Polyphenyl ether composition and application thereof in new energy automobile

Abstract

The invention relates to the field of high polymer materials, in particular to a polyphenyl ether composition and application in new energy automobiles, and the polyphenyl ether composition comprises epoxy-terminated polyphenyl ether, modified polyvinyl chloride resin and polyphenyl ether grafted maleic anhydride. The modified polyvinyl chloride resin is obtained by copolymerization of aminated polyvinyl chloride resin and N-styryl carbazole free radicals, and the polyphenyl ether composition not only has excellent mechanical properties, but also shows good dielectric properties, and has huge application potential in new energy automobiles.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, in particular to a polyphenylene ether composition and its application in new energy vehicles. Background Art

[0002] As the core material of printed circuit boards, copper clad laminate plays a key role in new energy vehicles. The battery management system (BMS) of new energy vehicles is responsible for monitoring the voltage and temperature of battery cells and realizing data collection and transmission. Traditional copper wiring harnesses are large and heavy, while flexible circuit boards are made of copper clad laminate substrates, which have the characteristics of lightweight, bendability, and high integration, and can replace traditional wiring harnesses. Copper clad laminates can also be used as heat dissipation substrates in insulated gate bipolar transistor (IGBT) modules, and are used in inverters and motor controllers. Copper clad laminates can also be used in 5G vehicle networks and millimeter wave radars. Their low dielectric constant and dielectric loss characteristics ensure high-speed signal transmission and reduce interference.

[0003] Polyphenylene ether is widely used in the preparation of copper clad laminates due to its low water absorption, low dielectric constant and excellent heat resistance. Driven by the electrification and intelligence of automobiles, the power source of the whole vehicle is gradually changing from traditional engines and systems to high-voltage power batteries and related systems. At the same time, the demand for data transmission is also growing, especially for high-real-time applications such as video and images. It is becoming increasingly important to modify polyphenylene ether to optimize its performance and adapt to specific application requirements. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention proposes a polyphenylene ether composition and its application in new energy vehicles.

[0005] The technical solutions adopted are as follows: A polyphenylene ether composition comprises epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin and polyphenylene ether grafted maleic anhydride; The modified polyvinyl chloride resin is obtained by copolymerizing aminated polyvinyl chloride resin with N-styrylcarbazole free radicals.

[0006] Furthermore, the aminated polyvinyl chloride resin is obtained by reacting polyvinyl chloride resin with an organic amine.

[0007] Furthermore, the organic amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, and hexamethylenediamine, or a combination of two or more thereof.

[0008] Furthermore, the preparation method of the modified polyvinyl chloride resin is as follows: The polyvinyl chloride resin is dissolved in a dipolar solvent and then an organic amine is added. After heating for reaction, a reaction solution containing aminated polyvinyl chloride resin is obtained. A free radical initiator and N-styrylcarbazole are then added to the reaction solution. After continuing the reaction, the reaction solution is concentrated under reduced pressure and water is added. The precipitated product is collected, washed and dried.

[0009] Furthermore, the mass ratio of the polyvinyl chloride resin, the organic amine and the N-styrylcarbazole is 10-15:0.1-1:1-5.

[0010] Furthermore, the mass ratio of the epoxy-terminated polyphenylene ether, the modified polyvinyl chloride resin and the polyphenylene ether grafted maleic anhydride is 8-10:1:0.1-0.5.

[0011] Furthermore, the epoxy-terminated polyphenylene ether is obtained by reacting a dihydroxy-terminated polyphenylene ether resin with a halogen-containing epoxy compound under the action of a composite strong base and a phase transfer catalyst tetra-n-butylammonium bromide.

[0012] Furthermore, the composite strong base is a mixture of any one or two of sodium hydroxide, potassium hydroxide, and lithium hydroxide and any one or two of n-butyl lithium and lithium hydride.

[0013] Furthermore, a calcium zinc stabilizer is also included.

[0014] The invention also discloses application of the polyphenylene ether composition in new energy vehicles.

[0015] It has the following beneficial effects: The invention provides a polyphenylene ether composition. The polyvinyl chloride resin has poor thermal stability. After being heated, hydrogen chloride is easily released, and allyl chloride is formed in the molecular chain, which is not conducive to material stability. In the invention, the polyvinyl chloride resin and an organic amine are subjected to substitution reaction and elimination reaction to remove part of chlorine to form double bonds and amino side chains, and then a rigid aromatic ring is introduced by copolymerizing N-styrylcarbazole free radicals, thereby improving the thermal stability of the polyvinyl chloride resin and improving dielectric properties. The epoxy groups in the epoxy-terminated polyphenylene ether can also undergo crosslinking reaction with the amino side chains, thereby increasing the crosslinking density of the material and the mechanical strength, and improving the compatibility between the compositions, avoiding phase separation, and improving processing properties. The polyphenylene ether composition of the invention not only has excellent mechanical properties, but also exhibits good dielectric properties, and has great application potential in new energy vehicles. DETAILED DESCRIPTION

[0016] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0017] Embodiment 1: A polyphenylene ether composition comprises epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride and calcium zinc stabilizer in a mass ratio of 8:1:0.25:0.03; Wherein, the preparation method of modified polyvinyl chloride resin is as follows: 130g of polyvinyl chloride resin (DG800, Tianjin Dagu) was dissolved in 500ml of N,N-dimethylacetamide, and then 1g of 1,3-propylenediamine was added. The mixture was heated to 60°C and reacted for 5h to obtain a reaction solution containing aminated polyvinyl chloride resin. 0.05g of free radical initiator BPO and 25g of N-styrylcarbazole (CAS: 52913-19-6) were added to the reaction solution. The reaction was continued for 10h and then concentrated under reduced pressure until the reaction solution had a residual volume of 100ml. 1000ml of water was added dropwise and the mixture was slowly stirred for 10h. The precipitated product was filtered out, washed with deionized water and ethanol, and then dried in vacuo.

[0018] The preparation method of epoxy-terminated polyphenylene ether is as follows: Add 100g of double-terminated hydroxyl polyphenylene ether resin (SEM-12, Shaanxi Shuobo Electronic Materials) into 500ml of toluene, heat to 70°C, stir thoroughly to dissolve, add 1g of lithium hydroxide, 1g of n-butyl lithium, and 1g of tetra-n-butylammonium bromide, stir and react at a constant temperature for 5h, cool to room temperature, add 15g of epibromopropane, stir and react at room temperature for 15h, concentrate the reaction solution under reduced pressure to 100ml, add 1000ml of methanol dropwise, filter the precipitated product, wash with methanol and dry in vacuo.

[0019] The above composition was made into a sample, and the specific method was as follows: The composition was stirred in a high-speed mixer for 5 minutes, and then put into a twin-screw extruder for melting, mixing, extrusion and granulation. The extrusion temperature was 230-270°C and the screw speed was 260r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were temperature 240-300°C, injection pressure 80MPa, injection rate 70g / s and mold temperature 60°C.

[0020] Embodiment 2: A polyphenylene ether composition comprises epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride and calcium zinc stabilizer in a mass ratio of 9:1:0.25:0.03; Wherein, the preparation method of modified polyvinyl chloride resin and epoxy-terminated polyphenylene ether is the same as that of Example 1; The above composition was made into a sample, and the specific method was as follows: The composition was stirred in a high-speed mixer for 5 minutes, and then put into a twin-screw extruder for melting, mixing, extrusion and granulation. The extrusion temperature was 230-270°C and the screw speed was 260r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were temperature 240-300°C, injection pressure 80MPa, injection rate 70g / s and mold temperature 60°C.

[0021] Embodiment 3: A polyphenylene ether composition comprises epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride and calcium zinc stabilizer in a mass ratio of 10:1:0.25:0.03; Wherein, the preparation method of modified polyvinyl chloride resin and epoxy-terminated polyphenylene ether is the same as that of Example 1; The above composition was made into a sample, and the specific method was as follows: The composition was stirred in a high-speed mixer for 5 minutes, and then put into a twin-screw extruder for melting, mixing, extrusion and granulation. The extrusion temperature was 230-270°C and the screw speed was 260r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were temperature 240-300°C, injection pressure 80MPa, injection rate 70g / s and mold temperature 60°C.

[0022] Comparative Example 1: It is basically the same as Example 1, except that the epoxy-terminated polyphenylene ether resin is replaced by a dihydroxy-terminated polyphenylene ether resin.

[0023] Comparative Example 2: basically the same as Example 1, except that polyvinyl chloride resin is used instead of modified polyvinyl chloride resin.

[0024] Comparative Example 3: is basically the same as Example 1, except that polyphenylene ether grafted maleic anhydride is not added.

[0025] Performance test: Performance test was performed on the samples prepared in Examples 1-3 of the present invention and Comparative Examples 1-3.

[0026] The tensile properties were tested according to GB / T 1040-1992, with a tensile rate of 10 mm / min; The bending strength is tested according to GB / T 9341-2000, and the test rate is 2 mm / min; Notched impact strength is tested according to GB / T 1043-1993; The sample was placed between the test electrodes and the dielectric constant and dielectric loss of the sample were tested using a vector grid tester at a test frequency of 10 GHz. The test results are shown in Table 1 below:

[0027] It can be seen from Examples 1-3 in Table 1 above that the polyphenylene ether composition of the present invention not only has excellent mechanical properties, but also exhibits good dielectric properties; By comparing Example 1 with Comparative Example 1, it can be seen that the introduction of epoxy groups plays a positive role in improving the performance of the polyphenylene ether composition; By comparing Example 1 with Comparative Example 2, it can be seen that after the polyvinyl chloride resin is modified, the performance of the polyphenylene ether composition is greatly improved; By comparing Example 1 with Comparative Example 3, it can be seen that the addition of polyphenylene ether grafted maleic anhydride plays a positive role in improving the performance of the polyphenylene ether composition.

[0028] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyphenylene ether composition, characterized in that Including epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin and polyphenylene ether grafted with maleic anhydride; The modified polyvinyl chloride resin is obtained by copolymerizing aminated polyvinyl chloride resin with N-styrylcarbazole free radicals.

2. The polyphenylene ether composition according to claim 1, characterized in that The aminated polyvinyl chloride resin is obtained by reacting polyvinyl chloride resin with organic amine.

3. The polyphenylene ether composition according to claim 2, characterized in that The organic amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine and hexamethylenediamine, or a combination of two or more thereof.

4. The polyphenylene ether composition according to claim 1, characterized in that The preparation method of the modified polyvinyl chloride resin is as follows: The polyvinyl chloride resin is dissolved in a dipolar solvent and then an organic amine is added. After heating for reaction, a reaction solution containing aminated polyvinyl chloride resin is obtained. A free radical initiator and N-styrylcarbazole are then added to the reaction solution. After continuing the reaction, the reaction solution is concentrated under reduced pressure and water is added. The precipitated product is collected, washed and dried.

5. The polyphenylene ether composition according to claim 4, characterized in that The mass ratio of the polyvinyl chloride resin, the organic amine and the N-styrylcarbazole is 10-15: 0.1-1：1-5。 6. The polyphenylene ether composition according to claim 1, characterized in that The mass ratio of the epoxy-terminated polyphenylene ether, the modified polyvinyl chloride resin and the polyphenylene ether grafted maleic anhydride is 8-10:1:0.1-0.

5.

7. The polyphenylene ether composition according to claim 1, characterized in that The epoxy-terminated polyphenylene ether is obtained by reacting a double-terminated hydroxyl polyphenylene ether resin with a halogen-containing epoxy compound under the action of a composite strong base and a phase transfer catalyst tetra-n-butylammonium bromide.

8. The polyphenylene ether composition according to claim 7, characterized in that The composite strong base is a mixture of any one or two of sodium hydroxide, potassium hydroxide and lithium hydroxide and any one or two of n-butyl lithium and lithium hydride.

9. The polyphenylene ether composition according to any one of claims 1 to 8, characterized in that Also included is a calcium zinc stabilizer.

10. Use of the polyphenylene ether composition according to claim 9 in new energy vehicles.

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