High performance composite material and method for making same

Abstract

The application belongs to the technical field of high polymer materials, and particularly relates to a high-performance composite material and a preparation method thereof. The high-performance composite material comprises the following raw materials in parts by weight: nylon resin 80-90 parts, POK resin 20-30 parts, hydroxyl-terminated polydimethylsiloxane 5-10 parts, antioxidant 0.1-0.3 parts, flame retardant 3-8 parts, lubricant 0.05-1 part, filler 15-21 parts, and glass fiber 20-30 parts. The filler and the hydroxyl-terminated polydimethylsiloxane are used in combination, so that the wear resistance and toughness of the composite material can be improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a high-performance composite material and a preparation method thereof. BACKGROUND

[0002] Nylon 66, also known as polyamide (PA66), is a thermoplastic resin containing repeating amide groups in the molecular backbone, which is widely used in automotive parts, mechanical parts, electronic and electrical products, engineering parts, and cable ties. Due to its excellent mechanical properties, it plays an important role in modern industry. However, its poor wear resistance and other shortcomings greatly limit its application.

[0003] POK (polyketone material) is a new green polymer material polymerized from carbon monoxide, ethylene and propylene. It is a high-performance engineering plastic with a tight crystalline structure formed by carbon and hydrogen through high crystallization. Due to its impact resistance, wear resistance and temperature resistance, it is widely used in automotive parts, electronic and electrical parts, medical devices, food packaging and other fields. However, it also has some inherent defects, such as low strength and modulus.

[0004] With the progress of technology and the improvement of performance requirements for special products, various nylon / POK composite materials have appeared on the market. However, the existing materials still have the technical problems of insufficient wear resistance and toughness, which limits their application in complex scenarios. Therefore, developing a nylon / POK composite material with high wear resistance and high toughness can effectively expand the application field of nylon / POK materials, and has important practical value. SUMMARY

[0005] To overcome the shortcomings of the prior art, the first purpose of the present application is to provide a high-performance composite material with high wear resistance and high toughness.

[0006] The second purpose of the present application is to provide a preparation method of a high-performance composite material, which has a simple preparation process.

[0007] To achieve the above purposes, the technical solution adopted by the present application is as follows:

[0008] A high-performance composite material comprises the following raw materials by weight: nylon resin 80-90 parts, POK resin 20-30 parts, hydroxyl-terminated polydimethylsiloxane 5-10 parts, antioxidant 0.1-0.3 parts, flame retardant 3-8 parts, lubricant 0.05-1 parts, filler 15-21 parts, and glass fiber 20-30 parts.

[0009] Further, the nylon resin is PA66.

[0010] Further, the preparation process of the filler is as follows:

[0011] (1) adding sodium carbonate into manganese nitrate solution to perform stirring reaction, aging at room temperature after reaction is completed, to obtain mixed solution;

[0012] (2) adding pretreated diatomite into water, then adding mixed solution of step (1) to perform heating reaction, aging at room temperature after reaction is completed, to obtain diatomite compound through filtering, washing and drying;

[0013] (3) adding diatomite compound of step (2) into toluene containing silane coupling agent to perform stirring, filtering, washing and drying after stirring is completed, to obtain the filler.

[0014] Further, the amount ratio of sodium carbonate and manganese nitrate solution in step (1) is 1g: (50-100) mL; the concentration of manganese nitrate solution is 0.2-0.5mol / L; the temperature of stirring reaction is 60-70℃, and the time of stirring reaction is 1-2h; the time of aging is 46-50h.

[0015] Further, the mass ratio of pretreated diatomite and mixed solution in step (2) is 1: (10-20); the temperature of heating reaction is 60-70℃, and the time of heating reaction is 4-6h; the time of aging is 22-26h.

[0016] Further, the preparation method of pretreated diatomite is as follows: adding diatomite into nitric acid with concentration of 3-5mol / L to perform stirring reaction, washing the product to neutral after reaction is completed, then calcining and sieving, to obtain the product.

[0017] Further, the temperature of stirring reaction is 60-70℃, and the time of stirring reaction is 6-9h; the temperature of calcining is 450-550℃, and the time of calcining is 0.5-1.5h; the mesh number of sieving is 300-500.

[0018] Further, the mass ratio of diatomite compound and silane coupling agent in step (3) is 1: (0.05-0.1); the silane coupling agent is propyl triethoxy silane isocyanate; the temperature of stirring is 60-70℃, and the time of stirring is 1-3h.

[0019] Further, the antioxidant is antioxidant 168 or antioxidant 1010, the flame retardant is melamine cyanurate, and the lubricant is pentaerythritol stearate or polyethylene wax.

[0020] The preparation method of the above high-performance composite material comprises the following steps:

[0021] According to the weight part ratio, each raw material is weighed and pre-mixed, and then melted, extruded, cooled, granulated, and dried to obtain the high-performance composite material.

[0022] Further, the pre-mixing time is 3-5 min; and the temperature range of each temperature zone in the melting and extrusion is 210-235 DEG C.

[0023] The beneficial technical effects of the present application are that:

[0024] The filler obtained by the present application can improve the wear resistance and toughness of the composite material when used with hydroxyl-terminated polydimethylsiloxane. This may be due to the increase in the internal pore structure of the pretreated diatomite, the columnar modification by the manganese nitrate solution, which can improve the stability and wear resistance of the material, and the surface modification by the silane coupling agent, which can improve the compatibility of the filler in the base material and form an ester bond between the silane coupling agent and the hydroxyl group of the hydroxyl-terminated polydimethylsiloxane, thereby improving the toughness of the material. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 SEM image of the filler obtained in Example 1. DETAILED DESCRIPTION

[0026] The following further detailed description of the present application is made in conjunction with specific preferred embodiments, and it is not to be recognized that the specific implementation of the present application is limited to these descriptions. For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of simple deductions or substitutions can also be made, which should be regarded as falling within the scope of protection of the present application. The specific conditions not mentioned in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used, such as those not specifically mentioned, are conventional products obtained through market channels.

[0027] The nylon resin involved in the examples and comparative examples of the present application is PA66.

[0028] Example 1

[0029] The present embodiment provides a high-performance composite material, which is composed of the following raw materials by weight: 85 parts of nylon resin, 22 parts of POK resin, 7 parts of hydroxyl-terminated polydimethylsiloxane, 0.2 parts of antioxidant 168, 5 parts of melamine cyanurate, 0.08 parts of pentaerythritol stearate, 19 parts of filler, and 22 parts of glass fiber.

[0030] The preparation method of the above-mentioned filler is as follows:

[0031] (1) according to the dosage ratio of sodium carbonate, manganese nitrate solution 1g: 80ml, sodium carbonate is added to the manganese nitrate solution with a concentration of 0.3mol / L, stirred at 65℃ for 1.5h, after the reaction is completed, it is aged at room temperature for 48h to obtain a mixed solution;

[0032] (2) diatomite is added to nitric acid with a concentration of 4mol / L, stirred at 65℃ for 7h, after the reaction is completed, the product is washed to neutral, calcined at 500℃ for 1h, and sieved through a 400 mesh sieve to obtain pretreated diatomite; according to the mass ratio of pretreated diatomite, mixed solution 1: 15, the pretreated diatomite is added to water, and then the mixed solution of step (1) is added dropwise, heated at 65℃ for 5h, after the reaction is completed, it is aged at room temperature for 24h, filtered, washed and dried to obtain a diatomite composite;

[0033] (3) according to the mass ratio of diatomite composite, propyl triethoxysilane isocyanate 1:0.07, the diatomite composite of step (2) is added to toluene containing propyl triethoxysilane isocyanate, stirred at 65℃ for 2h, after stirring is completed, it is filtered, washed and dried to obtain the filler, and the SEM diagram of the filler is shown in Figure 1 .

[0034] The embodiment also provides a preparation method of the high-performance composite material, and the specific preparation method is as follows:

[0035] According to the weight part ratio, each raw material is weighed and pre-mixed for 4min, and then is put into a double screw extruder for melt blending and extrusion granulation to obtain the high-performance composite material; the screw rotation speed of the double screw extruder is 300r / min, and the temperature of each temperature zone of the extruder is 220℃ for zone 1, 235℃ for zone 2, 235℃ for zone 3, 235℃ for zone 4, 210℃ for zone 5, 210℃ for zone 6, 210℃ for zone 7, 210℃ for zone 8, 210℃ for zone 9, and 230℃ for the die head; the vacuum degree is-0.1MPa.

[0036] Example 2

[0037] The embodiment provides a high-performance composite material, which is composed of the following raw materials in weight parts: nylon resin 90 parts, POK resin 30 parts, hydroxyl-terminated polydimethylsiloxane 10 parts, antioxidant 1010 0.3 parts, melamine cyanurate 8 parts, polyethylene wax 1 part, filler 21 parts, and glass fiber 30 parts.

[0038] The preparation method of the filler is as follows:

[0039] (1) according to the dosage ratio of sodium carbonate, manganese nitrate solution 1g: 100ml, sodium carbonate is added to the manganese nitrate solution with a concentration of 0.5mol / L, stirred at 70℃ for 1h, after the reaction is completed, it is aged at room temperature for 50h to obtain a mixed solution;

[0040] (2) according to the mass ratio of pretreated diatomite and mixed solution 1:20, the pretreated diatomite is added into water, and then the mixed solution of step (1) is added dropwise, heated at 70°C for 4h, after the reaction is completed, it is aged at room temperature for 26h, after filtration, washing and drying, the diatomite composite is obtained;

[0041] (3) according to the mass ratio of diatomite composite and propyl triethoxysilane isocyanate 1:0.1, the diatomite composite of step (2) is added into toluene containing propyl triethoxysilane isocyanate, stirred at 70°C for 1h, after stirring, it is filtered, washed and dried, and the filler is obtained.

[0042] The embodiment also provides a preparation method of the high-performance composite material.

[0043] According to the weight ratio, each raw material is weighed and pre-mixed for 5min, and then is put into a double screw extruder for melt blending and extrusion granulation, and the high-performance composite material is obtained; the screw rotation speed of the double screw extruder is 300r / min, and the temperature of each zone of the extruder is 220°C in zone 1, 235°C in zone 2, 235°C in zone 3, 235°C in zone 4, 210°C in zone 5, 210°C in zone 6, 210°C in zone 7, 210°C in zone 8, 210°C in zone 9, and the die head is 230°C, and the vacuum degree is-0.1MPa.

[0044] Example 3

[0045] The embodiment provides a high-performance composite material, which is composed of the following raw materials in parts by weight: nylon resin 80 parts, POK resin 20 parts, hydroxyl-terminated polydimethylsiloxane 5 parts, antioxidant 168 0.1 part, melamine cyanurate 3 parts, polyethylene wax 0.05 part, filler 15 parts and glass fiber 20 parts.

[0046] The preparation method of the filler is as follows:

[0047] (1) according to the dosage ratio of sodium carbonate and manganese nitrate solution 1g:50mL, sodium carbonate is added into a manganese nitrate solution with a concentration of 0.2mol / L, stirred at 60°C for 2h, after the reaction is completed, it is aged at room temperature for 46h, and the mixed solution is obtained.

[0048] (2) The diatomite is added to nitric acid with a concentration of 3 mol / L, and stirred at 60°C for 9h. After the reaction is completed, the product is washed to neutral, calcined at 450°C for 1.5h, and sieved through a 300 mesh sieve to obtain pretreated diatomite; the pretreated diatomite is added to water according to a mass ratio of pretreated diatomite to mixed solution of 1:10, and then the mixed solution of step (1) is added dropwise, and heated at 60°C for 6h. After the reaction is completed, the product is aged at room temperature for 22h, filtered, washed, and dried to obtain the diatomite composite.

[0049] (3) The diatomite composite of step (2) is added to toluene containing propyl triethoxysilane isocyanate according to a mass ratio of diatomite composite to propyl triethoxysilane isocyanate of 1:0.05, and stirred at 60°C for 3h. After the stirring is completed, the product is filtered, washed, and dried to obtain the filler.

[0050] The embodiment also provides a preparation method of the high-performance composite material.

[0051] According to the weight ratio, each raw material is weighed and pre-mixed for 3min, and then fed into a twin-screw extruder for melt blending and extrusion granulation to obtain the high-performance composite material. The screw rotation speed of the twin-screw extruder is 300r / min, and the temperatures of each temperature zone of the extruder are 220°C for zone 1, 235°C for zone 2, 235°C for zone 3, 235°C for zone 4, 210°C for zone 5, 210°C for zone 6, 210°C for zone 7, 210°C for zone 8, 210°C for zone 9, and 230°C for the die head. The vacuum degree is -0.1MPa.

[0052] Comparative Example 1

[0053] The difference between the comparative example and Example 1 is that the filler is replaced by diatomite, and the rest is the same as Example 1.

[0054] Comparative Example 2

[0055] The difference between the comparative example and Example 1 is that the preparation process of the filler is different, and the rest is the same as Example 1.

[0056] The preparation process of the filler of the comparative example is as follows:

[0057] (1) The diatomite is added to nitric acid with a concentration of 4 mol / L, and stirred at 65°C for 7h. After the reaction is completed, the product is washed to neutral, calcined at 500°C for 1h, and sieved through a 400 mesh sieve to obtain pretreated diatomite;

[0058] (2) The pretreated diatomite of step (1) is added to toluene containing propyl triethoxysilane isocyanate according to a mass ratio of pretreated diatomite to propyl triethoxysilane isocyanate of 1:0.07, and stirred at 65°C for 2h. After the stirring is completed, the product is filtered, washed, and dried to obtain the filler.

[0059] Comparative Example 3

[0060] The present comparative example differs from Example 1 in that the hydroxyl-terminated polydimethylsiloxane is replaced by polydimethylsiloxane, and the rest is the same as Example 1.

[0061] Comparative Example 4

[0062] The present comparative example differs from Example 1 in that the hydroxyl-terminated polydimethylsiloxane is omitted, and the rest is the same as Example 1.

[0063] The properties of the materials obtained in Examples 1-3 and Comparative Examples 1-4 of the present application are described below.

[0064] Mechanical property test: The mechanical properties of the composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were tested according to the American Society for Testing and Materials (ASTM) standards, in which the notched impact strength refers to the ASTM D256 standard, the tensile strength refers to the ASTM D638 standard, and the bending modulus refers to the ASTM D790 standard. The specific test results are shown in Table 1.

[0065] Wear resistance test: The friction coefficient of the composite materials prepared in Examples 1-3 and Comparative Examples 1-4 was tested according to the GB / T 3960-2016 standard, and the results are shown in Table 1.

[0066] Table 1

[0067]

[0068] As can be seen from Table 1, the composite materials obtained in Examples 1-3 have excellent toughness and wear resistance.

[0069] Compared with Example 1, Comparative Example 1 replaces the filler with diatomite, Comparative Example 2 adjusts the preparation method of the filler, Comparative Example 3 replaces the hydroxyl-terminated polydimethylsiloxane with polydimethylsiloxane, and Comparative Example 4 omits the hydroxyl-terminated polydimethylsiloxane. The wear resistance and toughness of the composite materials obtained in the above comparative examples are all reduced. The above results show that the use of the filler and the hydroxyl-terminated polydimethylsiloxane obtained in the present application can improve the wear resistance and toughness of the composite material. This may be due to the increase in the internal pore structure of the pretreated diatomite, and the subsequent column modification with manganese nitrate solution can improve the stability and wear resistance of the material. The surface of the filler is modified with a silane coupling agent, which can improve the compatibility of the filler in the substrate, and on the other hand, the silane coupling agent and the hydroxyl group of the hydroxyl-terminated polydimethylsiloxane can form an ester bond, thereby improving the toughness of the material.

[0070] Finally, it should be pointed out that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application. The basic principles and main features of the present application have been described above with specific embodiments, and some modifications or replacements can be made on the basis of the present application, but these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the present application.

Claims

1. A high-performance composite material, characterized in that, The raw materials include the following parts by weight: 80-90 parts nylon resin, 20-30 parts POK resin, 5-10 parts hydroxyl-terminated polydimethylsiloxane, 0.1-0.3 parts antioxidant, 3-8 parts flame retardant, 0.05-1 part lubricant, 15-21 parts filler, and 20-30 parts glass fiber. The preparation process of the filler is as follows: (1) Sodium carbonate was added to manganese nitrate solution and stirred to react. After the reaction was completed, the mixture was aged at room temperature to obtain a mixed solution. (2) Add the pretreated diatomite to water, and then add the mixed solution from step (1) for heating reaction. After the reaction is completed, age it at room temperature, filter, wash and dry to obtain diatomite composite. (3) Add the diatomaceous earth composite from step (2) to toluene containing silane coupling agent and stir. After stirring, filter, wash and dry to obtain the filler. The preparation method of the pretreated diatomite in step (2) is as follows: add diatomite to nitric acid with a concentration of 3-5 mol / L and stir to react. After the reaction is completed, wash the product until it is neutral, and then calcine and sieve to obtain the product.

2. The high-performance composite material according to claim 1, characterized in that, In step (1), the ratio of sodium carbonate to manganese nitrate solution is 1g:(50-100)mL; the concentration of manganese nitrate solution is 0.2-0.5mol / L; the temperature of the stirring reaction is 60-70℃, the stirring reaction time is 1-2h; and the aging time is 46-50h.

3. The high-performance composite material according to claim 1, characterized in that, In step (2), the mass ratio of the pretreated diatomaceous earth to the mixed solution is 1:(10-20); the heating reaction temperature is 60-70℃, the heating reaction time is 4-6h; and the aging time is 22-26h.

4. The high-performance composite material according to claim 1, characterized in that, In the preparation method of pretreated diatomaceous earth, the stirring reaction temperature is 60-70℃ and the stirring reaction time is 6-9h; the calcination temperature is 450-550℃ and the calcination time is 0.5-1.5h; and the sieve mesh size is 300-500 mesh.

5. The high-performance composite material according to claim 1, characterized in that, In step (3), the mass ratio of the diatomaceous earth composite to the silane coupling agent is 1:(0.05-0.1); the silane coupling agent is propyltriethoxysilane isocyanate; the stirring temperature is 60-70℃ and the stirring time is 1-3h.

6. The high-performance composite material according to claim 1, characterized in that, The antioxidant is antioxidant 168 or antioxidant 1010, the flame retardant is melamine cyanurate, and the lubricant is pentaerythritol stearate or polyethylene wax.

7. The method for preparing the high-performance composite material according to any one of claims 1-6, characterized in that, Includes the following steps: According to the stated weight proportions, each raw material is weighed and premixed, and then melt-extruded, cooled, granulated, and dried to obtain the high-performance composite material.

8. The method for preparing the high-performance composite material according to claim 7, characterized in that, The premixing time is 3-5 minutes; the temperature range of each temperature zone of the melt extrusion is 210-235℃.

Images