CN108102369A - High filled composite materials of heat resistant and wear resistant and preparation method thereof - Google Patents

Abstract

The invention discloses high filled composite materials of a kind of heat resistant and wear resistant and preparation method thereof, the high filled composite materials of heat resistant and wear resistant include：20 90 parts by weight of high temperature resistant crystal type or semicrystalline resin, multicomponent mix abrasion resistant fibrous 10 50 parts by weight, 10 50 parts of reinforcing filler, 5 10 parts by weight of coupling agent, 15 parts of chain extender, 5 10 parts by weight of polyesters plasticizer.The composite material of the present invention has the characteristics that high intensity, height are heat-resisting, wear-resisting, can be used under the harsh conditions such as high temperature；Simultaneously because abrasion resistant fibrous and reinforcing filler cost is relatively low, the manufacturing cost of composite material is reduced.

Description

High-temperature wear-resistant high-filling composite material and preparation method thereof

technical field

The invention relates to a high-temperature-resistant and wear-resistant high-filling composite material and a preparation method thereof.

Background technique

High temperature resistant crystalline or semi-crystalline resins include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide amide, polyether ketone, polyether ether ketone, aramid, polyphenylene ether amide, etc. A large class of engineering materials that are common in materials are widely used in automobiles, aerospace and electronic engineering technology due to their excellent high temperature resistance, corrosion resistance and excellent mechanical properties. At present, there are two main problems in the use of such materials. One is that the high temperature and wear resistance of pure resin has a certain upper limit, and better performance can be obtained through processing and modification. The other is that such materials are generally not suitable for processing and are relatively expensive. Therefore, the filler modification for this kind of material is an important research field in the direction of polymer research at present. Using this technology can make the thermal performance and wear resistance of the material have a higher level than that of the original bulk resin. A relatively large improvement, while reducing costs and broadening the scope of application.

Among the common technical means of modifying high-temperature and wear-resistant polymer fillers, one of the main solutions is to add high-performance inorganic fibers, such as carbon fibers, glass fibers, etc. Alloy, modified with boron fiber, Chinese invention CN201610301526.2 announced low moisture absorption and wear-resistant carbon fiber reinforced high temperature resistant nylon composite material, modified with chopped carbon fiber, etc. One problem with this technical method is that they generally only use one Inorganic materials are used as modified fillers, because the compatibility between the resin matrix and the inorganic materials and the mutual compatibility of the inorganic materials is a relatively complicated issue. Modifiers added for the compatibility between resins and a certain type of inorganic material may not be effective for another inorganic material, and if the compatibility adjustment of different inorganic fibers is considered, it may affect the overall addition of the material and performance, and if the properties of the two inorganic fibers are similar, it is generally not necessary to add two fillers at the same time. Therefore, it is rare to add multiple modified fillers at the same time. If necessary, different material forms will be used. For example, a high-temperature and wear-resistant composite coating and its preparation published by the Chinese invention CN201510581570.9 method, the scheme of blending glass microspheres and carbon fibers is adopted.

On the other hand, as a relatively new inorganic fiber, basalt fiber has high strength and high heat resistance properties similar to carbon fiber. The characteristics of materials and covalently bonded inorganic materials also make it have similar compatibility with general inorganic fiber materials. At present, reports on the use of basalt fibers to modify polymer materials are relatively rare. For example, the Chinese invention CN201710318662.7 published a A friction material for a clutch driven disc and a preparation method thereof uses basalt fiber as a wear-resistant modified filler.

Contents of the invention

The purpose of the present invention is to solve the technical problem that currently the modified fiber used to prepare the high-temperature-resistant and wear-resistant high-filling composite material through modification is single, and the high-temperature and wear-resistant performance of the obtained composite material needs to be improved.

In order to achieve the purpose of the above invention, on the one hand, the present invention provides a high-temperature and wear-resistant high-filling composite material, which includes the following components:

The high temperature resistant crystalline or semi-crystalline resin is any of polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide amide, polyether ketone, polyether ether ketone, aromatic polyamide, polyphenylene ether amide A sort of;

The wear-resistant fiber is a combination of basalt fiber and other inorganic fibers, and the other inorganic fibers include at least one of glass fiber, carbon fiber and quartz fiber;

The reinforcing filler is at least one of montmorillonite, silica, talc, graphite and carbon black;

The coupling agent is at least one of a silane coupling agent and a titanate coupling agent;

The chain extender is at least one of diethyltoluenediamine, dimethylthiotoluenediamine, isocyanate and diglycidyl ester;

The polyester plasticizer is polypropylene adipate.

Further, the particle diameter of the reinforcing filler is 50-500 nm, and the BET specific surface area is greater than 8 m ² g ^-1 .

Further, in the wear-resistant fiber combination, the mass proportion of the basalt fiber is 5%-95%.

Further, the wear-resistant fiber has a diameter of 2-30 μm and a length of 50-800 mm.

Further, the silane coupling agent is one of epoxy silane, amino silane, methoxy silane and vinyl silane.

Further, the number average molecular weight of the polytrimethylene adipate is 2000-10000.

In another aspect, the present invention provides a method for preparing a high-temperature-resistant and wear-resistant high-filling composite material, comprising the following steps:

(1) Drying the high temperature resistant crystalline or semi-crystalline resin at 120-180°C for 2-6 hours by mass, and drying the wear-resistant fiber and the reinforcing filler Drying at 80-100°C for 2-4 hours;

(2) Mechanically stir and mix the dried reinforcing filler and the coupling agent by mass for 10-30min at a stirring rate of 2000-5000rpm;

(3) Mechanically stir the dried high-temperature-resistant crystalline or semi-crystalline resin, the mixture in step (2), the polyester plasticizer in parts by mass, and the chain extender in parts by mass Mix for 10-30min, stirring speed is 100-300rpm;

(4) Put the mixture in step (3) into the main feeding port of the twin-screw extruder, put the dried wear-resistant fiber into the side feeding port of the twin-screw extruder, and adjust the extrusion temperature and The speed of the main machine is controlled at a certain value to extrude and granulate, and dry to obtain a high-temperature-resistant and wear-resistant high-filling composite material.

Further, the extrusion temperature is 260-330° C., and the rotation speed of the host is 300-500 rpm.

Compared with prior art, the beneficial effect of the present invention is:

The present invention uses basalt fiber and one or more other inorganic fibers to participate in resin modification. In terms of classification, the properties of basalt fiber are similar to those of carbon fiber, but the cost is lower. Both of them can participate in the modification without sacrificing performance. At the same time, the compatibility characteristics of the two and the resin matrix are similar; basalt fiber, glass fiber, quartz fiber, etc. are a combination of complementary properties. The former can provide excellent high temperature resistance and mechanical properties are stronger than the latter. , while the latter provides strength modification, it also has the advantages of low cost, easy processing and easy acquisition, and the compatibility characteristics of the two are also similar, so the high-temperature and wear-resistant high-filling composite material prepared by the present invention has excellent High temperature resistance, corrosion resistance, wear resistance and excellent mechanical properties, good fluidity, easy to form, suitable for injection molding, extrusion and other processes; can achieve a high filler rate, while maintaining the material properties are not affected; process The method is simple and low in cost, can be used as a reliable technical solution for preparing high-strength and high-hardness materials, and has wide application prospects.

Detailed ways

The present invention will be further described below by specific examples.

Example 1

(1) The raw materials are configured according to the following mass parts: 50 parts of polyphenylene sulfide resin; 10 parts of basalt fiber (diameter 5 μm, length 300 mm), 10 parts of carbon fiber (diameter 5 μm, length 500 mm), talc (particle size 180 nm, density 2.75 g/cm3) 25 parts, coupling agent (epoxy silane) 1 part, chain extender (diethyltoluenediamine) 2 parts, plasticizer (polytrimethylene adipate) 2 parts.

(2) Dry the polyphenylene sulfide resin at 140°C for 4 hours; dry the mixed fiber and talc at 90°C for 3 hours.

(3) Stir the dried talc and coupling agent mechanically for 20 minutes at a stirring rate of 3000 rpm.

(4) Mechanically stir the dried polyphenylene sulfide resin with the mixture, chain extender, and plasticizer in step (3) for 10 minutes at a stirring speed of 300 rpm.

(5) Put the mixture in step (4) into the main feed port of the twin-screw extruder, and put the dried mixed fiber into the side feed port of the twin-screw extruder. The processing technology is as follows:

The twin-screw extruder is divided into eight areas, of which the temperature of area 1-3 is 280 °C, the temperature of area 4-6 is 310 °C, and the temperature of area 7-8 is 320 °C; the temperature of the extrusion die is 330 °C; the screw The rotational speed was 300 rpm; the residence time of the mixture in the twin-screw extruder was 2 minutes.

(6) The product obtained in step (5) is subjected to post-processing such as stranding, pelletizing, and drying to obtain a high-temperature-resistant and wear-resistant high-filling composite material.

Example 2

(1) The raw materials are configured according to the following mass parts: 40 parts of polyether ether ketone resin; 20 parts of basalt fiber (diameter 30 μm, length 300 mm), 10 parts of glass fiber (diameter 10 μm, length 100 mm), graphite (particle size 100 nm, Density 2.25g/cm3) 20 parts, coupling agent (aminosilane) 1 part, chain extender (dimethylthiotoluenediamine) 3 parts, plasticizer (polytrimethylene adipate) 6 parts.

(2) Dry the polyetheretherketone resin at 180°C for 4 hours; dry the mixed fiber and graphite at 90°C for 3 hours.

(3) Stir the dried graphite and coupling agent mechanically for 20min at a stirring rate of 4000rpm.

(4) Mechanically stir the dried polyether ether ketone resin with the mixture, chain extender, and plasticizer in step (3) for 10 minutes at a stirring rate of 300 rpm.

(5) Put the mixture in step (4) into the main feed port of the twin-screw extruder, and put the dried mixed fiber into the side feed port of the twin-screw extruder. The processing technology is as follows:

The twin-screw extruder is divided into eight areas, of which the temperature of area 1-3 is 280 °C, the temperature of area 4-6 is 310 °C, and the temperature of area 7-8 is 320 °C; the temperature of the extrusion die is 330 °C; the screw The rotational speed was 300 rpm; the residence time of the mixture in the twin-screw extruder was 2 minutes.

(6) The product obtained in step (5) is subjected to post-processing such as stranding, pelletizing, and drying to obtain a high-temperature-resistant and wear-resistant high-filling composite material.

Example 3

(1) The raw materials are configured according to the following mass parts: 30 parts of polyether ether ketone resin; 10 parts of basalt fiber (diameter 30 μm, length 300 mm), 15 parts of carbon fiber (diameter 5 μm, length 500 mm), quartz fiber (diameter 10 μm, length 100mm) 5 parts, graphite (particle size 100nm, density 2.25g/cm3) 30 parts, coupling agent (aminosilane) 2 parts, chain extender (dimethylthiotoluenediamine) 3 parts, plasticizer (poly propylene glycol adipate) 5 parts.

(2) Dry the polyetheretherketone resin at 180°C for 4 hours; dry the mixed fiber and graphite at 90°C for 3 hours.

(3) Stir the dried graphite and coupling agent mechanically for 30min at a stirring rate of 4000rpm.

(4) Mechanically stir the dried polyether ether ketone resin with the mixture, chain extender, and plasticizer in step (3) for 10 minutes at a stirring speed of 300 rpm.

(5) Put the mixture in step (4) into the main feed port of the twin-screw extruder, and put the dried mixed fiber into the side feed port of the twin-screw extruder. The processing technology is as follows:

The twin-screw extruder is divided into eight areas, of which the temperature of area 1-3 is 280 °C, the temperature of area 4-6 is 310 °C, and the temperature of area 7-8 is 320 °C; the temperature of the extrusion die is 330 °C; the screw The rotational speed was 300 rpm; the residence time of the mixture in the twin-screw extruder was 2 minutes.

(6) The product obtained in step (5) is subjected to post-processing such as stranding, pelletizing, and drying to obtain a high-temperature-resistant and wear-resistant high-filling composite material.

Example 4

(1) The raw materials are configured according to the following mass parts: 25 parts of polyphenylene sulfide resin; 5 parts of basalt fiber (15 μm in diameter, 300 mm in length), 25 parts of glass fiber (20 μm in diameter, 500 mm in length), 100nm, density 2.25g/cm3) 30 parts, coupling agent (titanate) 2 parts, chain extender (isocyanate) 5 parts, plasticizer (polytrimethylene adipate) 8 parts.

(2) Dry the polyetheretherketone resin at 180°C for 4 hours; dry the mixed fiber and graphite at 90°C for 3 hours.

(3) Stir the dried silica and coupling agent mechanically for 30 minutes at a stirring rate of 5000 rpm.

(4) Mechanically stir the dried polyphenylene sulfide resin with the mixture, chain extender, and plasticizer in step (3) for 10 minutes at a stirring speed of 300 rpm.

(5) Put the mixture in step (4) into the main feed port of the twin-screw extruder, and put the dried mixed fiber into the side feed port of the twin-screw extruder. The processing technology is as follows:

The twin-screw extruder is divided into eight areas, of which the temperature of area 1-3 is 280 °C, the temperature of area 4-6 is 310 °C, and the temperature of area 7-8 is 320 °C; the temperature of the extrusion die is 330 °C; the screw The rotational speed was 300 rpm; the residence time of the mixture in the twin-screw extruder was 2 minutes.

(6) The product obtained in step (5) is subjected to post-processing such as stranding, pelletizing, and drying to obtain a high-temperature-resistant and wear-resistant high-filling composite material.

Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.

Claims (8)

1. The high-temperature and wear-resistant high-filling composite material is characterized in that it contains the following components: The high temperature resistant crystalline or semi-crystalline resin is any of polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide amide, polyether ketone, polyether ether ketone, aromatic polyamide, polyphenylene ether amide A sort of; The wear-resistant fiber is a combination of basalt fiber and other inorganic fibers, and the other inorganic fibers include at least one of glass fiber, carbon fiber and quartz fiber; The reinforcing filler is at least one of montmorillonite, silica, talc, graphite and carbon black; The coupling agent is at least one of a silane coupling agent and a titanate coupling agent; The chain extender is at least one of diethyltoluenediamine, dimethylthiotoluenediamine, isocyanate and diglycidyl ester; The polyester plasticizer is polypropylene adipate. 2. The high-temperature and wear-resistant high-filling composite material according to claim 1, characterized in that, the particle size of the reinforcing filler is 50-500 nm, and the BET specific surface area is greater than 8 m ² g ^-1 . 3. The high-temperature and wear-resistant high-filling composite material according to claim 1, characterized in that, in the wear-resistant fiber combination, the mass proportion of the basalt fiber is 5%-95%. 4. The high-temperature and wear-resistant high-filling composite material according to claim 1, wherein the wear-resistant fiber has a diameter of 2-30 μm and a length of 50-800 mm. 5. The high temperature and wear resistant high filling composite material according to claim 1, characterized in that the silane coupling agent is one of epoxy silane, amino silane, methoxy silane and vinyl silane. 6. The high-temperature-resistant and wear-resistant high-filling composite material according to claim 1, characterized in that the number-average molecular weight of the polytrimethylene adipate is 2000-10000. 7. The preparation method of the high-temperature and wear-resistant high-filling composite material according to any one of claims 1-6, characterized in that it comprises the following steps: (1) Drying the high temperature resistant crystalline or semi-crystalline resin at 120-180°C for 2-6 hours by mass, and drying the wear-resistant fiber and the reinforcing filler Drying at 80-100°C for 2-4 hours; (2) Mechanically stir and mix the dried reinforcing filler and the coupling agent by mass for 10-30min at a stirring rate of 2000-5000rpm; (3) Mechanically stir the dried high-temperature-resistant crystalline or semi-crystalline resin, the mixture in step (2), the polyester plasticizer in parts by mass, and the chain extender in parts by mass Mix for 10-30min, stirring speed is 100-300rpm; (4) Put the mixture in step (3) into the main feeding port of the twin-screw extruder, put the dried wear-resistant fiber into the side feeding port of the twin-screw extruder, and adjust the extrusion temperature and The speed of the main machine is controlled at a certain value to extrude and granulate, and dry to obtain a high-temperature-resistant and wear-resistant high-filling composite material. 8 . The preparation method according to claim 7 , characterized in that, the extrusion temperature is 260-330° C., and the rotation speed of the host is 300-500 rpm.