Preparation method of polyphenyl ether composite material and application thereof

Abstract

The application provides a preparation method of a polyphenyl ether composite material and application thereof, and the preparation method comprises the following steps: pre-heating treatment of polyphenyl ether at 275-285 DEG C for 30-60 min; colorimetric test is conducted on the polyphenyl ether before and after the pre-heating treatment to obtain Δb; raw materials including polyphenyl ether, a heat-conducting material and an antioxidant are subjected to extrusion granulation treatment to obtain the polyphenyl ether composite material; and the extrusion temperature T, the extrusion rotating speed and Δb in the extrusion granulation treatment satisfy a specific relationship, so that the change of the yellowness of the polyphenyl ether in the processing process can be effectively reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a preparation method of a polyphenylene ether composite material. Background Art

[0002] Polyphenylene ether is a high-strength engineering plastic developed in the 1960s. Its chemical name is poly 2,6-dimethyl-1,4-phenylene ether, abbreviated as PPO. It is one of the world's five major general-purpose engineering plastics. It has excellent mechanical properties, heat resistance and electrical properties, and is widely used in electronic appliances, household appliances, office equipment, automobiles, chemicals and industrial machinery.

[0003] However, PPO is prone to yellowing in practical applications, resulting in large color variations and severely impacting the production and use of light-colored PPO products. Currently, efforts to suppress this yellowing are generally made by adding additives such as UV absorbers and antioxidants, or by modifying the PPO, but these efforts have limited success.

[0004] Therefore, it is necessary to further improve the processing method of polyphenylene ether to improve its yellowing phenomenon. Summary of the Invention

[0005] In response to the above-mentioned defects, the present invention provides a method for preparing a polyphenylene ether composite material, in which the chromaticity change value Δb of the polyphenylene ether before and after heating is obtained by preheating the polyphenylene ether, and then the polyphenylene ether is extruded and granulated with a thermally conductive material and an antioxidant, and the extrusion temperature T and Δb in the extrusion granulation process satisfy a specific relationship, which can effectively improve the yellowing phenomenon during the processing of the polyphenylene ether and reduce its yellowness.

[0006] The present invention also provides a polyphenylene ether composite material, which is prepared by the above-mentioned preparation method. The polyphenylene ether composite material has a lower yellowness and can be used for the production of light-colored products.

[0007] A first aspect of the present invention provides a method for preparing a polyphenylene ether composite material, comprising the following steps:

[0008] The polyphenylene ether is preheated at 275-285° C. for 30-60 minutes, and the colorimetric test of the polyphenylene ether before and after the preheating treatment is performed to obtain Δb; wherein Δb is the difference between the yellow-blue color value of the polyphenylene ether after the preheating treatment and the yellow-blue color value of the polyphenylene ether before the preheating treatment;

[0009] Extruding and granulating the raw materials including the polyphenylene ether, the thermal conductive material and the antioxidant to obtain the polyphenylene ether composite material;

[0010] Wherein, the extrusion temperature T and Δb in the extrusion granulation process satisfy any of the following relationships, and the extrusion speed R, the extrusion temperature T and Δb satisfy Formula 1,

[0011] 20 < Δb ≤ 30, 250℃ ≤ T < 270℃;

[0012] 15 < Δb ≤ 20, 270℃ ≤ T < 280℃;

[0013] 10 < Δb ≤ 15, 280℃ ≤ T < 300℃;

[0014]

[0015] The method for preparing the polyphenyl ether composite material as described above, wherein the extrusion speed R is 200-600 r / min.

[0016] The method for preparing the polyphenyl ether composite material as described above, wherein the heat-conducting material comprises at least one of boron nitride, aluminum oxide, silicon oxide, zinc oxide, aluminum nitride, silicon carbide and graphite.

[0017] The method for preparing the polyphenyl ether composite material as described above, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, the primary antioxidant comprises a hindered phenol antioxidant, and the secondary antioxidant comprises a phosphite antioxidant.

[0018] Preferably, the hindered phenol antioxidant comprises at least one of antioxidant 1076, antioxidant 1010, antioxidant 1024 and antioxidant 2246; and / or the phosphite antioxidant comprises at least one of antioxidant 618, antioxidant 168, antioxidant 126 and PEPQ antioxidant.

[0019] The method for preparing the polyphenyl ether composite material as described above, wherein the polyphenyl ether in the raw materials is 14-76 parts by mass, and / or the heat-conducting material is 1-10 parts by mass, and / or the primary antioxidant is 0.01-1 part by mass, and / or the secondary antioxidant is 0.01-1 part by mass.

[0020] The method for preparing the polyphenyl ether composite material as described above, wherein the raw materials further comprise a thermoplastic resin, and the thermoplastic resin comprises at least one of high-impact polystyrene, nylon, polypropylene and polyester.

[0021] The method for preparing the polyphenyl ether composite material as described above, wherein the mass ratio of the thermoplastic resin to the polyphenyl ether is 2:8-8:2.

[0022] Preferably, the thermoplastic resin in the raw materials is 14-76 parts by mass.

[0023] The method for preparing the polyphenyl ether composite material as described above, wherein the raw materials further comprise a flame retardant, and the flame retardant comprises a phosphorus-based flame retardant.

[0024] Preferably, the phosphorus-based flame retardant includes at least one of flame retardant TPP, flame retardant RDP, flame retardant BDP, flame retardant RDX, and flame retardant PX220.

[0025] The method for preparing the polyphenylene ether composite material as described above, wherein the flame retardant in the raw material is 5-20 parts by mass.

[0026] A second aspect of the present invention provides a polyphenylene ether composite material, which is prepared by the preparation method of the polyphenylene ether composite material described in the first aspect.

[0027] The preparation method of the polyphenylene ether composite material of the present invention comprises preheating the polyphenylene ether raw material at 275-285°C for 30-60 minutes to obtain a change Δb in the yellow-blue value of the polyphenylene ether before and after heating, determining the extrusion temperature T based on Δb, and then determining the extrusion speed R according to a specific relationship (Equation 1). The polyphenylene ether is then subjected to an extrusion granulation treatment with an antioxidant and a thermally conductive material. This method can effectively reduce the yellowness change of the polyphenylene ether during processing and facilitate the dyeing of the product. DETAILED DESCRIPTION

[0028] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0029] Polyphenylene ether (PPO), one of the world's top five general-purpose engineering plastics, possesses excellent mechanical, heat-resistant, and electrical properties. However, it is susceptible to yellowing during processing, severely impacting the production and application of light-colored products. While various methods are currently available to inhibit this yellowing, their effectiveness is limited. Therefore, there is an urgent need to develop new methods to further reduce the extent of this yellowing.

[0030] The inventors analyzed that the main reason for the yellowing of polyphenylene ether materials is the simultaneous occurrence of end group oxidation and condensation crosslinking reactions during processing. The end group oxidation causes changes in the chemical structure of PPO, leading to the production of color-causing substances (quinones) and causing yellowing. Therefore, to prevent yellowing, it is necessary to inhibit the occurrence of end group oxidation.

[0031] The inventors discovered that the extrusion temperature and speed during PPO processing significantly affect end group oxidation. Higher extrusion temperatures and higher extrusion speeds increase the likelihood of oxidation and the severity of yellowing. However, the effects of extrusion temperature and speed vary for different PPO raw materials, making it difficult to optimally match processing conditions to each.

[0032] Therefore, the present invention first preheats the PPO raw material within a specific temperature range for a certain period of time to obtain a change in the yellow-blue value of the polyphenylene ether before and after heating, Δb. The extrusion temperature T during the processing is determined based on Δb. The extrusion speed R is then determined based on the specific relationship between Δb, T, and the extrusion speed R (Formula 1), thereby obtaining the optimal processing parameters of the PPO raw material. Under these processing conditions, the yellowness of the polyphenylene ether can be effectively reduced.

[0033] Furthermore, the inventors found that thermal conductive materials can improve the heat transfer inside the material during processing, and antioxidants can inhibit the oxidation of end groups, making the end groups more inclined to condensation and cross-linking rather than oxidation, thereby further inhibiting the production of color-causing substances and reducing the yellowness of the polyphenylene ether material.

[0034] Based on the above analysis, the first aspect of the present invention provides a method for preparing a polyphenylene ether composite material, comprising the following steps:

[0035] The polyphenylene ether is preheated at 275-285° C. for 30-60 minutes, and the colorimetric test of the polyphenylene ether before and after the preheating treatment is performed to obtain Δb; wherein Δb is the difference between the yellow-blue color value of the polyphenylene ether after the preheating treatment and the yellow-blue color value of the polyphenylene ether before the preheating treatment;

[0036] Extrusion granulation is performed on raw materials including polyphenylene ether, a thermal conductive material and an antioxidant to obtain a polyphenylene ether composite material;

[0037] In the extrusion granulation process, the extrusion temperature T and Δb satisfy any of the following relationships, and the extrusion speed R, the extrusion temperature T and Δb satisfy Formula 1,

[0038] 20<Δb≤30, then 250℃≤T<270℃;

[0039] 15<Δb≤20, then 270℃≤T<280℃;

[0040] 10<Δb≤15, then 280℃≤T<300℃;

[0041]

[0042] Specifically, a colorimetric test is performed on the polyphenylene ether raw material to obtain a yellow-blue color value b0 of the polyphenylene ether before treatment; the polyphenylene ether raw material is preheated at 275-285°C for 30-60 minutes, and a colorimetric test is performed on the treated polyphenylene ether raw material to obtain a yellow-blue color value b1 of the treated polyphenylene ether, then Δb is b1-b0.

[0043] The raw materials including the above-mentioned polyphenylene ether raw material, thermal conductive material and antioxidant are subjected to extrusion granulation treatment, wherein the extrusion temperature T and Δb satisfy any of the following relationships, and the extrusion speed R, the extrusion temperature T and Δb satisfy Formula 1,

[0044] 20<Δb≤30, then 250℃≤T<270℃;

[0045] 15<Δb≤20, then 270℃≤T<280℃;

[0046] 10<Δb≤15, then 280℃≤T<300℃;

[0047]

[0048] The polyphenylene ether composite material is obtained by processing according to the extrusion speed R and extrusion temperature T determined above.

[0049] The preparation method of the polyphenylene ether composite material of the present invention comprises the following steps: preheating the raw material polyphenylene ether for a certain period of time within a specific temperature range to obtain a yellow-blue value change Δb of the polyphenylene ether before and after heating; determining the extrusion temperature T according to Δb; and determining the extrusion speed R according to Δb and the extrusion temperature T; and then extruding and granulating the raw material including the polyphenylene ether, the thermal conductive material and the antioxidant according to the aforementioned determined processing parameters. This can effectively eliminate the yellowing phenomenon during the processing and obtain a polyphenylene ether composite material that is easy to dye. This is mainly because: the preparation method can be designed according to different polyphenylene ether raw materials The corresponding processing parameters are used to avoid exacerbating yellowing due to the mismatch between the extrusion temperature or the extrusion speed and the polyphenylene ether. At the same time, since polyphenylene ether undergoes both end group oxidation and polycondensation cross-linking reactions during processing, and the end group oxidation will lead to the production of quinone substances, exacerbating the yellowing of the material, the present invention combines polyphenylene ether with a thermally conductive material and an antioxidant for processing. On the one hand, the oxidation reaction of the end group can be inhibited, making the end group more inclined to polycondensation cross-linking reaction rather than oxidation. On the other hand, the heat conductivity inside the material during processing can be improved, further avoiding end group oxidation caused by excessively high local temperature of the material. Therefore, the preparation method of the present invention can comprehensively reduce the yellowness value of polyphenylene ether and improve its processing performance.

[0050] In addition, the polyphenylene ether composite material prepared by the preparation method of the present invention also has high heat resistance and excellent mechanical and dielectric properties.

[0051] The present invention does not specifically limit the method of preheating treatment. For example, preheating treatment can be performed by compression molding, maintaining a heating temperature of 275-285°C, a pressure of 400kN, and a heating time of 30-60min.

[0052] The color test in the present invention is carried out according to ASTM D 6290.

[0053] The present invention does not specifically limit the source of the polyphenylene ether, and any commercially available product or a product prepared by a conventional preparation method known to those skilled in the art may be used, for example, SABIC's 630, or China Bluestar's LXR035, LXR040, or LXR045.

[0054] Furthermore, before the extrusion granulation process, the raw materials including the polyphenylene ether, the thermal conductive material and the antioxidant are mixed evenly to further improve the performance of the polyphenylene ether composite material.

[0055] The present invention does not impose any specific limitation on the mixing method, and for example, uniform mixing can be performed in a high-speed mixer.

[0056] The present invention does not specifically limit the method of extrusion granulation treatment, for example, a dedicated extruder is used for extrusion granulation treatment.

[0057] The present invention does not specifically limit the types and sources of the thermal conductive material and antioxidant, and commercially available products or products prepared by conventional preparation methods well known to those skilled in the art may be used.

[0058] Furthermore, the yellowing phenomenon of polyphenylene ether can be further suppressed by controlling the extrusion speed R. Too high an extrusion speed will lead to a violent reaction and aggravate the oxidation of the end groups. Too low an extrusion speed will also lead to uneven mixing and poor performance.

[0059] In a specific embodiment, the extrusion speed R is 200-600 r / min. Within this range, the yellowing degree of the polyphenylene ether during processing can be further reduced, and its processing performance can be improved.

[0060] Illustratively, R is 200 r / min, 250 r / min, 300 r / min, 350 r / min, 400 r / min, 450 r / min, 500 r / min, 550 r / min or 600 r / min.

[0061] At the same time, the type of antioxidant and thermal conductive material also has a certain impact on the yellowing inhibition effect. Therefore, in order to further improve the thermal conductivity and antioxidant properties, further screening of thermal conductive materials and antioxidants is required.

[0062] In one embodiment, the thermally conductive material includes at least one of boron nitride, aluminum oxide, silicon oxide, zinc oxide, aluminum nitride, silicon carbide, and graphite. The use of these thermally conductive materials can achieve better thermal conductivity, facilitate heat transfer during processing, further reduce yellowing of the material, and enhance heat resistance.

[0063] When the thermally conductive material is a mixture of the aforementioned multiple specific substances, the present invention does not impose any specific limitation on the ratio between the specific substances.

[0064] In one embodiment, the antioxidant includes a primary antioxidant and a secondary antioxidant, the primary antioxidant includes a hindered phenol antioxidant, and the secondary antioxidant includes a phosphite antioxidant;

[0065] Preferably, the hindered phenol antioxidant includes at least one of antioxidant 1076, antioxidant 1010, antioxidant 1024, and antioxidant 2246; and / or the phosphite antioxidant includes at least one of antioxidant 618, antioxidant 168, antioxidant 126, and PEPQ antioxidant.

[0066] When the antioxidant includes a hindered phenol antioxidant and a phosphite antioxidant, and further includes the aforementioned antioxidant, a better antioxidant effect can be achieved, thereby further inhibiting the yellowing of the material.

[0067] When the primary antioxidant and the auxiliary antioxidant are respectively a mixture of the aforementioned specific compounds, the present invention does not impose any specific limitation on the ratio between the specific compounds.

[0068] Furthermore, the mass fractions of polyphenylene ether, thermal conductive material, primary antioxidant and auxiliary antioxidant in the processing raw materials also have a significant impact on the yellowness of the polyphenylene ether composite material.

[0069] Among them, too much thermal conductive material will lead to poor mechanical properties of polyphenylene ether composite materials; too little thermal conductive material will lead to poor thermal conductivity, affecting the heat transfer effect during the processing process, making the end group more prone to oxidation, and aggravating the yellowing of the material.

[0070] Similarly, if the primary antioxidant and the auxiliary antioxidant are too little, they will not be able to exert their antioxidant effect, resulting in the oxidation of some end groups, generating coloring substances, and affecting the yellowness of the material; too much primary antioxidant and the auxiliary antioxidant will also affect the mechanical properties of the polyphenylene ether composite material, and the cost is high, which is not conducive to production.

[0071] In one embodiment, the raw materials include 14 to 76 parts by weight of polyphenylene ether, 1 to 10 parts by weight of thermal conductive material, 0.01 to 1 part by weight of primary antioxidant, and 0.01 to 1 part by weight of auxiliary antioxidant. The polyphenylene ether composite material exhibits both low yellowness and high mechanical properties.

[0072] Illustratively, the polyphenylene ether in the raw material is 14 parts, 24 parts, 34 parts, 44 parts, 54 parts, 64 parts, 74 parts or 76 parts.

[0073] Exemplarily, the thermal conductive material in the raw material is 1 part, 3 parts, 5 parts, 7 parts, 9 parts or 10 parts.

[0074] Illustratively, the primary antioxidant in the raw material is 0.01 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part or 1 part.

[0075] Illustratively, the auxiliary antioxidant in the raw material is 0.01 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part or 1 part.

[0076] Furthermore, since thermoplastic resins soften when heated and harden when cooled, they can deform when subjected to stress and better disperse and withstand stress. Therefore, thermoplastic resins can also be added to the raw materials to improve the mechanical properties and processing properties of polyphenylene ether composites.

[0077] In one embodiment, the raw materials further include a thermoplastic resin, and the thermoplastic resin includes at least one of high-impact polystyrene, nylon, polypropylene, and polyester. When the raw materials further include the aforementioned thermoplastic resin, the processability and mechanical properties of the polyphenylene ether can be effectively improved.

[0078] When the thermoplastic resin is a mixture of the aforementioned multiple specific compounds, the present invention does not specifically limit the ratio of each specific compound.

[0079] The present invention does not impose any particular limitation on the molecular weight of the thermoplastic resin.

[0080] The present invention does not specifically limit the source of the thermoplastic resin, and any commercially available product or a product prepared by a conventional preparation method well known to those skilled in the art may be used.

[0081] Furthermore, the ratio of thermoplastic resin to polyphenylene ether also has a certain impact on the processing performance and dielectric properties of polyphenylene ether composites. If the thermoplastic resin is too much, the dielectric properties of the composite will be reduced, and if the polyphenylene ether is too much, the processing performance will be reduced. Therefore, it is necessary to further control the mass ratio of thermoplastic resin to polyphenylene ether to ensure a balance between the processing performance and dielectric properties of the polyphenylene ether composite.

[0082] In one embodiment, the mass ratio of thermoplastic resin to polyphenylene ether is 2:8 to 8:2. Within this range, the polyphenylene ether composite material has both good dielectric properties and processing properties.

[0083] Illustratively, the mass ratio is 2:8, 3:7, 4:6, 5:5, 6:4, 7:3 or 8:2.

[0084] Preferably, the thermoplastic resin in the raw material is 14-76 parts by mass. Within this range, the processing performance of the polyphenylene ether composite material can be improved while ensuring high dielectric properties.

[0085] Illustratively, the thermoplastic resin in the raw material is 14 parts, 24 parts, 34 parts, 44 parts, 54 parts, 64 parts, 74 parts or 76 parts.

[0086] Further, in order to improve the fireproof performance of the polyphenylene ether composite material, a flame retardant can also be added to the raw material.

[0087] In one specific embodiment, the raw material further comprises a flame retardant, and the flame retardant comprises a phosphorus-based flame retardant.

[0088] Preferably, the phosphorus-based flame retardant comprises at least one of flame retardant TPP, flame retardant RDP, flame retardant BDP, flame retardant RDX, and flame retardant PX220.

[0089] When the raw material comprises the flame retardant, the flame retardant effect of the polyphenylene ether composite material can be effectively improved.

[0090] Further, when the raw material comprises the aforementioned phosphorus-based flame retardant, not only a good flame retardant effect can be obtained, but also low smoke, low toxicity, and no corrosive gas during combustion, which is more environmentally friendly and safe.

[0091] When the flame retardant is a mixture of the aforementioned various specific flame retardants, the present application does not make specific limitations on the ratio between each specific flame retardant.

[0092] The present application does not make specific limitations on the source of the flame retardant, and products prepared by commercially available products or conventional preparation methods known to those skilled in the art can be used.

[0093] Further, the mass fraction of the flame retardant in the raw material can also adversely affect the mechanical properties of the polyphenylene ether composite material.

[0094] In one specific embodiment, the flame retardant in the raw material is 5-20 parts by mass. Within this range, not only can a high flame retardant effect be ensured, but also the mechanical properties of the polyphenylene ether composite material will not be affected.

[0095] Illustratively, the flame retardant in the raw material is 5 parts, 8 parts, 11 parts, 14 parts, 17 parts or 20 parts.

[0096] The second aspect of the present application provides a polyphenylene ether composite material prepared by the preparation method of the polyphenylene ether composite material of the first aspect. Therefore, the polyphenylene ether composite material has low yellowness and can be used for the production of light-colored products.

[0097] The preparation method of the polyphenylene ether composite material provided by the present invention will be specifically introduced below through specific examples.

[0098] Unless otherwise specified, the reagents, materials, and instruments used in the following examples are conventional reagents, conventional materials, and conventional instruments in the art and can be obtained commercially. The reagents involved can also be synthesized by conventional methods in the art.

[0099] Example 1

[0100] The raw materials include: 1504g of polyphenylene ether (PPO) powder (end group content is 1300ppm), 376g of high impact polystyrene (HIPS), 20g of boron nitride, 100g of flame retardant TPP, 0.2g of primary antioxidant 1076, and 0.2g of auxiliary antioxidant 168;

[0101] 1) The PPO powder was molded into tablets at a temperature of 280°C and a pressure of 400 kN. The colorimetric test of the PPO powder before and after heating was performed, and a Δb value of 30 was obtained. Therefore, the extrusion temperature T was determined to be 250°C and the extrusion speed R was determined to be 300 r / min.

[0102] 2) The above raw materials were mixed uniformly in a high-speed mixer, and the mixed raw materials were added to a twin-screw extruder, and melt-extruded under a nitrogen atmosphere according to the above processing parameters to obtain the polyphenylene ether composite material of this embodiment.

[0103] Example 2

[0104] The raw materials include: 320g of polyphenylene ether (PPO) powder (end group content 930ppm), 1280g of high impact polystyrene (HIPS), 200g of aluminum oxide, 200g of flame retardant RDP, 20g of primary antioxidant 1010, and 20g of auxiliary antioxidant 618;

[0105] 1) The PPO powder was molded into tablets at a temperature of 280°C and a pressure of 400 kN. The colorimetric test of the PPO powder before and after heating was performed, and a Δb value of 15 was obtained. Therefore, the extrusion temperature T was determined to be 280°C and the extrusion speed R was determined to be 300 r / min.

[0106] 2) The above raw materials were mixed uniformly in a high-speed mixer, and the mixed raw materials were added to a twin-screw extruder, and melt-extruded under a nitrogen atmosphere according to the above processing parameters to obtain the polyphenylene ether composite material of this embodiment.

[0107] Example 3

[0108] The raw materials include: 750 g of polyphenylene ether (PPO) powder (the content of end group is 820 ppm), 750 g of high-impact polystyrene (HIPS), 100 g of graphite, 400 g of flame retardant PX220, 2 g of primary antioxidant 1024, and 4 g of auxiliary antioxidant PEPQ;

[0109] 1) The PPO powder is subjected to mold pressing at a temperature of 280°C and a pressure of 400 kN. Colorimetric test is performed on the PPO powder before and after heating, and the Δb is 10. Then the extrusion temperature T is determined to be 300°C, and the extrusion speed R is determined to be 300 r / min.

[0110] 2) The raw materials are uniformly mixed in a high-speed mixer, and then the mixed raw materials are added into a twin-screw extruder. The raw materials are subjected to melt extrusion in a nitrogen atmosphere according to the above processing parameters, and the polyphenylene ether composite material of the present embodiment is obtained.

[0111] Example 4

[0112] The preparation method of the polyphenylene ether composite material in the present embodiment is basically the same as that in Example 1, except that in step 1), the content of end group of the polyphenylene ether is 1080 ppm, the Δb of the polyphenylene ether is 23, the extrusion temperature T is set to be 265°C, and the extrusion speed R is set to be 400 r / min.

[0113] Example 5

[0114] The preparation method of the polyphenylene ether composite material in the present embodiment is basically the same as that in Example 1, except that in step 1), the content of end group of the polyphenylene ether is 1000 ppm, the Δb of the polyphenylene ether is 20, the extrusion temperature T is set to be 270°C, and the extrusion speed R is set to be 250 r / min.

[0115] Example 6

[0116] The preparation method of the polyphenylene ether composite material in the present embodiment is basically the same as that in Example 1, except that in step 1), the content of end group of the polyphenylene ether is 970 ppm, the Δb of the polyphenylene ether is 16, the extrusion temperature T is set to be 275°C, and the extrusion speed R is set to be 430 r / min.

[0117] Example 7

[0118] The preparation method of the polyphenylene ether composite material in the present embodiment is basically the same as that in Example 1, except that in step 1), the content of end group of the polyphenylene ether is 860 ppm, the Δb of the polyphenylene ether is 11, the extrusion temperature T is set to be 295°C, and the extrusion speed R is set to be 410 r / min.

[0119] Example 8

[0120] The preparation method of the polyphenylene ether composite material in this embodiment is basically the same as that in Example 1, except that in step 1), the mass of the polyphenylene ether (PPO) powder is adjusted to 1520 g, and the mass of the high-impact polystyrene (HIPS) is adjusted to 360 g.

[0121] Comparative Example 1

[0122] The preparation method of the polyphenylene ether composite material in this comparative example is basically the same as that in Example 1, except that the raw materials do not contain the thermal conductive material boron nitride.

[0123] Comparative Example 2

[0124] The preparation method of the polyphenylene ether composite material in this comparative example is basically the same as that in Example 1, except that in step 1), the extrusion temperature is 320°C.

[0125] Comparative Example 3

[0126] The preparation method of the polyphenylene ether composite material in this comparative example is basically the same as that in Example 1, except that in step 1), the extrusion speed R is 600 r / min.

[0127] Comparative Example 4

[0128] The preparation method of the polyphenylene ether composite material in this comparative example is basically the same as that in Example 1, except that the raw materials do not contain a primary antioxidant and an auxiliary antioxidant.

[0129] Comparative Example 5

[0130] The preparation method of the polyphenylene ether composite material in this comparative example is basically the same as that in Example 1, except that in step 1), the extrusion speed R is 200 r / min.

[0131] The specific sources of the raw materials used in the above examples and comparative examples are shown in Table 1.

[0132] Table 1

[0133]

[0134] Test example

[0135] The heat resistance, yellowness, mechanical properties and dielectric properties of the polyphenylene ether composite materials prepared in the above examples and comparative examples were tested. The test results are shown in Table 2.

[0136] 1) Heat Resistance: The Vicat temperature of the polyphenylene ether composite material was obtained by testing according to GB / T 1633-2000. The test results are shown in Table 2. The higher the Vicat temperature, the smaller the thermal deformation of the material when heated and the better the thermal stability.

[0137] 2) Yellowness: The yellow-blue value b of the polyphenylene ether composite material was obtained by testing according to ASTM D 6290. The test results are shown in Table 2. The lower the b, the less yellowing the material is and the easier it is to dye.

[0138] 3) Mechanical properties: The tensile strength of the polyphenylene ether composite material was obtained by testing according to ISO 527-2. The test results are shown in Table 2. The higher the tensile strength, the better the mechanical properties.

[0139] 4) Dielectric Properties: The dielectric constant of the polyphenylene ether composite material was obtained by testing at 50 Hz according to the GB / T 1409-2006 method. The test results are shown in Table 2. The lower the dielectric constant, the better the dielectric properties.

[0140] Table 2

[0141]

[0142] As can be seen from Table 2, compared with Comparative Examples 1 to 5, the polyphenylene ether composite materials in Examples 1 to 8 have higher Vicat temperatures and lower b values. It can be seen that the preparation method of the present invention can effectively reduce the yellowness of the composite material and effectively improve the heat resistance of the composite material.

[0143] Among them, the tensile strength of the polyphenylene ether composite material in Example 3 is low and the dielectric constant is increased. This is mainly because the high impact polystyrene (HIPS) content in the polyphenylene ether composite material is high and the polyphenylene ether content is low. However, the processing performance of the composite material is relatively excellent, and the heat resistance of the composite material is relatively high, and the yellowness change is also small. Overall, it has good comprehensive performance.

[0144] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a polyphenylene ether composite material, characterized in that: The following steps are involved: The polyphenylene ether was preheated at 275-285°C for 30-60 minutes, and the color of the polyphenylene ether before and after the preheating treatment was tested. ;in, is the difference between the yellow-blue value of the polyphenylene ether after preheating and the yellow-blue value of the polyphenylene ether before preheating; Extruding and granulating the raw materials including the polyphenylene ether, the thermal conductive material and the antioxidant to obtain the polyphenylene ether composite material; Wherein, the extrusion temperature T and Satisfy any of the following relationships, and the extrusion speed R and the extrusion temperature T and Satisfying formula 1, 20< ≤30, then 250℃≤T<270℃; 15< ≤20, then 270℃≤T<280℃; 10< ≤15, then 280℃≤T<300℃; Formula 1.

2. The method for preparing the polyphenylene ether composite material according to claim 1, wherein: The extrusion speed R is 200~600r / min.

3. The method for preparing the polyphenylene ether composite material according to claim 1 or 2, wherein: The thermal conductive material includes at least one of boron nitride, aluminum oxide, silicon oxide, zinc oxide, aluminum nitride, silicon carbide, and graphite.

4. The method for preparing the polyphenylene ether composite material according to claim 1 or 2, wherein: The antioxidant includes a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant includes a hindered phenol antioxidant and the secondary antioxidant includes a phosphite antioxidant; The hindered phenol antioxidant includes at least one of antioxidant 1076, antioxidant 1010, antioxidant 1024, and antioxidant 2246; and / or the phosphite antioxidant includes at least one of antioxidant 618, antioxidant 168, antioxidant 126, and PEPQ antioxidant.

5. The method for preparing the polyphenylene ether composite material according to claim 4, characterized in that: In terms of mass parts, the polyphenylene ether in the raw material is 14 to 76 parts, and / or the thermal conductive material is 1 to 10 parts, and / or the primary antioxidant is 0.01 to 1 part, and / or the auxiliary antioxidant is 0.01 to 1 part.

6. The method for preparing the polyphenylene ether composite material according to claim 5, characterized in that: The raw materials also include thermoplastic resin, and the thermoplastic resin includes at least one of high-impact polystyrene, nylon, polypropylene, and polyester.

7. The method for preparing the polyphenylene ether composite material according to claim 6, characterized in that: The mass ratio of the thermoplastic resin to the polyphenylene ether is 2:8 to 8:2; In terms of parts by mass, the thermoplastic resin in the raw material is 14 to 76 parts.

8. The method for preparing the polyphenylene ether composite material according to claim 6, characterized in that: The raw materials also include a flame retardant, and the flame retardant includes a phosphorus-based flame retardant; The phosphorus-based flame retardant includes at least one of flame retardant TPP, flame retardant RDP, flame retardant BDP, flame retardant RDX, and flame retardant PX220.

9. The method for preparing the polyphenylene ether composite material according to claim 8, characterized in that: According to parts by mass, the flame retardant in the raw materials is 5-20 parts.

10. A polyphenylene ether composite material, characterized in that: The polyphenylene ether composite material is prepared by the preparation method of the polyphenylene ether composite material according to any one of claims 1 to 9.

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