A polyphenylene ether composition and its application in new energy vehicles

Abstract

The present invention relates to the field of polymer materials, and specifically to a polyphenylene ether composition and its application in new energy vehicles. The composition comprises 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. The polyphenylene ether composition of the present invention not only has excellent mechanical properties but also exhibits good dielectric properties, and has great application potential in new energy vehicles.

Description

Technical Field

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

[0002] Copper-clad laminate, a core material for printed circuit boards, plays a key role in new energy vehicles. Its battery management system (BMS) monitors battery cell voltage and temperature, and collects and transmits data. Traditional copper wiring harnesses are bulky and heavy. Flexible circuit boards, made with copper-clad laminate as a substrate, offer lightweight, bendable, and highly integrated alternatives. Copper-clad laminate also serves as a heat sink in insulated-gate bipolar transistor (IGBT) modules, used in inverters and motor controllers. Copper-clad laminate is also used in 5G connected vehicles and millimeter-wave radar, where its low dielectric constant and low dielectric loss ensure high-speed signal transmission and minimize interference.

[0003] Polyphenylene ether (PPE) is widely used in copper-clad laminates (CCLs) due to its low water absorption, low dielectric constant, and excellent heat resistance. Driven by the electrification and intelligentization of automobiles, vehicle power sources are gradually shifting from traditional engines and systems to high-voltage batteries and related systems. Simultaneously, the demand for data transmission is also growing, especially for high-real-time applications such as video and imaging. Modifying PPE to optimize its performance and adapt it to specific application requirements is becoming increasingly important. Summary of the Invention

[0004] Purpose of the invention: In response to 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:

[0006] A polyphenylene ether composition comprising epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin and polyphenylene ether grafted maleic anhydride;

[0007] The modified polyvinyl chloride resin is obtained by copolymerizing aminated polyvinyl chloride resin and N-styrylcarbazole free radical.

[0008] Furthermore, the aminated polyvinyl chloride resin is obtained by reacting polyvinyl chloride resin with organic amine.

[0009] Furthermore, the organic amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, and hexamethylenediamine, or a combination of two or more thereof.

[0010] Furthermore, the preparation method of the modified polyvinyl chloride resin is as follows:

[0011] 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 further reaction, the reaction solution is concentrated under reduced pressure and water is added. The precipitated product is collected, washed and dried.

[0012] Furthermore, the mass ratio of the polyvinyl chloride resin, the organic amine, and the N-styrylcarbazole is 10-15:0.1-1:1-5.

[0013] 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.

[0014] Furthermore, the epoxy-terminated polyphenylene ether is obtained by reacting a dihydroxy-terminated polyphenylene ether resin with a halogen-containing epoxy compound in the presence of a composite strong base and a phase transfer catalyst, tetra-n-butylammonium bromide.

[0015] 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.

[0016] Furthermore, a calcium zinc stabilizer is also included.

[0017] The present invention also discloses the application of the polyphenylene ether composition in new energy vehicles.

[0018] It has the following beneficial effects:

[0019] The present invention provides a polyphenylene ether composition. Polyvinyl chloride resin has poor thermal stability, and hydrogen chloride is easily released after being heated, forming allyl chloride in the molecular chain, which is not conducive to material stability. In the present invention, substitution reaction and elimination reaction are performed between the polyvinyl chloride resin and an organic amine to remove part of the chlorine to form double bonds and amino side chains, and then rigid aromatic rings are introduced through N-styrylcarbazole free radical copolymerization, thereby improving the thermal stability of the polyvinyl chloride resin and improving the dielectric properties. The epoxy groups in the epoxy-terminated polyphenylene ether can also undergo cross-linking reaction with the amino side chains, thereby increasing the cross-linking density and mechanical strength of the material, improving the compatibility between the compositions, avoiding phase separation, and improving processing performance. The polyphenylene ether composition of the present invention not only has excellent mechanical properties, but also exhibits good dielectric properties, and has great application potential in new energy vehicles. DETAILED DESCRIPTION

[0020] Unless otherwise specified, the following examples and comparative examples were conducted in parallel, using the same processing steps and parameters.

[0021] Example 1:

[0022] A polyphenylene ether composition comprising epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride, and a calcium zinc stabilizer in a mass ratio of 8:1:0.25:0.03;

[0023] Wherein, the preparation method of modified polyvinyl chloride resin is as follows:

[0024] 130 g of polyvinyl chloride resin (DG800, Tianjin Dagu) was dissolved in 500 ml of N,N-dimethylacetamide, and 1 g of 1,3-propylenediamine was added. The mixture was heated to 60°C and reacted for 5 h to obtain a reaction solution containing aminated polyvinyl chloride resin. 0.05 g of free radical initiator BPO and 25 g of N-styrylcarbazole (CAS: 52913-19-6) were then added to the reaction solution. The reaction was continued for 10 h, and the reaction solution was concentrated under reduced pressure until the remaining volume of the reaction solution was 100 ml. 1000 ml of water was added dropwise, and the mixture was slowly stirred for 10 h. The precipitated product was filtered out, washed with deionized water and ethanol, and then dried in vacuo.

[0025] The preparation method of epoxy-terminated polyphenylene ether is as follows:

[0026] Add 100 g of double-terminated hydroxyl polyphenylene ether resin (SEM-12, Shaanxi Shuobo Electronic Materials) to 500 ml of toluene, heat to 70°C, stir thoroughly to dissolve, add 1 g of lithium hydroxide, 1 g of n-butyl lithium, and 1 g of tetra-n-butylammonium bromide, and react with stirring at a constant temperature for 5 h. Then cool to room temperature, add 15 g of epibromopropane, and react with stirring at room temperature for 15 h. The reaction solution is concentrated under reduced pressure to 100 ml, and 1000 ml of methanol is added dropwise. The precipitated product is filtered, washed with methanol, and dried in vacuo.

[0027] The above composition was prepared into a sample, and the specific method was as follows:

[0028] 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 260 r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were a temperature of 240-300°C, an injection pressure of 80 MPa, an injection rate of 70 g / s, and a mold temperature of 60°C.

[0029] Example 2:

[0030] A polyphenylene ether composition comprising epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride, and a calcium zinc stabilizer in a mass ratio of 9:1:0.25:0.03;

[0031] The preparation methods of the modified polyvinyl chloride resin and the epoxy-terminated polyphenylene ether are the same as those in Example 1;

[0032] The above composition was prepared into a sample, and the specific method was as follows:

[0033] 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 260 r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were a temperature of 240-300°C, an injection pressure of 80 MPa, an injection rate of 70 g / s, and a mold temperature of 60°C.

[0034] Example 3:

[0035] A polyphenylene ether composition comprising epoxy-terminated polyphenylene ether, modified polyvinyl chloride resin, polyphenylene ether grafted maleic anhydride, and a calcium zinc stabilizer in a mass ratio of 10:1:0.25:0.03;

[0036] The preparation methods of the modified polyvinyl chloride resin and the epoxy-terminated polyphenylene ether are the same as those in Example 1;

[0037] The above composition was prepared into a sample, and the specific method was as follows:

[0038] 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 260 r / min. Then, an injection molding machine was used to injection mold standard specimens. The injection molding process conditions were a temperature of 240-300°C, an injection pressure of 80 MPa, an injection rate of 70 g / s, and a mold temperature of 60°C.

[0039] Comparative Example 1: basically the same as Example 1, except that dihydroxy-terminated polyphenylene ether resin is used instead of epoxy-terminated polyphenylene ether.

[0040] Comparative Example 2: basically the same as Example 1, except that polyvinyl chloride resin is used instead of modified polyvinyl chloride resin.

[0041] Comparative Example 3: basically the same as Example 1, except that polyphenylene ether grafted maleic anhydride is not added.

[0042] Performance test: Performance test was performed on the samples prepared in Examples 1-3 of the present invention and Comparative Examples 1-3.

[0043] The tensile properties were tested according to GB / T 1040-1992 at a tensile rate of 10 mm / min;

[0044] Bending strength is tested according to GB / T 9341-2000 at a test rate of 2 mm / min;

[0045] Notched impact strength is tested according to GB / T 1043-1993;

[0046] 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:

[0047]

[0048] As can be seen from Examples 1-3 in Table 1 above, the polyphenylene ether composition of the present invention not only has excellent mechanical properties, but also exhibits good dielectric properties;

[0049] 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;

[0050] By comparing Example 1 with Comparative Example 2, it can be seen that the performance of the polyphenylene ether composition is greatly improved after the polyvinyl chloride resin is modified;

[0051] 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.

[0052] 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 they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. 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 various 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 and N-styrylcarbazole free radical.

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

3. The polyphenylene ether composition according to claim 2, wherein 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, wherein 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 further 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, wherein 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, wherein 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, wherein The epoxy-terminated polyphenylene ether is obtained by reacting a double-hydroxyl-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.

8. The polyphenylene ether composition according to claim 7, wherein 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, wherein Also includes calcium zinc stabilizer.

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

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