Preparation method and application of polyphenyl ether composite material

Abstract

The invention provides a preparation method and application of a polyphenyl ether composite material, and the preparation method comprises the following steps: carrying out preheating treatment on polyphenyl ether at 275-285 DEG C for 30-60 minutes, and carrying out chromaticity test on the polyphenyl ether before and after preheating treatment to obtain delta b; the preparation method comprises the following steps: carrying out extrusion granulation treatment on raw materials including polyphenyl ether, a heat conduction material and an antioxidant to obtain a polyphenyl ether composite material; and the extrusion temperature T, the extrusion rotation speed and the delta b in the extrusion granulation treatment are controlled to meet a specific relationship, so that the yellowness change 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 method for preparing 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 actual applications, resulting in large product color differences, which has a serious negative impact on the production and use of light-colored PPO products. Currently, the yellowing of PPO is generally suppressed by adding additives such as ultraviolet absorbers and antioxidants or modifying PPO, but the improvement effect is limited.

[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 view of the above-mentioned defects, the present invention provides a method for preparing a polyphenylene ether composite material, by preheating the polyphenylene ether to obtain the chromaticity change value Δb of the polyphenylene ether before and after heating, and then subjecting the polyphenylene ether to extrusion granulation treatment with a thermal conductive material and an antioxidant, and making the extrusion temperature T and Δb in the extrusion granulation treatment satisfy a specific relationship, which can effectively improve the yellowing phenomenon in 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] The 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 to 285° C. for 30 to 60 minutes, and the polyphenylene ether before and after the preheating treatment is tested for chromaticity to obtain Δb; wherein Δb is the difference between the yellow-blue chromaticity value of the polyphenylene ether after the preheating treatment and the yellow-blue chromaticity 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, in the extrusion granulation process, the extrusion temperature T and Δb satisfy any of the following relationships, and the extrusion speed R and the extrusion temperature T and Δb satisfy Formula 1,

[0011] 20<Δb≤30, then 250℃≤T<270℃;

[0012] 15<Δb≤20, then 270℃≤T<280℃;

[0013] 10<Δb≤15, then 280℃≤T<300℃;

[0014]

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

[0016] In the method for preparing the polyphenylene ether composite material as described above, the thermally conductive 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 polyphenylene ether composite material as described above, wherein the antioxidant comprises a primary antioxidant and an auxiliary antioxidant, the primary antioxidant comprises a hindered phenol antioxidant, and the auxiliary antioxidant comprises a phosphite antioxidant;

[0018] 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.

[0019] The preparation method of the polyphenylene ether composite material as described above, wherein, in terms of mass percentage, 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.

[0020] In the method for preparing the polyphenylene ether composite material as described above, the raw materials further include a thermoplastic resin, and the thermoplastic resin includes at least one of high-impact polystyrene, nylon, polypropylene, and polyester.

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

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

[0023] The method for preparing the polyphenylene ether composite material as described above, wherein the raw material further comprises 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, wherein the polyphenylene ether composite material 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 the following steps: preheating the polyphenylene ether raw material at 275-285°C for 30-60 minutes 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 then determining the extrusion speed R according to a specific relationship (Formula 1), and then extruding and granulating the polyphenylene ether with an antioxidant and a thermal conductive material, thereby effectively reducing the yellowness change of the polyphenylene ether during the processing and facilitating the dyeing of the product. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination 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 creative work are within the scope of protection of the present invention.

[0029] As one of the world's top five general-purpose engineering plastics, polyphenylene ether (PPO) has excellent mechanical properties, heat resistance and electrical properties. However, the material is prone to yellowing during processing, which has a serious impact on the production and application of light-colored products. Even though there are currently a variety of methods to inhibit its yellowing, the inhibitory effect is limited. Therefore, it is urgent to develop a new method to further reduce its yellowing degree.

[0030] The inventors analyzed that the main reason for the yellowing of polyphenylene ether materials is that the end group oxidation and polycondensation cross-linking reactions occur simultaneously during the processing, wherein the end group oxidation causes the chemical structure of PPO to change, resulting in the generation of coloring substances (quinone substances), which triggers yellowing. Therefore, if yellowing is to be suppressed, the occurrence of end group oxidation needs to be suppressed.

[0031] The inventors found that the extrusion temperature and extrusion speed during the PPO processing have a great influence on the end group oxidation. The higher the extrusion temperature and the faster the extrusion speed, the easier it is to oxidize and the more serious the yellowing. However, the extrusion temperature and extrusion speed have different effects on different PPO raw materials, and it is impossible to match the best processing conditions according to different PPO raw materials.

[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 Δb in the yellow-blue value of the polyphenylene ether before and after heating, determines the extrusion temperature T during the processing according to Δb, and then determines the extrusion speed R according to the specific relationship among Δb, T and the extrusion speed R (Formula 1), thereby obtaining the optimal processing parameters of the PPO raw material, under which the yellowness of the polyphenylene ether can be effectively reduced.

[0033] Furthermore, the inventors found that thermal conductive materials can improve the heat conductivity inside the material during processing, and antioxidants can inhibit the oxidation of end groups, making the end groups more inclined to condensation cross-linking rather than oxidation, thereby further inhibiting the generation of coloring 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 to 285° C. for 30 to 60 minutes, and the polyphenylene ether before and after the preheating treatment is tested for chromaticity to obtain Δb; wherein Δb is the difference between the yellow-blue chromaticity value of the polyphenylene ether after the preheating treatment and the yellow-blue chromaticity value of the polyphenylene ether before the preheating treatment;

[0036] The raw materials including polyphenylene ether, thermal conductive material and antioxidant are subjected to extrusion granulation treatment 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 and 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, thereby effectively eliminating the yellowing phenomenon during the processing and obtaining 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 aggravating yellowing due to the mismatch between the extrusion temperature or the extrusion speed and the polyphenylene ether; at the same time, since the 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, aggravating the yellowing of the material, the present invention can suppress the oxidation reaction of the end group by mixing the polyphenylene ether with a thermal conductive material and an antioxidant, so that the end group is more inclined to polycondensation cross-linking reaction rather than oxidation, and on the other hand, the heat conductivity inside the material during processing can be improved, further avoiding end group oxidation caused by excessive local temperature of the material. Therefore, the preparation method of the present invention can comprehensively reduce the yellowness value of the 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 properties and dielectric properties.

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

[0052] The chromaticity 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, 630 from SABIC, or LXR035, LXR040 or LXR045 from China Bluestar.

[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 specifically limit the mixing method, 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 the 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 violent reaction and aggravate the oxidation of the end group. 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 types of antioxidants and thermal conductive materials also have a certain impact on the yellowing inhibition effect. Therefore, in order to further improve the thermal conductivity and antioxidant properties, it is necessary to further screen the thermal conductive materials and antioxidants.

[0062] In a specific embodiment, the thermal conductive material includes at least one of boron nitride, aluminum oxide, silicon oxide, zinc oxide, aluminum nitride, silicon carbide, and graphite. When the aforementioned thermal conductive materials are selected, better thermal conductivity can be achieved, heat can be better transferred during processing, the yellowing degree of the material can be further reduced, and its heat resistance can be improved.

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

[0064] In a specific 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 specifically limit 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 the deterioration of the mechanical properties of the polyphenylene ether composite material; too little thermal conductive material will lead to poor thermal conductivity, affecting the heat transfer effect during the processing, 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 a specific embodiment, the raw material contains 14 to 76 parts of polyphenylene ether, 1 to 10 parts of thermal conductive material, 0.01 to 1 part of primary antioxidant, and 0.01 to 1 part of auxiliary antioxidant, in terms of mass fractions. In this case, the polyphenylene ether composite material not only has a lower yellowness but also has higher 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] Exemplarily, 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 have the characteristics of softening when heated and hardening when cooled, they can deform when subjected to force 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 the polyphenylene ether composite material.

[0077] In a specific embodiment, the raw material further includes a thermoplastic resin, and the thermoplastic resin includes at least one of high-impact polystyrene, nylon, polypropylene, and polyester. When the raw material further includes 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 influence on the processing performance and dielectric properties of the polyphenylene ether composite material. If there is too much thermoplastic resin, the dielectric properties of the composite material will decrease, and if there is too much polyphenylene ether, the processing performance will decrease. Therefore, it is necessary to further control the mass ratio of thermoplastic resin to polyphenylene ether to ensure the balance between the processing performance and dielectric properties of the polyphenylene ether composite material.

[0082] In a specific embodiment, the mass ratio of the thermoplastic resin to the 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 to 76 parts by weight. 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] Furthermore, in order to improve the fire resistance of the polyphenylene ether composite material, a flame retardant may be added to the raw materials.

[0087] In a specific embodiment, the raw material further includes a flame retardant, and the flame retardant includes a phosphorus-based flame retardant;

[0088] 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.

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

[0090] Furthermore, when the raw materials include the aforementioned phosphorus-based flame retardant, not only can a better flame retardant effect be obtained, but also low smoke, low toxicity, and no corrosive gas are produced during combustion, which is more environmentally friendly and safe.

[0091] When the flame retardant is a mixture of the aforementioned multiple specific flame retardants, the present invention does not specifically limit the ratio between the specific flame retardants.

[0092] The present invention does not specifically limit the source of the flame retardant, 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.

[0093] Furthermore, the mass fraction of the flame retardant in the raw material will also have an adverse effect on the mechanical properties of the polyphenylene ether composite material.

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

[0095] Exemplarily, 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 invention provides a polyphenylene ether composite material, which is prepared by the preparation method of the polyphenylene ether composite material of the first aspect. Therefore, the polyphenylene ether composite material has a lower 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 is molded into tablets at a temperature of 280°C and a pressure of 400 kN. The PPO powder before and after heating is tested for colorimetry, and a Δb of 30 is obtained. The extrusion temperature T is determined to be 250°C and the extrusion speed R is determined to be 300 r / min.

[0102] 2) The above raw materials are mixed uniformly in a high-speed mixer, and the mixed raw materials are 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 alumina, 200g of flame retardant RDP, 20g of primary antioxidant 1010, and 20g of auxiliary antioxidant 618;

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

[0106] 2) The above raw materials are mixed uniformly in a high-speed mixer, and the mixed raw materials are 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: 750g of polyphenylene ether (PPO) powder (end group content 820ppm), 750g of high impact polystyrene (HIPS), 100g of graphite, 400g of flame retardant PX220, 2g of primary antioxidant 1024, and 4g of auxiliary antioxidant PEPQ;

[0109] 1) The PPO powder is molded into tablets at a temperature of 280°C and a pressure of 400 kN. The PPO powder before and after heating is tested for colorimetry, and a Δb of 10 is obtained. 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 above raw materials are mixed uniformly in a high-speed mixer, and the mixed raw materials are 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.

[0111] Example 4

[0112] 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 end group content of the polyphenylene ether is 1080 ppm, the Δb of the polyphenylene ether is 23, the extrusion temperature T is set to 265°C, and the extrusion speed R is 400 r / min.

[0113] Example 5

[0114] 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 end group content of the polyphenylene ether is 1000 ppm, the Δb of the polyphenylene ether is 20, the extrusion temperature T is set to 270°C, and the extrusion speed R is 250 r / min.

[0115] Example 6

[0116] 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 end group content of the polyphenylene ether is 970 ppm, the Δb of the polyphenylene ether is 16, the extrusion temperature T is set to 275°C, and the extrusion speed R is 430 r / min.

[0117] Example 7

[0118] 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 end group content of the polyphenylene ether is 860 ppm, the Δb of the polyphenylene ether is 11, the extrusion temperature T is set to 295° C., and the extrusion speed R is 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 material does 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 the GB / T 1633-2000 method. 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 the ASTM D 6290 method. The test results are shown in Table 2. The lower b is, the lower the yellowing degree of 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 method. 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] It can be seen from Table 2 that, 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned 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 is preheated at 275 to 285° C. for 30 to 60 minutes, and the polyphenylene ether before and after the preheating treatment is tested for chromaticity to obtain Δb; wherein Δb is the difference between the yellow-blue chromaticity value of the polyphenylene ether after the preheating treatment and the yellow-blue chromaticity value of the polyphenylene ether before the preheating treatment; 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, 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, 20<Δb≤30, then 250℃≤T<270℃; 15<Δb≤20, then 270℃≤T<280℃; 10<Δb≤15, then 280℃≤T<300℃; 2. The method for preparing the polyphenylene ether composite material according to claim 1, characterized in that: The extrusion speed R is 200-600 r / min.

3. The method for preparing the polyphenylene ether composite material according to claim 1 or 2, characterized in that: The thermally 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 any one of claims 1 to 3, characterized in that: The antioxidant includes a primary antioxidant and an auxiliary antioxidant, wherein the primary antioxidant includes a hindered phenol antioxidant, and the auxiliary antioxidant includes a phosphite antioxidant; 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.

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

6. The method for preparing the polyphenylene ether composite material according to any one of claims 1 to 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; Preferably, the thermoplastic resin in the raw material is 14 to 76 parts by mass.

8. The method for preparing the polyphenylene ether composite material according to any one of claims 1 to 7, characterized in that: The raw material also includes a flame retardant, and the flame retardant includes a phosphorus-based flame retardant; 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.

9. The method for preparing the polyphenylene ether composite material according to claim 8, characterized in that: According to the mass percentage, the flame retardant in the raw material 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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