CN107383763B - Preparation method of halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg - Google Patents

Preparation method of halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg Download PDF

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CN107383763B
CN107383763B CN201710633658.XA CN201710633658A CN107383763B CN 107383763 B CN107383763 B CN 107383763B CN 201710633658 A CN201710633658 A CN 201710633658A CN 107383763 B CN107383763 B CN 107383763B
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hot
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prepreg
phenolic
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CN107383763A (en
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栾贻浩
周宇
樊孟金
凌辉
胡亮
蒋文革
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China Academy of Launch Vehicle Technology CALT
Aerospace Research Institute of Materials and Processing Technology
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Aerospace Research Institute of Materials and Processing Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a preparation method of a halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg, which comprises the steps of adopting a reasonable synthesis process, controlling the solid content and the viscosity-temperature flow characteristic of phenolic resin, uniformly mixing the solid phenolic resin and liquid epoxy resin through formula design to obtain a resin system suitable for preparing the prepreg through a hot-melt process, controlling the gelation time of the resin to be 140-250 seconds, preparing a hot-melt resin adhesive film from the hot-melt phenolic resin system, controlling the coating temperature to be 40-65 ℃, and compounding the hot-melt phenolic resin adhesive film and unidirectional fibers or fiber fabrics under the heating and pressurizing conditions to prepare the hot-melt prepreg; the hot-melt prepreg and the composite material have the flame-retardant characteristics of low smoke, no halogen and low smoke toxicity, and meet the service performance requirements of interior trim and structural composite materials for transportation tools such as high-speed rails, airplanes and ships.

Description

Preparation method of halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg
Technical Field
The invention relates to a preparation method of a composite material, in particular to a preparation method of a halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg, belonging to the technical field of preparation of phenolic resin-based composite materials.
Background
Phenolic resin is one of three synthetic thermosetting resins, and is the synthetic resin which is the earliest to realize industrialization in the world. The phenolic resin has a large specific gravity in the industries of industry, agriculture, construction and the like, and the application field of the phenolic resin also relates to the departments of national defense, military industry, traffic and the like. Because of its flame retardant property incomparable with other resins, it is widely used in the industries of airplane, high-speed rail, automobile and building. The use of fiber reinforced phenolic resin based composites is on a growing trend. Taking the increasingly developed rail transit field as an example, in order to achieve the purposes of weight reduction and efficiency increase, composite materials are increasingly adopted, and fiber reinforced phenolic resin matrix composite materials are increasingly applied because the fiber reinforced phenolic resin matrix composite materials can meet relevant requirements of DIN5510, TB/T3139, TB/T3237, EN45545, BS6853 and the like. At present, the preparation of the phenolic resin composite material mostly adopts a prepreg laying process, and the production of the prepreg mainly adopts a wet process. The wet process prepreg has the defects of high volatile matter, low production efficiency, unstable resin content, serious environmental pollution and the like, and the wet process can not meet the increasingly expanded application requirements. In addition, the unidirectional fiber prepreg produced by the wet process has low production efficiency, and the defects of the composite material product are not easy to control. The research on resin system design and hot melting process needs to be developed, and the production process of the phenolic prepreg by the hot melting method is invented to meet the production requirement which is not expanded.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic resin prepreg.
The above purpose of the invention is mainly realized by the following technical scheme:
a preparation method of a halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg comprises the following steps:
(1) adding liquid epoxy resin into the high-solid-content phenolic resin, and uniformly stirring, wherein the solid content of the high-solid-content phenolic resin is more than or equal to 93%, and the viscosity of the high-solid-content phenolic resin is 5000-30000 cp;
(2) adding solid thermosetting resin into the phenolic resin mixed system obtained in the step (1), and uniformly stirring under a heating condition to obtain a hot-melt prepreg resin system; the solid thermosetting resin is phenolic resin, benzoxazine resin or phosphorus-containing epoxy resin;
(3) adopting the hot-melt prepreg resin system to prepare an adhesive film, wherein the coating process conditions are as follows: the temperature is 40-80 ℃, and the coating speed is 3-10 m/min;
(4) impregnating and compounding the adhesive film and unidirectional fibers or fiber fabrics to obtain fiber hot-melt prepreg;
the high-solid-content phenolic resin, the solid thermosetting resin and the liquid epoxy resin comprise the following components in percentage by mass:
85-98% of high-solid-content phenolic resin;
1-10% of solid thermosetting resin;
1-10% of liquid epoxy resin.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the high-solid content phenolic resin is frozen and then crushed in the step (1), the liquid epoxy resin is added into the crushed high-solid content phenolic resin and stirred uniformly, and the stirring conditions are as follows: the temperature is 50-80 ℃, and the stirring time is less than or equal to 2 hours.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the freezing temperature of the high-solid content phenolic resin is-18 to-10 ℃, and the freezing time is more than or equal to 6 hours.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, in the step (2), the heating temperature is 50-80 ℃, and the stirring time is 20-60 min.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the viscosity of the liquid epoxy resin is 6000-15000 cp, and the epoxy value is as follows: 0.7 to 0.9 mol/100 g-1。
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, in the step (4), the impregnation temperature is controlled to be 45-85 ℃, and the impregnation speed is 3-7 m/min.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the unidirectional fiber in the step (4) is glass fiber, quartz fiber or carbon fiber; the weaving mode of the fiber fabric is plain weave, twill weave or satin weave, or the fiber fabric is a uniaxial, biaxial or multiaxial stitch-bonded fabric.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the area density of the fiber fabric is 200-400 g/m2。
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the solid content of the high-solid content phenolic resin in the step (1) is 93-96%.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the gelling time of the high-solid content phenolic resin in the step (1) and the resin system of the hot melt prepreg obtained in the step (2) is 150-300 seconds at 120-180 ℃; and (3) the gelling time of the fiber hot-melt prepreg obtained in the step (4) is 150-300 seconds at the temperature of 120-180 ℃.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the step (3) adopts a hot melt film coating machine, the film coating temperature is 50-65 ℃, the film coating speed is 4-8 m/min, and the surface density of the film is 40-160 g/m2After film forming, the lower surface of the adhesive film is covered with release paper, and the upper surface is covered with a PE film.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot-melt phenolic prepreg, the fiber hot-melt prepreg obtained in the step (4) is subjected to layering and curing to obtain a composite material, wherein the curing process conditions are as follows: the curing temperature is 120-160 ℃, the curing pressure is 0.1-0.8 MPa, and the curing time is 30 min-4 h.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the curing process conditions are as follows: the curing temperature is 125-135 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 2-4 h; or the curing temperature is 145-155 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 30-100 min.
In the preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg, the area density of the fiber hot melt prepreg prepared in the step (4) is 100-800 g/m2The resin content is 30-45%.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the hot-melt prepreg with uniform texture and stable resin content can be obtained through resin synthesis, formula design and process design, the prepreg can be cured at 120-160 ℃, the composite material prepared from the prepreg has the flame-retardant characteristics of low smoke, no halogen and low smoke toxicity, and the obtained composite material has excellent comprehensive performance and can meet the service performance requirements of interior and structural composite materials for transportation vehicles such as high-speed rails, airplanes and ships.
(2) The resin has better film-forming property through formula design and process control, the content of the resin in the prepreg is stable, the deviation of the resin content is +/-3%, the content of volatile matters in the prepreg is less than or equal to 4%, and compared with the currently adopted solution method, the resin content is stable and the volatile matters are obviously reduced.
(3) The invention prepares the prepreg by the hot melting method, has high production efficiency, and relieves the problem of environmental pollution caused by the prepreg by the solution method because the intermediate process does not adopt a solvent.
(4) According to the invention, the viscosity is adjusted by adding the liquid epoxy resin into the high-solid-content phenolic resin obtained after freezing ice crushing, the intrinsic flame-retardant resin is used as a matrix and an additive, the selected components are screened through a large number of tests, the component proportion and the process conditions are optimized, the spreadability and the manufacturability of the resin are obviously improved, and the prepared prepreg has excellent flame-retardant property and can meet the highest-level flame-retardant requirement in standard requirements of DIN5510, EN45545 and the like.
(5) The preparation method has simple process flow, easy realization and stronger practicability;
(6) the invention adopts hot-melt prepregThe flame retardant property of the prepared composite material can meet the requirement of DIN5510-2 standard test, and the combustion grade is as follows: s4, smoke grade is SR2, and drippings grade is ST 2; combustion Smoke toxicity test, conventional toxicity index (CIT) of composite materialsG)≤0.2。
Drawings
FIG. 1 is a schematic diagram of a hot melt prepreg manufacturing process according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the preparation method of the toughness-controllable epoxy resin-based composite material comprises the following steps:
(1) preparing raw materials: the high-solid-content phenolic resin has a resin solid content of more than or equal to 93% and a viscosity of 5000-30000 cp. Freezing the colloidal phenolic resin at-18 to-10 ℃ for more than or equal to 6h, taking out the frozen phenolic resin, and quickly breaking the phenolic resin by a physical method. The solid content of the resin is preferably 93-96%.
Pulverizing solid thermosetting resin at room temperature, wherein the solid thermosetting resin comprises phenolic resin, benzoxazine resin or phosphorus-containing epoxy resin.
(2) And (2) adding the crushed high-solid-content phenolic resin matrix obtained in the step (1) into a reaction kettle with a temperature control device, simultaneously adding low-viscosity and high-activity liquid epoxy resin, stirring at a low speed, stirring and hot melting at the temperature of 50-80 ℃, and stirring for less than or equal to 2 hours to obtain the transparent colloid resin. The liquid epoxy resin is polyfunctional epoxy resin, preferably epoxy resin such as AFG-90, TDE-85, AG-80 and the like in domestic rectification process, has the characteristics of low viscosity and high reaction activity, the viscosity of the liquid epoxy resin is 6000-15000 cp, and the epoxy value is as follows: 0.7 to 0.9 mol/100 g-1。
(3) Adding the solid thermosetting resin powder obtained in the step (1) into the phenolic resin mixed system obtained in the step (2), stirring and mixing under the heating condition of 50-80 ℃, wherein the stirring adopts comprehensive stirring with simultaneous revolution and rotation, and the stirring time is controlled within 20-60 min, so as to obtain the transparent colloid hot-melt prepreg resin system.
(4) Preparing an adhesive film from the hot-melt prepreg resin system obtained in the step (3) by using a hot-melt film coating machine, wherein the film coating process conditions are as follows: the temperature is 40-80 ℃, the speed ratio is 25-40, and the coating speed is 3-10 m/min. After film forming, the lower surface of the adhesive film is covered with release paper, and the upper surface is covered with a PE film. Preferably, the coating temperature is 50-65 ℃, the coating speed is 4-8 m/min, and the surface density of the adhesive film is 40-160 g/m2。
(5) And (3) impregnating and compounding the phenolic resin adhesive film obtained in the step (4) and the unidirectional fiber or the fiber fabric by adopting a hot-melt impregnating machine, placing the hot-melt phenolic adhesive films respectively from top to bottom under the condition of heating by a compression roller, placing the fiber or the fiber fabric in the middle, performing hot-press compounding to obtain the fiber hot-melt prepreg, controlling the temperature of the compression roller to be 45-85 ℃, and controlling the impregnation speed to be 3-7 m/min. The fiber surface density of the hot-melt prepreg can be 100-800 g/m2Adjusting the content within the range, wherein the resin content is adjusted within the range of 30-45%. The gel time of the fiber hot-melt prepreg is 150-300 seconds at 120-180 ℃.
The unidirectional fiber is glass fiber, quartz fiber or carbon fiber; the weaving mode of the fiber fabric is plain weave, twill weave or satin weave, or the fiber fabric is uniaxial, biaxial or multiaxial stitch-bonded fabric. The surface density of the fiber fabric is 200-400 g/m2；
(6) And after the impregnation of the prepreg is finished, storing the prepreg in a refrigeration house for at most 20 days at room temperature.
(7) And when in use, the prepreg is taken out from a refrigeration house, is blanked and laid according to requirements, and is cured according to curing requirements.
(8) Curing the layered prepreg under the conditions of heating and pressurizing, wherein the curing temperature is 120-160 ℃, the curing pressure is 0.1-0.8 MPa, and the curing time is 30 min-4 h. The preferred curing process conditions are: the curing temperature is 125-135 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 2-4 h; or the curing temperature is 145-155 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 30-100 min.
The high solid content liquid phenolic resin, the solid thermosetting resin and the liquid epoxy resin comprise the following components in percentage by mass:
85-98% of high-solid-content liquid phenolic resin;
1-10% of solid thermosetting resin;
1-10% of liquid epoxy resin.
And (3) gelling time of the high-solid-content phenolic resin in the step (1) and the hot-melt prepreg resin system obtained in the step (3) is 150-300 seconds at 120-180 ℃.
The flame retardant property of the composite material prepared by the hot-melt prepreg can meet the requirement of DIN5510-2 standard test, and the combustion grade is as follows: s4, smoke rating SR2, and drippings rating ST 2. Combustion Smoke toxicity test, conventional toxicity index (CIT) of composites prepared with Hot melt prepregG)≤0.2。
Examples 1,
The solid content of the synthetic phenolic resin is 95%, the gel time of the synthetic phenolic resin is 230 seconds, and the following matrix components in percentage by mass are determined:
92% of phenolic resin;
5 percent of solid phenolic resin
3 percent of liquid epoxy resin
The reinforcing fiber is: t700 grade carbon fiber
Step one, storing the colloidal phenolic resin for 10h at the temperature of-15 ℃, taking out the colloidal phenolic resin, and breaking the colloidal phenolic resin. The solid phenolic resin is crushed.
And (II) putting the phenolic resin and the liquid epoxy resin into a temperature-controlled reaction kettle, stirring at a low speed, and stirring for hot melting at 60 ℃ for 1.5 hours to obtain a transparent colloid.
And (III) adding solid phenolic resin, and stirring and mixing the solid phenolic resin and the phenolic resin for 20min under the heating condition of 70 ℃ to obtain the finished resin.
Step four, putting the obtained finished product resin mixture into a film coating machine, coating at the temperature of 50-60 ℃, adjusting the coating speed to be 6m/min and the speed ratio to be 28, and obtaining a hot melt adhesive film with the adhesive film surface density of 67g/m2。
And (V) performing impregnation compounding on the phenolic resin adhesive film and the T700-grade carbon fiber, wherein the impregnation temperature is controlled to be 45-55 ℃, and the impregnation speed is 5 m/min. Obtaining the carbon fiber unidirectional hot-melt prepreg, wherein the fiber surface density of the carbon fiber unidirectional hot-melt prepreg tape is 200 +/-5 g/m2And testing the resin content in the prepreg to be 39-41%.
And step six, laying the obtained prepreg according to the design requirement.
And step seven, curing and molding the layered prepreg by adopting an autoclave, wherein the curing temperature is 130 ℃, the curing pressure is 0.3MPa, the heating rate is 1 ℃/min, and the temperature is kept for 2h after the temperature reaches 130 ℃.
And (eight), testing the composite material test board obtained after curing according to the standard requirement of DIN5510-2, wherein the combustion grade is as follows: s4, smoke rating SR2, and drippings rating ST 2. Toxicity index (CIT)G) Is 0.03.
Example 2
The solid content of the synthetic phenolic resin is 96%, the gel time of the synthetic phenolic resin is tested to be 170 seconds, and the synthetic phenolic resin is determined to comprise the following matrix components in percentage by mass:
95% of phenolic resin;
3 percent of solid phosphorus-containing epoxy resin
2 percent of liquid epoxy resin
The reinforcing fiber is: EW200 glass fiber cloth
Step one, storing the colloidal phenolic resin for 24h at the temperature of-15 ℃, taking out the colloidal phenolic resin, and breaking the colloidal phenolic resin. The solid phosphorous epoxy resin is crushed.
And (II) putting the phenolic resin and the liquid epoxy resin into a temperature-controlled reaction kettle, stirring at a low speed, and stirring for hot melting at 70 ℃ for 1h to obtain the transparent colloid.
And (III) adding solid phosphorus-containing epoxy resin, and stirring and mixing the solid phosphorus-containing epoxy resin and phenolic resin for 30min under the heating condition of 80 ℃ to obtain the finished resin.
Step four, putting the obtained finished product resin mixture into a film coating machine, coating at the temperature of 45-55 ℃, and adjusting the coating speed to be 5m/min and the speed ratio according to actual conditions28, obtaining a hot melt adhesive film with the surface density of 54g/m2。
And (V) compounding the phenolic resin adhesive film and the EW200 glass fiber fabric under the heating and pressurizing conditions by using impregnation equipment, controlling the impregnation temperature to be 45-55 ℃, and controlling the impregnation speed to be 4m/min to obtain the glass fiber cloth hot-melt prepreg, wherein the fiber surface density of the hot-melt prepreg is 200 +/-10 g/m2And testing the resin content in the prepreg to be 34-36%.
And step six, laying the obtained prepreg according to the design requirement.
And step seven, curing and molding the layered prepreg by adopting an autoclave, wherein the curing temperature is 130 ℃, the curing pressure is 0.3MPa, the heating rate is 1 ℃/min, and the temperature is kept for 2h after the temperature reaches 130 ℃.
And (eight), testing the composite material test board obtained after curing according to the standard requirement of DIN5510-2, wherein the combustion grade is as follows: s4, smoke rating SR2, and drippings rating ST 2.
The tensile strength of the composite material is: 450MPa, compressive strength 380 MPa: the bending strength is: 570MPa, interlaminar shear strength: 55 MPa.
Example 3
The solid content of the synthetic phenolic resin is 94%, the gel time of the synthetic phenolic resin is tested to be 200 seconds, and the base component comprising the following mass percentage contents is determined:
96% of phenolic resin;
2 percent of liquid epoxy resin
2% of solid benzoxazine resin
The reinforcing fiber is: biaxial glass fiber stitch-bonded fabric having an areal density of 400g/m2。
Step one, storing the colloidal phenolic resin for 24h at the temperature of-15 ℃, taking out the colloidal phenolic resin, and breaking the colloidal phenolic resin. The solid phenolic resin is crushed.
And (II) putting the phenolic resin and the liquid epoxy resin into a temperature-controlled reaction kettle, stirring at a low speed, and stirring for hot melting at 60 ℃ for 1.5 hours to obtain a transparent colloid.
And (III) adding solid benzoxazine resin, and stirring and mixing the solid benzoxazine resin and the phenolic resin for 30min under the heating condition of 70 ℃ to obtain the finished resin.
Putting the obtained finished resin mixture into a film coating machine, coating at 40-50 ℃, adjusting the coating speed to 5m/min and the speed ratio to 30 to obtain a hot melt adhesive film with the adhesive film surface density of 134g/m2。
And (V) carrying out impregnation compounding on the phenolic resin adhesive film and the biaxial glass fiber stitch-bonded fabric, controlling the impregnation temperature to be 60-65 ℃ and the impregnation speed to be 6m/min, so as to obtain the biaxial stitch-bonded fabric hot-melt prepreg, wherein the surface density of the hot-melt prepreg is 400 +/-5 g/m2And testing the resin content in the prepreg to be 40-41%.
And step six, laying the obtained prepreg according to the design requirement.
And step seven, curing and molding the layered prepreg by adopting an autoclave, wherein the curing temperature is 150 ℃, the curing pressure is 0.3MPa, the heating rate is 1 ℃/min, and the temperature is kept for 0.5h after the temperature reaches 150 ℃.
And (eight), testing the composite material test board obtained after curing according to the standard requirement of DIN5510-2, wherein the combustion grade is as follows: s4, smoke rating SR2, and drippings rating ST 2. Toxicity index (CIT)G) Is 0.02.
The above description is only for the best mode of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Those skilled in the art will appreciate that the invention may be practiced without these specific details.

Claims (14)

1. A preparation method of a halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg is characterized by comprising the following steps: the method comprises the following steps:
(1) adding liquid epoxy resin into the high-solid-content phenolic resin, and uniformly stirring, wherein the solid content of the high-solid-content phenolic resin is more than or equal to 93%, and the viscosity of the high-solid-content phenolic resin is 5000-30000 cp;
(2) adding solid thermosetting resin into the phenolic resin mixed system obtained in the step (1), and uniformly stirring under a heating condition to obtain a hot-melt prepreg resin system; the solid thermosetting resin is phenolic resin, benzoxazine resin or phosphorus-containing epoxy resin;
(3) adopting the hot-melt prepreg resin system to prepare an adhesive film, wherein the coating process conditions are as follows: the temperature is 40-80 ℃, and the coating speed is 3-10 m/min;
(4) impregnating and compounding the adhesive film and unidirectional fibers or fiber fabrics to obtain fiber hot-melt prepreg;
the high-solid-content phenolic resin, the solid thermosetting resin and the liquid epoxy resin comprise the following components in percentage by mass:
85-98% of high-solid-content phenolic resin;
1-10% of solid thermosetting resin;
1-10% of liquid epoxy resin.
2. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: freezing and crushing the high-solid-content phenolic resin in the step (1), adding the liquid epoxy resin into the crushed high-solid-content phenolic resin, and uniformly stirring, wherein the stirring conditions are as follows: the temperature is 50-80 ℃, and the stirring time is less than or equal to 2 hours.
3. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 2, characterized in that: the freezing temperature of the high solid content phenolic resin is-18 to-10 ℃, and the freezing time is more than or equal to 6 hours.
4. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: in the step (2), the heating temperature is 50-80 ℃, and the stirring time is 20-60 min.
5. The halogen-free, flame retardant, low smoke, low toxic heat of claim 1The preparation method of the fused phenolic prepreg is characterized by comprising the following steps: the viscosity of the liquid epoxy resin is 6000-15000 cp, and the epoxy value is as follows: 0.7 to 0.9 mol/100 g-1。
6. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: in the step (4), the impregnation temperature is controlled to be 45-85 ℃, and the impregnation speed is 3-7 m/min.
7. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: the unidirectional fiber in the step (4) is glass fiber, quartz fiber or carbon fiber; the weaving mode of the fiber fabric is plain weave, twill weave or satin weave, or the fiber fabric is a uniaxial, biaxial or multiaxial stitch-bonded fabric.
8. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 7, characterized by comprising the following steps: the surface density of the fiber fabric is 200-400 g/m2。
9. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: the high-solid-content phenolic resin in the step (1) has a resin solid content of 93-96%.
10. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: the gel time of the high-solid-content phenolic resin in the step (1) and the hot-melt prepreg resin system obtained in the step (2) is 150-300 seconds at 120-180 ℃; and (3) the gelling time of the fiber hot-melt prepreg obtained in the step (4) is 150-300 seconds at the temperature of 120-180 ℃.
11. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 1, which is characterized by comprising the following steps: the step (3) adoptsThe hot-melt film coating machine has the film coating temperature of 50-65 ℃, the film coating speed of 4-8 m/min and the surface density of 40-160 g/m2After film forming, the lower surface of the adhesive film is covered with release paper, and the upper surface is covered with a PE film.
12. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to any one of claims 1 to 11, which is characterized by comprising the following steps: laying and curing the fiber hot-melt prepreg obtained in the step (4) to obtain the composite material, wherein the curing process conditions are as follows: the curing temperature is 120-160 ℃, the curing pressure is 0.1-0.8 MPa, and the curing time is 30 min-4 h.
13. The method for preparing the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to claim 12, characterized in that: the curing process conditions are as follows: the curing temperature is 125-135 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 2-4 h; or the curing temperature is 145-155 ℃, the curing pressure is 0.3-0.6 MPa, and the curing time is 30-100 min.
14. The preparation method of the halogen-free flame-retardant low-smoke low-toxicity hot melt phenolic prepreg according to any one of claims 1 to 11, which is characterized by comprising the following steps: the area density of the fiber hot-melt prepreg prepared in the step (4) is 100-800 g/m2The resin content is 30-45%.
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