodiphenyl sulfone: 45.8 portions of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of MY0510, MHR-070 and DER 354 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to 80 ℃ after PES is completely dissolved, adding 4, 4' -diaminodiphenyl sulfone powder, 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 gel film surface is 28.5g/m2。
2) Preparation of toughening layer
The formula of the toughening layer resin comprises the following components:
trifunctional epoxy resin (MY0510, Huntsman corporation): 30 portions of
5, 5-dimethyl hydantoin epoxy (MHR-070, Hubei stannate corporation): 30 portions of
Bisphenol F epoxy resin (DER 354, DOW): 40 portions of
Polyethersulfone (5003P, sumitomo, japan): 17.6 parts
Polyamide 12 particles (Orgasol 2001 UD): 25.2 parts of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of MY0510, MHR-070 and DER 354 epoxy resin, stirring and heating to 180 ℃ under the protection of nitrogen, cooling to below 120 ℃ after PES is completely dissolved, discharging and cooling to room temperature.
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 130 ℃ to obtain the surface density of 23.8g/m2The toughening layer of (1).
The prepreg and laminate preparation process was the same as in example 1.
[ COMPARATIVE EXAMPLE 1 ]
Preparation of fiber with areal density of 125g/m by Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
thermoplastic resin toughening epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 65 wt.%
Toughening layer: 10% by weight
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 16.5 portions of
4, 4' -diaminodiphenyl sulfone: 49 parts of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to 80 ℃ after PES is completely dissolved, adding 4, 4' -diaminodiphenyl sulfone powder, 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 gel film surface is 24g/m2。
2) Preparation of toughening layer
The formula of the toughening layer resin comprises the following components:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 38.9 portions
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, discharging after PES is completely dissolved, and naturally cooling to room temperature.
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 130 ℃ to obtain the surface density of 19.2g/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. The temperatures of the first heating roller, the second heating roller, the third heating roller and the heating plate of the pre-soaking machine are all 110 ℃.
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 panels were tested for post impact compressive strength according to the standard.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of fiber with areal density of 125g/m by Toray T700X 12k carbon fiber2The prepreg of (a), which consists of:
thermoplastic resin toughening epoxy resin matrix: 25 wt.%
T700 × 12k carbon fiber: 65 wt.%
A toughening layer: 10% by weight
1) Preparation of resin adhesive film
The formula of the resin matrix comprises:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barlingite): 30 portions of
Polyethersulfone (5003P, sumitomo, japan): 16.5 portions
4, 4' -diaminodiphenyl sulfone: 49 parts by weight of
The mixing process comprises the following steps: adding the polyether sulfone 5003P into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 150 ℃ under the protection of nitrogen, cooling to 80 ℃ after PES is completely dissolved, adding 4, 4' -diaminodiphenyl sulfone powder, and uniformly mixing.
Preparing a resin adhesive film: and 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 gel film surface is 24g/m2。
2) Preparation of toughening layer
The toughening layer resin comprises the following components in formula:
tetrafunctional epoxy resin (XB 9721, Huntsman corporation): 50 portions of
Trifunctional epoxy resin (MY0510, Huntsman corporation): 20 portions of
Bisphenol a epoxy resin (CYD128, barnyard petrochemical): 30 portions of
Polyamide 12 particles (Orgasol 2001 UD): 38.9 portions
The mixing process comprises the following steps: adding polyamide Orgasol2001 particles into a mixture of XB 9721, MY0510 and CYD128 epoxy resin, stirring and heating to 90 ℃ under the protection of nitrogen, uniformly stirring, discharging, and cooling to room temperature.
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 130 ℃ to obtain the surface density of 19.2g/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. The temperatures of the first heating roller, the second heating roller, the third heating roller and the heating plate of the pre-soaking machine are all 110 ℃.
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 panels were tested for post impact compressive strength according to the standard.
Attached table 1
Figure BDA0001838034390000101

Claims (12)

1. The high-temperature-resistant high-toughness prepreg comprises the following components in percentage by mass of 100 percent:
epoxy resin matrix: 22-35%;
reinforcing fibers: 50-70%;
a toughening layer: 8-15%;
the epoxy resin is characterized in that the epoxy resin matrix comprises 100 parts by mass of epoxy resin, 0-15 parts by mass of soluble thermoplastic resin and 22-55 parts by mass of curing agent; the toughening layer contains 100 parts of epoxy resin, more than 0 part and less than or equal to 25 parts of soluble thermoplastic resin and more than 0 part and less than or equal to 25 parts of insoluble thermoplastic resin; the toughening layer is positioned on one side of the reinforced fiber layer with the epoxy resin matrix.
2. The high temperature resistant, high toughness prepreg according to claim 1, characterized in that the epoxy resin in said epoxy resin matrix and the epoxy resin in said toughening layer are the same or different and are independently selected from at least one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine epoxy resin.
3. High temperature resistant, high tenacity prepreg according to claim 1, characterized in that the curing agent is diaminodiphenyl sulfone or its derivatives, isomers.
4. The high temperature resistant and high toughness prepreg according to claim 3, wherein when the curing agent is a derivative of diaminodiphenyl sulfone, the benzene ring of diaminodiphenyl sulfone contains at least one of alkyl and halogen.
5. The high temperature resistant high tenacity prepreg according to claim 1, characterized in that said soluble thermoplastic resin is one or more than two of polyethersulfone, polyetherimide, polyetheretherketone, polysulfone.
6. High temperature resistant, high tenacity prepreg according to claim 1, characterized in that said insoluble thermoplastic resin is polyamide.
7. High temperature resistant, high tenacity prepreg according to claim 6, characterized in that the particle size D90 of said polyamide is not more than 10 μm.
8. The high temperature resistant, high toughness prepreg according to claim 1, characterized in that said epoxy resin matrix further comprises a latent accelerator.
9. The high temperature resistant, high toughness prepreg according to claim 8, characterized in that said latent accelerator is a boron-amine complex or passivated imidazole.
10. The high temperature resistant, high tenacity prepreg according to claim 1, characterized in that said reinforcing fibers are at least one of carbon fibers, aramid fibers, glass fibers, basalt fibers, and the like; the reinforcing fibers are in the form of continuous unidirectional fibers or a fabric.
11. A preparation method of the high temperature resistant and high toughness prepreg according to any one of claims 1 to 10, comprising the following steps:
a) preparation of epoxy resin matrix: dissolving a required amount of soluble thermoplastic resin in epoxy resin, cooling, and adding a curing agent to obtain an epoxy resin matrix;
b) preparing a resin adhesive film: uniformly coating the epoxy resin matrix on the surface of release paper on a hot-melt method coating machine to obtain a resin adhesive film;
c) preparing a toughening layer: dissolving soluble thermoplastic resin in epoxy resin to obtain uniform and transparent melt, cooling to below 120 ℃, adding insoluble thermoplastic resin powder, stirring uniformly, and uniformly coating the mixture on release paper on a hot-melt film coating machine;
d) preparing a prepreg: on a pre-dipping machine provided with a plurality of groups of winding and unwinding stations, firstly, dipping the reinforced fibers by the resin adhesive film, and then covering the reinforced fiber layer with the toughening layer to obtain the high-temperature-resistant high-toughness prepreg.
12. Use of a prepreg according to any one of claims 1 to 10.
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