CN114656748A - Phenolic resin composition, preparation method thereof and application thereof in preparation of stamping die - Google Patents
Phenolic resin composition, preparation method thereof and application thereof in preparation of stamping die Download PDFInfo
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- CN114656748A CN114656748A CN202210565956.0A CN202210565956A CN114656748A CN 114656748 A CN114656748 A CN 114656748A CN 202210565956 A CN202210565956 A CN 202210565956A CN 114656748 A CN114656748 A CN 114656748A
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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
- C08L61/14—Modified phenol-aldehyde condensates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/01—Selection of materials
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
Abstract
The invention belongs to the field of polymer composite materials, and particularly relates to a phenolic resin composition, a preparation method thereof and application thereof in preparing a stamping die. The composition comprises, by mass, 10-40 parts of modified phenolic resin, 10-40 parts of styrene butadiene rubber, 5-12 parts of iron powder, 6-8 parts of carbon-based material, 7-13 parts of non-ferrous metal powder, 0.2-3 parts of metal oxide, 10-13 parts of modified basalt fiber and 2.4-5.3 parts of dispersant. The phenolic resin composition, the preparation method and the application thereof provided by the invention creatively combine and reinforce the polyimide modified phenolic resin by various reinforcing phases, comprehensively utilize the reinforcing characteristics and the synergistic reinforcing effect of various reinforcing phases and improve the comprehensive performance of a high polymer composite material.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a phenolic resin composition, a preparation method thereof and application thereof in preparing a stamping die.
Background
With the vigorous development of the global automobile industry, a plurality of automobile enterprises need continuous innovation, the shorter the period of a finished automobile manufacturing enterprise for launching a new automobile type is, and the faster the market brand is occupied. Whether a new vehicle type is released or an original vehicle type is transformed and upgraded, the automobile product needs to be trial-manufactured so as to visually reflect whether the appearance, the shape, the size reasonability and the quality of the whole automobile are qualified. After the design engineer finishes designing the appearance and the automobile parts, the sample car is required to be manufactured according to design data, the defects of the sample car are excavated through test evaluation so as to change the design, then the next sample car is prepared, and after the trial manufacture and the test evaluation of a plurality of sample cars, the design and the sizing as well as the batch production of new car types can be carried out. In the trial-manufacturing process of the sample car, a large number of stamping dies are needed to complete the stamping and forming of sheet metal parts (for example, parts such as automobile bodies and chassis) by applying external force to the sheet metal through the dies and the press machine to obtain the required shape and size, so the importance of the stamping dies in the trial-manufacturing of the sample car is self-evident. In order to shorten the development period and cost of sample vehicle trial production and improve the competitiveness and timeliness of automobile products, the rapid die technology is widely concerned by people. The Rapid Tooling technology (Rapid Tooling-RT) is a new method and a new process for rapidly manufacturing a mold, which are evolved from the Rapid Prototyping technology (Rapid Tooling-RP). However, the method is limited by the defects of high material price, high pollution and energy consumption in the preparation process, long processing period and the like of the traditional ferrous metal (such as cast iron and cast steel) system mold, the traditional sample vehicle trial-manufacturing mold becomes a bottleneck limiting the development of the sample vehicle trial-manufacturing technology in the development process of new vehicle types in the automobile industry, and the requirements of low cost, short period, energy conservation and environmental protection in the existing sample vehicle trial-manufacturing field cannot be met; meanwhile, the existing ferrous metal mold material cannot meet the use requirements of high-standard, high-utilization rate, high-efficiency, multi-class and personalized molds of medium and large-sized enterprises, and cannot be matched with the molding performance of automobile parts made of materials such as aluminum alloy, magnesium alloy and the like, so that the product stamping molding quality is poor. Therefore, it is urgently needed to develop a prototype press mold and a matching technology thereof, and the development trends of green manufacturing, short cycle, multiple varieties and low cost in the automobile manufacturing industry (particularly in the field of new energy automobiles) are followed from mold materials, mold design to mold manufacturing. Under this background, the novel polymer composite material is developed and used for the stamping die required by the trial production of the sample car, so that the die manufacturing time is shortened, the die manufacturing cost is reduced, and the die manufacturing precision is improved, and the novel polymer composite material has the unique advantages of light weight, corrosion resistance, shock resistance, wear resistance, energy conservation, environmental protection and the like, and is highly consistent with the use demand of the trial production field of the sample car for the stamping die.
The phenolic resin is a kind of synthetic resin prepared by the addition polycondensation reaction of phenolic compounds and aldehyde compounds, and is one of the earliest used varieties and the largest used amount in high polymer materials. However, the phenolic resin has low production efficiency due to high temperature and long curing time required for curing, and the phenolic resin has high brittleness, poor toughness and poor mechanical property, thereby seriously restricting the wider application of the phenolic resin. Therefore, the phenolic resin with poor comprehensive performance cannot be directly applied to a sample car trial-manufacture stamping die material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a phenolic resin composition, a preparation method thereof and application thereof in preparing a stamping die.
In order to achieve the purpose, the invention adopts the technical scheme that:
according to the first aspect, the invention provides a phenolic resin composition which comprises, by mass, 10-40 parts of modified phenolic resin, 10-40 parts of styrene butadiene rubber, 5-12 parts of iron powder, 6-8 parts of carbon-based material, 7-13 parts of non-ferrous metal powder, 0.2-3 parts of metal oxide, 10-13 parts of modified basalt fiber and 2.4-5.3 parts of dispersing agent.
In alternative embodiments, the carbon-based material is selected from carbon nanotubes and/or carbon fibers; the non-ferrous metal powder is selected from at least one of Zr, Ni or Cu; the metal oxide is Al2O3、TiO2、Ni2O3、Fe3O2Or CoO.
In an optional embodiment, the modified phenolic resin is a polyimide modified phenolic resin, and the mass ratio of the phenolic resin to the polyimide in the polyimide modified phenolic resin is 1: 0.125-2.
In an alternative embodiment, the iron powder is selected from reduced iron powder and/or electrolytic iron powder, and the mesh number of the iron powder is selected from 800 to 1600 meshes.
Preferably, the iron powder comprises 2-4 parts of 1600-mesh electrolytic iron powder, 1-3 parts of 1600-mesh reduced iron powder and 2-5 parts of 800-mesh reduced iron powder.
In an optional embodiment, the modified basalt fiber is composite nano SiO2The basalt fiber, the composite nano SiO2Among the basalt fibers, basalt fibers and nano SiO2The mass ratio of (A) to (B) is 8-12: 1.
In an alternative embodiment, the carbon-based material comprises carbon fibers or carbon nanotubes, preferably copper-coated carbon fibers.
The invention also provides application of the composition of any one of the previous embodiments in preparing a stamping die, wherein the stamping die is an automobile die.
The present invention also provides a method of preparing a composition according to any one of the preceding embodiments, comprising the steps of: weighing the components according to the formula ratio, sequentially adding styrene butadiene rubber and a dispersing agent into the modified phenolic resin, and uniformly mixing to obtain a mixed solution A; mixing iron powder, a carbon-based material, non-iron metal powder, a metal oxide and modified basalt fiber to obtain a mixture B; and adding the mixture B into the mixed solution A, uniformly mixing and cooling to obtain the phenolic resin composition.
In an optional embodiment, the modified phenolic resin is a polyimide modified phenolic resin, and the preparation method of the polyimide modified phenolic resin comprises the following steps of weighing the phenolic resin and the polyimide in a mass ratio of 1: 0.125-2, uniformly mixing the weighed phenolic resin and the polyimide at 90-100 ℃ by primary stirring, adding a curing agent at 100 ℃ and uniformly mixing the mixture by secondary stirring to obtain the polyimide modified phenolic resin.
Preferably, the stirring speed of the primary stirring and uniform mixing and the secondary stirring and uniform mixing is 300-500 r/min.
In an alternative embodiment, the modified basalt fibers comprise composite nano-SiO2The basalt fiber, the composite nano SiO2The preparation method of the basalt fiber comprises the steps of weighing the basalt fiber and the nano SiO according to the mass ratio of 8-12: 12 Nano SiO 22Mixing the hydroxylated surface silicon with a polyurethane aqueous solution to obtain slurry, and leaching basalt fibers by using the slurry to obtain the composite nano SiO2The basalt fiber.
In an optional embodiment, the carbon-based material is copper-plated carbon fiber, and the preparation method of the copper-plated carbon fiber comprises the steps of treating the carbon fiber with a copper sulfate plating solution under the condition that the pH value is 11.5-12.5, and drying the carbon fiber to obtain the copper-plated carbon fiber.
Preferably, the composition of the copper sulfate plating solution comprises CuSO 420 parts of HCHO 20 parts, EDTA-2Na 25 parts, NaKC4H4O620 parts of, K4[Fe(CN)6]10 parts and 8 parts of 2, 2' -dipyridine.
The phenolic resin composition comprises the following components in percentage by weight:
zr element: so that the strength of the high molecular composite material prepared from the phenolic resin composition is increased after curing, and the cold brittleness is reduced.
Ni element: the strength and hardness of the high-molecular composite material prepared from the phenolic resin composition after curing are improved, and the mechanical property of the high-molecular composite material is improved, so that the high-molecular composite material disclosed by the invention has corrosion resistance and oxidation resistance.
Cu element: the strength and the abrasion resistance of the high-molecular composite material prepared from the phenolic resin composition are improved, so that the comprehensive mechanical property of the high-molecular composite material is improved.
Al2O3: improve the binding power of the macromolecular composite material prepared by the phenolic resin composition and improve the mechanical strength of the macromolecular composite material.
Fe: (1) after Fe metal particles with active chemical properties are introduced into a matrix of a high-molecular composite material prepared from the phenolic resin composition, when the matrix generates micro cracks under the action of external force, micron-sized Fe metal particles uniformly distributed in the matrix can be contacted with oxygen to generate oxidation and accompanied with volume expansion, and the expansion generates pressure stress on the surrounding matrix, so that the continuous expansion of the initiated cracks can be prevented, and the fracture toughness of the matrix is improved. (2) The introduction of the Fe metal particles can improve the barrier property of the matrix and increase the tortuosity of the path when water molecules are diffused, thereby improving the damp-heat resistance of the matrix. (3) The introduction of the micron-sized Fe metal particles improves the mechanical properties and the wear resistance of the solidified matrix such as strength, hardness and the like, and a high polymer composite material with excellent comprehensive performance can be obtained. (4) The reduced iron powder has high purity, low impurity content, good consistency, good compression performance and forming performance, and can provide higher binding power for the polymer composite material. Iron with more active chemical properties reacts with oxygen to obtain iron oxide, and the iron oxide has an oxidizing effect, can prevent the generation of active carbon and overcomes the vein defect; meanwhile, the ferric oxide can form a glass substance in a heating state, thereby reducing the heat permeability, preventing permeation and steam pollution and enhancing the heat toughness of the polymer composite material. The two can synergistically enhance the mechanical property of the polymer composite material. (5) The iron powder with different meshes is jointly used, so that the space stacking type among the powder with different meshes is better in terms of a micro space structure, and the powder can be mutually supported, so that the whole polymer composite material is higher in compactness and stronger in structural strength and structural stability.
The Carbon Nanotubes (CNTs) have good mechanical properties, the tensile strength of the CNTs reaches 50-200 GPa, which is 100 times that of steel, the density of the CNTs is only 1/6 of the steel, and the CNTs are at least one order of magnitude higher than that of conventional graphite fibers; its elastic modulus can reach 1TPa, which is equivalent to that of diamond, about 5 times that of steel. The tensile strength of the single-walled carbon nanotube with an ideal structure is about 800 GPa. Carbon nanotubes are the highest specific strength material that can be produced at present. The carbon nano tube is added into the phenolic resin composition to prepare the high polymer composite material, so that the high polymer composite material has good strength, elasticity, fatigue resistance and isotropy, and the performance of the high polymer composite material is obviously improved.
Compared with the prior art, the invention has the beneficial effects that:
the phenolic resin composition, the preparation method thereof and the application thereof in preparing the stamping die are innovatively combined and enhanced by various enhancing phases to modify the polyimide modified phenolic resin, the enhancing characteristics and the synergistic enhancing effect of various enhancing phases are comprehensively utilized, the comprehensive performance of the high polymer composite material prepared from the phenolic resin composition is improved, and the prepared high polymer composite material trial-manufacturing die has the following advantages:
(1) the applicability is good: the mechanical property of the polymer composite material can be synergistically enhanced by adding the additive, so that the sample vehicle trial-manufacturing stamping die prepared from the phenolic resin composition can meet the use requirements of sample vehicle trial-manufacturing and small-batch production; the phenolic resin composition has the outstanding advantages that the mechanical property of the phenolic resin composition is matched with the molding property of automobile parts made of aluminum alloy, magnesium alloy and other materials, and is mainly embodied as follows: (a) the hardness of the phenolic resin composition is close to that of light metal plates such as aluminum alloy and magnesium alloy, and the like, so that the scratch of the traditional black metal die material with higher hardness on the aluminum alloy and magnesium alloy plates with lower hardness is avoided; (b) because the wettability between the high polymer material and the light metal material is poor, the phenolic resin composition avoids the adhesion of aluminum alloy and magnesium alloy with better plasticity on the surface of a stamping die, and the lower friction coefficient between the aluminum alloy and the magnesium alloy is more beneficial to the plastic deformation in the material forming process.
(2) Light in weight, use cost are low: the polymer composite material prepared by the phenolic resin composition of the invention has the equivalent weight price with the traditional ferrous metal mold material (such as Cr12MoV, Cr12WV, 5CrMnMo, etc.), but the density is only about 1.5885-2.4360g/cm3Specific ferrous metal density (Cr 12MoV about 7.85 g/cm)35CrMnMo is about 7.53g/cm3) The die is much smaller, so that the die weight is obviously reduced under the same die volume, namely the volume price is low, and the material cost of the stamping die is reduced by more than 60%. The small test, the pilot test and the test production verification show that the phenolic resin composition developed by the invention has good processing performance, the rotating speed of a machine tool spindle can reach 10000 r/min and the abrasion to a cutter is very little in the process of processing the molded surface of the material die by using a numerical control milling machine; the traditional ferrous metal die material has high hardness and poor processing performance, and the spindle of the machine tool generally has the rotating speed of 6000 revolutions per minute and seriously wears the cutter in the process of processing the molded surface of the die by using a numerical control milling machine. Therefore, the die processing period using the material is short, and the comprehensive cost of mechanical processing is reduced by about 50%.
(3) The preparation period is short: the phenolic resin composition prepared by the invention has short manufacturing period and high die processing efficiency, so that the contract-delivery acceptance period of the stamping die is about 25 days; in comparison, the raw materials used by the traditional ferrous metal material die need to be subjected to the production process of casting alloy, the processing efficiency of the die is low, and the contract-delivery acceptance period is about 60 days.
(4) Environmental protection advantage: the phenolic resin composition does not need high temperature in the manufacturing process (the highest temperature in the preparation link is 100 ℃), does not generate waste water, waste gas and waste materials, and has low energy consumption. In comparison, the manufacturing process of the traditional ferrous metal mold material relates to links such as smelting, pouring, cleaning and the like, generally needs high temperature of more than 1200 ℃, has high energy consumption, needs to waste a large amount of cooling water for equipment cooling, generates a large amount of dust, smoke and solid wastes (mainly solid waste sand, slag and the like), and does not meet the requirements of energy conservation and environmental protection.
Therefore, the phenolic resin composition disclosed by the invention is applied to the field of stamping dies, can change the production and manufacturing mode of mainly adopting a ferrous metal die in the traditional stamping industry, has the characteristics of high performance/price ratio, short manufacturing period, energy conservation and environmental friendliness, is suitable for the production characteristics of small-batch and various sample vehicle trial production, and meets the production requirements of sample vehicle trial production.
Drawings
FIG. 1 is a compressive stress-strain curve of the phenolic resin composition prepared in example 3;
FIG. 2 is a compressive stress-strain curve of the phenolic resin composition prepared in example 12;
FIG. 3 is a compressive stress-strain curve of the phenolic resin composition prepared in example 15;
FIG. 4 is a component diagram for a particular embodiment;
FIG. 5 is a graph of results corresponding to the example embodiment.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
The implementation case is as follows: the phenolic resin composition comprises, by mass, 10-40 g of phenolic resin, 10-40 g of styrene butadiene rubber, 5-12 g of iron powder, 6-8 g of carbon-based material, 7-13 g of non-iron metal powder, 0.2-3 g of metal oxide, 10-13 g of basalt fiber and 2.4-5.3 g of dispersing agent. The carbon-based material is selected from carbon nano tubes and/or carbon fibers; the non-ferrous metal powder is selected from at least one of Zr, Ni or Cu; the metal oxide is Al2O3,TiO2,Ni2O3,Fe3O2Or CoO. The modified phenolic resin is modified by polyimideThe mass ratio of the phenolic resin to the polyimide in the polyimide modified phenolic resin is 1: 0.125-2. The iron powder is selected from reduced iron powder and/or electrolytic iron powder, and the mesh number of the iron powder is selected from 800-1600 meshes. The iron powder comprises 2-4 parts of 1600-mesh electrolytic iron powder, 1-3 parts of 1600-mesh reduced iron powder and 2-5 parts of 800-mesh reduced iron powder. The modified basalt fiber is composite nano SiO2The basalt fiber, the composite nano SiO2Among the basalt fibers, basalt fibers and nano SiO2The mass ratio of (A) to (B) is 8-12: 1. The carbon fiber is copper-plated carbon fiber.
The dispersant may be selected from TEGO Dispers, SOLPLUS D540, KH550, or BYK-110.
A method for preparing said composition comprising the steps of: weighing the components according to the formula ratio, sequentially adding styrene butadiene rubber and a dispersing agent into the phenolic resin, and uniformly mixing to obtain a mixed solution A; mixing iron powder, a carbon-based material, non-iron metal powder, metal oxide and basalt fiber to obtain a mixture B; and adding the mixture B into the mixed solution A, uniformly mixing and cooling to obtain the phenolic resin composition.
The preparation method of the polyimide modified phenolic resin comprises the following steps of weighing the phenolic resin and the polyimide in a mass ratio of 1: 0.125-2, uniformly mixing the phenolic resin and the polyimide through primary stirring at 90-100 ℃, adding a curing agent at 100 ℃ and uniformly mixing the curing agent through secondary stirring to obtain the polyamide-based modified phenolic resin; the stirring speed of the primary stirring and mixing and the secondary stirring and mixing is 300-500 r/min.
Wherein the basalt fiber comprises composite nano SiO2The basalt fiber, the composite nano SiO2The preparation method of the basalt fiber comprises the steps of weighing the basalt fiber and the nano SiO according to the mass ratio of 8-12: 12Nano SiO2Mixing the hydroxylated surface silicon with a polyurethane aqueous solution to obtain slurry, and leaching basalt fibers by using the slurry to obtain the composite nano SiO2The basalt fiber.
The carbon fiber is copper-plated carbon fiber, and the preparation method of the copper-plated carbon fiberThe method comprises the steps of treating carbon fibers with copper sulfate plating solution under the condition that the pH value is 11.5-12.5, and drying to obtain the copper-plated carbon fibers. The copper sulfate plating solution comprises CuSO 420 parts of HCHO 20 parts, EDTA-2Na 25 parts, NaKC4H4O620 parts of, K4[Fe(CN)6]10 parts and 8 parts of 2, 2' -dipyridine.
The compressive stress-strain curves of the examples are shown in FIGS. 1-3; the components and results corresponding to the specific examples are shown in fig. 4 and 5; wherein FIG. 1 is a compressive stress-strain curve of the phenolic resin composition prepared in example 3; FIG. 2 is a compressive stress-strain curve of the phenolic resin composition prepared in example 12; FIG. 3 is a compressive stress-strain curve of the phenolic resin composition prepared in example 15.
As can be seen from FIGS. 1 to 5, the polymer composite material prepared by the method has the advantages of the Richter hardness of 487-692, the compressive strength of 100.24-175.61 MPa and the impact toughness of 2.87-6.72kJ/m2(ii) a The die can meet the requirements of trial production of sample parts and small-batch trial production in the process of stamping sheet metal parts, the accuracy of stamped parts is higher, and products with more quantity can be stamped. The wear resistance test of the high molecular composite material is carried out on an M-2000 type friction wear testing machine, the size of a sample of the used high molecular composite material is 6mm multiplied by 7mm multiplied by 30mm, the material of a lower side grinding ring is Cr12 quenched steel, the diameter of the grinding ring is 40mm, the rotating speed of the grinding ring is 200r/min, the load is 100N, the wear time is 15min, and the wear rate of the composite material is 0.0105-0.0144 mg/M. The composite material contains partial resin, so that the composite material has the free-cutting characteristic of plastics. Different from the traditional metal die, the alloy material does not damage the cutter during processing, greatly shortens the processing time and reduces the processing cost, the processing time is 30-50% of the traditional gray cast iron (FC30), and the plastic characteristic of the alloy material ensures that the cutter is not vibrated during processing, thereby ensuring the high precision of processing.
Claims (5)
1. The phenolic resin composition is characterized by comprising, by mass, 10-40 parts of modified phenolic resin, 10-40 parts of styrene butadiene rubber, 5-12 parts of iron powder, 6-8 parts of carbon-based material, 7-13 parts of non-ferrous metal powder, 0.2-3 parts of metal oxide, 10-13 parts of modified basalt fiber and 2.4-5.3 parts of a dispersing agent;
the carbon-based material is copper-plated carbon fiber, and the preparation method of the copper-plated carbon fiber comprises the steps of treating the carbon fiber with a copper sulfate plating solution under the condition that the pH value is 11.5-12.5, and drying to obtain the copper-plated carbon fiber;
the non-ferrous metal powder is selected from at least one of Zr, Ni or Cu; the metal oxide is Al2O3、TiO2、Ni2O3、Fe3O2Or CoO;
the modified phenolic resin is polyimide modified phenolic resin, and the mass ratio of phenolic resin to polyimide in the polyimide modified phenolic resin is 1: 0.125-2;
the iron powder comprises 2-4 parts of 1600-mesh electrolytic iron powder, 1-3 parts of 1600-mesh reduced iron powder and 2-5 parts of 800-mesh reduced iron powder;
the modified basalt fiber is composite nano SiO2The basalt fiber, the composite nano SiO2Among the basalt fibers, basalt fibers and nano SiO2The mass ratio of (A) to (B) is 8-12: 1.
2. Use of the composition of claim 1 for the preparation of a stamping die, wherein the stamping die is an automotive die.
3. A method of preparing the composition of claim 1, comprising the steps of: weighing the components according to the formula ratio, sequentially adding styrene butadiene rubber and a dispersing agent into the modified phenolic resin, and uniformly mixing to obtain a mixed solution A; mixing iron powder, a carbon-based material, non-iron metal powder, a metal oxide and modified basalt fiber to obtain a mixture B; and adding the mixture B into the mixed solution A, uniformly mixing and cooling to obtain the phenolic resin composition.
4. The preparation method of the polyimide modified phenolic resin is characterized in that the modified phenolic resin is polyimide modified phenolic resin, and the preparation method of the polyimide modified phenolic resin comprises the following steps of weighing phenolic resin and polyimide in a mass ratio of 1: 0.125-2, uniformly mixing the phenolic resin and the polyimide through primary stirring at 90-100 ℃, adding a curing agent at 100 ℃ and uniformly mixing the curing agent through secondary stirring to obtain the polyimide modified phenolic resin.
5. The preparation method according to claim 3, wherein the modified basalt fiber is composite nano SiO2The basalt fiber, the composite nano SiO2The preparation method of the basalt fiber comprises the steps of weighing the basalt fiber and the nano SiO according to the mass ratio of 8-12: 12Nano SiO2Mixing the hydroxylated surface silicon with a polyurethane aqueous solution to obtain slurry, and leaching basalt fibers by using the slurry to obtain the composite nano SiO2The basalt fiber of (1).
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