Piston material for new energy automobile brake calipers and preparation method of piston material

Abstract

The invention discloses a piston material for new energy automobile brake calipers and a preparation method thereof, and belongs to the technical field of piston materials, the piston material comprises the following raw materials by weight: 10-20 parts of phenolic resin, 3-8 parts of a modified reinforcing filler, 30-50 parts of a filler agent, and 1-2.5 parts of an auxiliary agent; the preparation method comprises the following steps: adding the raw materials into a mixer, uniformly mixing to obtain a mixture, feeding the mixture into a double-screw extruder, mixing, extruding and granulating to obtain the piston material for the brake calipers of the new energy automobile. When the modified reinforcing filler is added into a matrix, on one hand, the toughening effect of the glass fibers can be played, on the other hand, the introduced maleimide and residual amino groups can also participate in curing of the phenolic resin, and the curing effect of the system at high temperature can also be guaranteed through an introduced heat-resistant structure.

Description

Technical Field

[0001] The present invention relates to the technical field of piston materials, and in particular to a piston material for a new energy vehicle brake caliper and a preparation method thereof. Background Art

[0002] Caliper pistons used in automobiles are made of phenolic molding compounds. The basic requirements for phenolic molding compounds used in automobiles are that they should have high mechanical strength, heat resistance, chemical resistance and dimensional stability. Caliper pistons are mainly used for braking. They are an indispensable and important part of the automobile braking system.

[0003] In order to achieve the above performance requirements, the usual practice is to use linear phenolic resin as a binder, glass fiber as a reinforcing material, and silicone rubber as a toughening agent, where the phenolic resin is about 35 points, the glass fiber is about 40 points, the mineral filler is about 30 points, and other additives plus curing agent are about 10 points. With traditional mixing production, the material production and processing are difficult, the glass fiber in the molding compound particles is easy to be exposed and pilling, causing trouble for subsequent processing, and the performance is low.

[0004] Due to the increasingly stringent requirements for high mechanical strength, heat resistance, and dimensional stability of materials, inorganic fibers are becoming more and more common as reinforcing and heat-resistant materials. Although inorganic fiber materials have been found, the amount added still cannot meet these performance requirements. Secondly, the domestic production process basically uses the most traditional mixing process, which is unable to completely melt and knead the fibers.

[0005] Therefore, there is an urgent need for a phenolic molding compound for automobile caliper piston molding and a preparation method thereof, the performance of which has been greatly improved, and which can be processed by melt kneading while meeting environmental friendliness. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a piston material for a new energy vehicle brake caliper and a preparation method thereof.

[0007] The purpose of the present invention can be achieved through the following technical solutions: A piston material for a new energy vehicle brake caliper, comprising the following raw materials in parts by weight: 10-20 parts of phenolic resin, 3-8 parts of modified reinforcing filler, 30-50 parts of filler, and 1-2.5 parts of auxiliary agent; The modified reinforcing filler is prepared by the following steps: Step S1, adding N-p-hydroxyphenylmaleamic acid to toluene, adding p-toluenesulfonic acid and N,N-dimethylformamide, heating to 100-110° C., keeping warm for 2-4 hours, pouring into deionized water after the reaction, cooling and crystallizing, filtering, and vacuum drying at 65-75° C. to obtain an intermediate; In step S1, p-toluenesulfonic acid is used as a catalyst to dehydrate and ring-close N-p-hydroxyphenylmaleamic acid to prepare an intermediate; Step S2, adding 4,4'-biphenyl dimethyl ether and the intermediate into a three-necked flask, adding p-toluenesulfonic acid, heating to 100-110°C, keeping warm and reacting for 4-6 hours, cooling to room temperature after the reaction, washing with hot ethanol five times, and then placing at 50-65°C for vacuum drying for 6-8 hours to obtain a modifier; In step S2, p-toluenesulfonic acid is used as a catalyst, and 4,4'-biphenyl dimethyl ether reacts with the intermediate to prepare a modifier, which has both a biphenyl structure and a maleimide structure, both of which are heat-resistant structures.

[0008] Step S3, adding the modified glass fiber and the modifier into N,N-dimethylformamide, heating to 60-65° C., stirring at a constant speed and reacting for 4-6 hours, and obtaining a modified reinforced filler after the reaction is completed.

[0009] In step S3, the maleic anhydride on the modifier reacts with the amino group on the modified glass fiber, and the modifier structure is connected to the surface of the glass fiber. When the modified reinforcing filler is added to the matrix, on the one hand, it can play a toughening effect on the glass fiber, and on the other hand, the introduced maleimide and the remaining amino group can also participate in the curing of the phenolic resin. The introduced heat-resistant structure can also ensure the curing effect of the system at high temperature.

[0010] Furthermore, the filler is wollastonite.

[0011] Furthermore, the auxiliary agent is a mixture of a release agent, a colorant and an active agent in a weight ratio of 1:5:1.

[0012] Furthermore, the release agent is zinc stearate, the colorant is carbon black, and the activator is silane.

[0013] Furthermore, in step S1, the dosage ratio of N-p-hydroxyphenylmaleamic acid, p-toluenesulfonic acid, N,N-dimethylformamide and deionized water is controlled to be 7.5-8.0 g: 0.8-1.2 g: 3-4 mL: 15-20 mL.

[0014] Furthermore, in step S2, the dosage ratio of 4,4'-biphenyl dimethyl ether, the intermediate and p-toluenesulfonic acid is controlled to be 2-4 g: 5-6 g: 0.03-0.05 g.

[0015] Furthermore, in step S3, the dosage ratio of the modified glass fiber, the modifier and N,N-dimethylformamide is controlled to be 10-12 g: 3-5 g: 20-25 mL.

[0016] A method for preparing a piston material for a new energy vehicle brake caliper comprises the following steps: The raw materials are added into a mixer and mixed evenly to obtain a mixture, which is then sent into a twin-screw extruder for mixing and extrusion granulation to obtain a piston material for a brake caliper of a new energy vehicle.

[0017] Beneficial effects of the present invention: The invention prepares a piston material for a brake caliper of a new energy vehicle. The phenolic resin is used as a matrix and a modified reinforcing filler is used as the reinforcing filler. In the preparation process of the reinforcing filler, p-toluenesulfonic acid is first used as a catalyst to prepare an intermediate by dehydration and ring-closing of N-p-hydroxyphenylmaleamic acid. Then 4,4'-biphenyl dimethyl ether reacts with the intermediate to prepare a modifier. The modifier has both a biphenyl structure and a maleimide structure, both of which are heat-resistant structures. Finally, the maleic anhydride on the modifier reacts with the amino group on the modified glass fiber to connect the modifier structure to the surface of the glass fiber. When the modified reinforcing filler is added to the matrix, on the one hand, the toughening effect of the glass fiber can be exerted, and on the other hand, the introduced maleimide and the remaining amino group can also participate in the curing of the phenolic resin. The introduced heat-resistant structure can also ensure the curing effect of the system at high temperature. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1: A piston material for a new energy vehicle brake caliper comprises the following raw materials in parts by weight: 10 parts of phenolic resin (S604A-1-2 / S604A-1-3), 3 parts of modified reinforcing filler, 30 parts of filler, and 1 part of auxiliary agent; A method for preparing a piston material for a new energy vehicle brake caliper comprises the following steps: The raw materials are added into a mixer and mixed evenly to obtain a mixture, which is then sent into a twin-screw extruder for mixing and extrusion granulation to obtain a piston material for a brake caliper of a new energy vehicle.

[0020] The modified reinforcing filler is prepared by the following steps: Step S1, adding N-p-hydroxyphenylmaleamic acid to toluene, adding p-toluenesulfonic acid and N,N-dimethylformamide, heating to 100°C, keeping warm for 2h, pouring into deionized water after the reaction, cooling and crystallizing, filtering, and vacuum drying at 65°C to obtain an intermediate, wherein the amount ratio of N-p-hydroxyphenylmaleamic acid, p-toluenesulfonic acid, N,N-dimethylformamide and deionized water is controlled to be 7.5g:0.8g:3mL:15mL; Step S2, add 4,4'-biphenyl dimethyl ether and the intermediate into a three-necked flask, add p-toluenesulfonic acid, heat to 100°C, keep warm and react for 4 hours, cool to room temperature after the reaction, wash five times with hot ethanol, and then place at 50°C for vacuum drying for 6 hours to obtain a modifier, and control the dosage ratio of 4,4'-biphenyl dimethyl ether, the intermediate and p-toluenesulfonic acid to be 2g: in step S3, control the dosage ratio of modified glass fiber, modifier and N,N-dimethylformamide to be 10g:3g:20mL; Step S3, adding the modified glass fiber and the modifier to N,N-dimethylformamide, heating to 60°C, stirring at a uniform speed and reacting for 4 hours, and obtaining a modified reinforced filler after the reaction is completed, and controlling the usage ratio of the modified glass fiber, the modifier and N,N-dimethylformamide to be 10g:3g:20mL.

[0021] The filler is wollastonite.

[0022] The auxiliary agent is a mixture of a release agent, a colorant and an active agent in a weight ratio of 1:5:1.

[0023] The release agent is zinc stearate, the colorant is carbon black, and the active agent is silane (model SCA1113).

[0024] The modified glass fiber is a glass fiber modified by silane coupling agent KH550.

[0025] Example 2: A piston material for a new energy vehicle brake caliper, comprising the following raw materials in parts by weight: 15 parts of phenolic resin (S604A-1-2 / S604A-1-3), 5 parts of modified reinforcing filler, 40 parts of filler, and 1.5 parts of auxiliary agent; A method for preparing a piston material for a new energy vehicle brake caliper comprises the following steps: The raw materials are added into a mixer and mixed evenly to obtain a mixture, which is then sent into a twin-screw extruder for mixing and extrusion granulation to obtain a piston material for a brake caliper of a new energy vehicle.

[0026] The modified reinforcing filler is prepared by the following steps: Step S1, adding N-p-hydroxyphenylmaleamic acid to toluene, adding p-toluenesulfonic acid and N,N-dimethylformamide, heating to 100°C, keeping warm for reaction for 3 hours, pouring into deionized water after the reaction, cooling and crystallizing, filtering, and vacuum drying at 70°C to obtain an intermediate, wherein the amount ratio of N-p-hydroxyphenylmaleamic acid, p-toluenesulfonic acid, N,N-dimethylformamide and deionized water is controlled to be 7.8g:1g:3mL:20mL; Step S2, add 4,4'-biphenyl dimethyl ether and the intermediate into a three-necked flask, add p-toluenesulfonic acid, heat to 110°C, keep warm and react for 5 hours, cool to room temperature after the reaction, wash five times with hot ethanol, and then place at 60°C for vacuum drying for 8 hours to obtain a modifier, and control the amount ratio of 4,4'-biphenyl dimethyl ether, the intermediate and p-toluenesulfonic acid to be 2.5g: in step S3, control the amount ratio of modified glass fiber, modifier and N,N-dimethylformamide to be 11g:4g:20mL; Step S3, adding the modified glass fiber and the modifier to N,N-dimethylformamide, heating to 60°C, stirring at a uniform speed and reacting for 4-6 hours, and obtaining a modified reinforced filler after the reaction is completed, and controlling the usage ratio of the modified glass fiber, the modifier and N,N-dimethylformamide to be 12g:4g:24mL.

[0027] The filler is wollastonite.

[0028] The auxiliary agent is a mixture of a release agent, a colorant and an active agent in a weight ratio of 1:5:1.

[0029] The release agent is zinc stearate, the colorant is carbon black, and the active agent is silane (model SCA1113).

[0030] The modified glass fiber is a glass fiber modified by silane coupling agent KH550.

[0031] Example 3: A piston material for a new energy vehicle brake caliper, comprising the following raw materials in parts by weight: 20 parts of phenolic resin (S604A-1-2 / S604A-1-3), 8 parts of modified reinforcing filler, 50 parts of filler, and 2.5 parts of auxiliary agent; A method for preparing a piston material for a new energy vehicle brake caliper comprises the following steps: The raw materials are added into a mixer and mixed evenly to obtain a mixture, which is then sent into a twin-screw extruder for mixing and extrusion granulation to obtain a piston material for a brake caliper of a new energy vehicle.

[0032] The modified reinforcing filler is prepared by the following steps: Step S1, adding N-p-hydroxyphenylmaleamic acid to toluene, adding p-toluenesulfonic acid and N,N-dimethylformamide, heating to 110°C, keeping warm for 4 hours, pouring into deionized water after the reaction, cooling and crystallizing, filtering, and vacuum drying at 75°C to obtain an intermediate, wherein the amount ratio of N-p-hydroxyphenylmaleamic acid, p-toluenesulfonic acid, N,N-dimethylformamide and deionized water is controlled to be 8.0g:1.2g:4mL:20mL; Step S2, add 4,4'-biphenyl dimethyl ether and the intermediate into a three-necked flask, add p-toluenesulfonic acid, heat to 110°C, keep warm and react for 6 hours, cool to room temperature after the reaction, wash five times with hot ethanol, and then place at 65°C for vacuum drying for 8 hours to obtain a modifier, and control the amount ratio of 4,4'-biphenyl dimethyl ether, the intermediate and p-toluenesulfonic acid to be 4g: in step S3, control the amount ratio of modified glass fiber, modifier and N,N-dimethylformamide to be 12g:5g:25mL; Step S3, adding the modified glass fiber and the modifier to N,N-dimethylformamide, heating to 65°C, stirring at a uniform speed and reacting for 6 hours, and obtaining a modified reinforced filler after the reaction is completed, and controlling the usage ratio of the modified glass fiber, the modifier and N,N-dimethylformamide to be 12g:5g:25mL.

[0033] The filler is wollastonite.

[0034] The auxiliary agent is a mixture of a release agent, a colorant and an active agent in a weight ratio of 1:5:1.

[0035] The release agent is zinc stearate, the colorant is carbon black, and the active agent is silane (model SCA1113).

[0036] The modified glass fiber is a glass fiber modified by silane coupling agent KH550.

[0037] Comparative Example 1: Compared with Example 1, this comparative example uses commercially available glass fiber instead of the modified reinforcing filler of the present invention, and the rest is the same as Example 1.

[0038] The performance of the piston materials prepared in Examples 1 to 3 and Comparative Example 1 was tested, and the results are shown in Table 1 below: Tensile strength: According to GB / T1040.2-2006 standard; Elongation at break: According to GB / T1040.2-2006 standard; Friction coefficient: in accordance with GB / T 3960-2016 standard; Volume wear rate: in accordance with GB / T 3960-2016 standard.

[0039] Table 1 Tensile strength MPa Friction coefficient <![CDATA[Volume wear rate X 10 -7 mm 3 / N•m]]> Example 1 75 0.12 1.2 Example 2 78 0.14 1.4 Example 3 78 0.15 1.3 Comparative Example 1 62 0.22 2.5 It can be seen from Table 1 above that the piston materials prepared in Examples 1-3 of the present invention have excellent performance.

[0040] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A piston material for a new energy vehicle brake caliper, characterized in that: The method comprises the following raw materials in parts by weight: 10-20 parts of phenolic resin, 3-8 parts of modified reinforcing filler, 30-50 parts of filler, and 1-2.5 parts of auxiliary agent; The modified reinforcing filler is prepared by the following steps: Step S1, adding N-p-hydroxyphenylmaleamic acid to toluene, adding p-toluenesulfonic acid and N,N-dimethylformamide, heating to 100-110°C, keeping warm for 2-4 hours, pouring into deionized water after the reaction, cooling and crystallizing, filtering, vacuum drying to obtain an intermediate; Step S2, adding 4,4'-biphenyl dimethyl ether and the intermediate into a three-necked flask, adding p-toluenesulfonic acid, heating to 100-110°C, keeping warm and reacting for 4-6 hours, cooling to room temperature after the reaction, washing with hot ethanol five times, and then vacuum drying for 6-8 hours to obtain a modifier; Step S3, adding the modified glass fiber and the modifier into N,N-dimethylformamide, heating to 60-65° C., stirring at a constant speed and reacting for 4-6 hours, and obtaining a modified reinforced filler after the reaction is completed.

2. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The filler is wollastonite.

3. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The auxiliary agent is a mixture of a release agent, a colorant and an active agent in a weight ratio of 1:5:

1.

4. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The release agent is zinc stearate, the colorant is carbon black, and the activator is silane.

5. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: In step S1, the dosage ratio of N-p-hydroxyphenylmaleamic acid, p-toluenesulfonic acid, N,N-dimethylformamide and deionized water is controlled to be 7.5-8.0 g: 0.8-1.2 g: 3-4 mL: 15-20 mL.

6. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The vacuum drying temperature in step S1 is 65-75°C.

7. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: In step S2, the dosage ratio of 4,4'-biphenyl dimethyl ether, the intermediate and p-toluenesulfonic acid is controlled to be 2-4 g: 5-6 g: 0.03-0.05 g.

8. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The vacuum drying temperature in step S2 is 50-65°C.

9. The piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: In step S3, the dosage ratio of the modified glass fiber, the modifier and N,N-dimethylformamide is controlled to be 10-12 g: 3-5 g: 20-25 mL.

10. The method for preparing a piston material for a new energy vehicle brake caliper according to claim 1, characterized in that: The steps include: The raw materials are added into a mixer and mixed evenly to obtain a mixture, which is then sent into a twin-screw extruder for mixing and extrusion granulation to obtain a piston material for a brake caliper of a new energy vehicle.