A highly oil-resistant polyphenylene sulfide flame retardant material for automobile charging system

Abstract

The invention relates to the technical field of polyphenylene sulfide flame retardant materials, and discloses a highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system. The invention provides a highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system by mixing, melting and stirring polyphenylene sulfide, a silicon-containing flame retardant, a modified benzoxazine and an antioxidant 1035, and feeding the mixture into a twin-screw extruder to extrude the highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system. The highly oil-resistant polyphenylene sulfide flame retardant material contains a large amount of silicon elements and has a good flame retardant effect, and benzoxazine can form a heat-resistant phenolic resin structure at high temperature, so that the highly oil-resistant polyphenylene sulfide has a good flame retardant effect. The polyphenylene sulfide in the polyphenylene sulfide and the modified benzoxazine is synergistically oil-resistant, and has a good oil-resistant effect. The cardanol has a relatively long chain, which can be entangled with the polyphenylene sulfide to form a cross-linked network, so that the highly oil-resistant polyphenylene sulfide has a good tensile property.

Description

Technical Field

[0001] The invention relates to the technical field of polyphenylene sulfide flame retardant materials, in particular to a highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system. Background Art

[0002] Polyphenylene sulfide resin has good oil resistance and fatigue resistance, and is widely used in automotive parts. Automobile charging systems are widely used in today's society, but its flame retardant effect is not good. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, the document "Research Progress of New Phenolic Resin-Benzoxazine" reports that benzoxazine is prepared from phenolic, aldehyde, and primary amine compounds, and has good flame retardancy. The present invention modifies it with polyphenylene sulfide, and then mixes it with silicon-containing flame retardant, polyphenylene sulfide, and antioxidant to prepare a highly oil-resistant polyphenylene sulfide flame retardant material for automobile charging systems. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system, which has good flame retardancy, oil resistance and tensile properties.

[0005] (II) Technical solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: A highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system, comprising the following components by weight: 40-60 parts by weight of polyphenylene sulfide, 5-7 parts by weight of a silicon-containing flame retardant, 8-12 parts by weight of a modified benzoxazine, and 1-3 parts by weight of an antioxidant 1035.

[0007] Preferably, the preparation method of the silicon-containing flame retardant is:

[0008] (1) Add cardanol and 2,2-di(bromomethyl)-1,3-propylene glycol to an acetone solvent and stir evenly, then dropwise add a sodium hydroxide solution with a molar concentration of 4-7 mol / L, react at 60-80° C. for 7-15 h, and then dropwise add dilute hydrochloric acid with a molar concentration of 2-4 mol / L to neutralize, concentrate, filter, wash and dry to obtain an intermediate 1;

[0009] (2) adding acetone solvent to a reactor, passing nitrogen protection, adding intermediate 1 and phosphorus oxychloride thereto, reacting for 5-8 hours at 30-40 minutes, adding ice water after the reaction, concentrating, adding ethyl acetate for extraction, drying the organic phase over anhydrous magnesium sulfate, concentrating the filtrate, washing with ether, and then recrystallizing with ethyl acetate to obtain intermediate 2;

[0010] (3) Add intermediate 2 and pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stir to dissolve, react at 80-110° C. for 6-12 hours, and then remove the solvent by distillation under reduced pressure, filter and dry to obtain a silicon-containing flame retardant.

[0011] Preferably, the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol in (1) is 1:0.8-1.1.

[0012] Preferably, the mass ratio of the intermediate 1 to phosphorus oxychloride in (2) is 1.3-1.5:1.

[0013] Preferably, the mass ratio of the intermediate 2 to pentaerythritol methyl silicate in (3) is 1:2.5-3.4.

[0014] Preferably, the preparation method of the modified benzoxazine is:

[0015] S1. 5-10 parts by weight of polyphenylene sulfide are added to 1-2 parts by weight of chloromethyl ether and 0.5-1 parts by weight of tin tetrachloride, stirred and mixed, reacted at 75-90 ° C for 10-13h, filtered after the reaction, washed and dried to obtain chloromethylated polyphenylene sulfide;

[0016] S2. Add chloromethylated polyphenylene sulfide and p-aminophenol to N,N-dimethylformamide solvent, stir for 20-35 min, add sodium acetate, heat to 60-85 ° C, reflux for 3-5 h, cool, concentrate, and wash with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0017] S3. Add 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide and formaldehyde to a mixed solvent of toluene and 1,4-dioxane to carry out a cyclization reaction. After the reaction, distillation is performed under reduced pressure, and the product is washed with distilled water and methanol in turn. The crude product is recrystallized with dichloromethane to obtain a modified benzoxazine.

[0018] Preferably, the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate in S2 is 1.2-1.5:1:2-4.

[0019] Preferably, the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide and formaldehyde in S3 is 1:2.1-2.5:3.1-4.2.

[0020] Preferably, the preparation method of the highly oil-resistant polyphenylene sulfide flame retardant material for the automobile charging system is: polyphenylene sulfide, silicon-containing flame retardant, modified benzoxazine, and antioxidant 1035 are mixed and melted and stirred for 6-9 minutes, and fed into a twin-screw extruder, the blending temperature is 180-195°C, and the extrusion temperature is 170-180°C to obtain the highly oil-resistant polyphenylene sulfide flame retardant material for the automobile charging system.

[0021] (III) Beneficial technical effects

[0022] The invention prepares a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system by mixing, melting and stirring polyphenylene sulfide, a silicon-containing flame retardant, a modified benzoxazine and an antioxidant 1035, and feeding the mixture into a twin-screw extruder to extrude the mixture.

[0023] The highly oil-resistant polyphenylene sulfide flame retardant material contains a large amount of silicon element. The intermediate 1 is reacted through phosphorus oxychloride and further grafted with pentaerythritol methyl silicate to increase its degree of substitution, so that it has a good flame retardant effect. In addition, benzoxazine will form a heat-resistant phenolic resin structure at high temperature, so that it has a good flame retardant effect; polyphenylene sulfide and the polyphenylene sulfide in the modified benzoxazine are synergistically oil-resistant and have a good oil-resistant effect; modified benzoxazine and polyphenylene sulfide both have a polyphenylene sulfide structure, so they have good compatibility, and cardanol has a longer chain, which will be entangled with polyphenylene sulfide to form a cross-linked network, so that it has good tensile properties. DETAILED DESCRIPTION

[0024] Example 1

[0025] (1) Adding cardanol and 2,2-bis(bromomethyl)-1,3-propylene glycol to 60 ml of acetone solvent and stirring evenly, wherein the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:0.8, then dropping a sodium hydroxide solution with a molar concentration of 4 mol / L, reacting at 6° C. for 7 h, and then dropping a dilute hydrochloric acid with a molar concentration of 2 mol / L to neutralize, concentrating, filtering, washing and drying to obtain an intermediate 1;

[0026] (2) Add 50 ml of acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, wherein the mass ratio of intermediate 1 to phosphorus oxychloride is 1.3:1, react for 5 hours at 30 minutes, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2;

[0027] (3) adding intermediate 2 and pentaerythritol methyl silicate to 65 ml of N,N-dimethylformamide solvent, stirring and dissolving, wherein the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:2.5, reacting at 80° C. for 6 h, and then removing the solvent by reduced pressure distillation, filtering and drying to obtain a silicon-containing flame retardant;

[0028] (4) adding 5 parts by weight of polyphenylene sulfide to 1 part by weight of chloromethyl ether and 0.5 parts by weight of tin tetrachloride, stirring and mixing, reacting at 75° C. for 10 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0029] (5) adding chloromethylated polyphenylene sulfide and p-aminophenol to 80 ml of N,N-dimethylformamide solvent, stirring for 20 min, adding sodium acetate, wherein the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate is 1.2:1:2, heating to 60° C. and reflux reaction for 3 h, cooling, concentrating, and washing with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0030] (6) adding 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde to a mixed solvent of 40 ml of toluene and 50 ml of 1,4-dioxane, wherein the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde is 1:2.1:3.1, and performing a cyclization reaction. After the reaction, the mixture is distilled under reduced pressure, washed with distilled water and methanol in turn, and the crude product is recrystallized with dichloromethane to obtain a modified benzoxazine;

[0031] (7) 40 parts by weight of polyphenylene sulfide, 5 parts by weight of a silicon-containing flame retardant, 8 parts by weight of a phenol-based polyphenylene sulfide, and 1 part by weight of an antioxidant 1035 were mixed and melted and stirred for 6 minutes, and then fed into a twin-screw extruder at a blending temperature of 180° C. and an extrusion temperature of 170° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0032] Example 2

[0033] (1) Add cardanol and 2,2-bis(bromomethyl)-1,3-propylene glycol to 80 ml of acetone solvent and stir evenly, wherein the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:1.1, then dropwise add a 7 mol / L sodium hydroxide solution, react at 80° C. for 15 h, and then dropwise add 4 mol / L dilute hydrochloric acid for neutralization, concentrate, filter, wash and dry to obtain intermediate 1;

[0034] (2) Add 70 ml of acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, wherein the mass ratio of intermediate 1 to phosphorus oxychloride is 1.5:1, react for 8 hours at 40 min, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2;

[0035] (3) adding intermediate 2 and pentaerythritol methyl silicate to 80 ml of N,N-dimethylformamide solvent, stirring and dissolving, wherein the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:3.4, reacting at 110° C. for 12 h, and then removing the solvent by reduced pressure distillation, filtering and drying to obtain a silicon-containing flame retardant;

[0036] (4) adding 10 parts by weight of polyphenylene sulfide to 2 parts by weight of chloromethyl ether and 1 part by weight of tin tetrachloride, stirring and mixing, reacting at 90° C. for 13 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0037] (5) adding chloromethylated polyphenylene sulfide and p-aminophenol to 100 ml of N,N-dimethylformamide solvent, stirring for 35 min, adding sodium acetate, wherein the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate is 1.5:1:4, heating to 85° C. and reflux reaction for 5 h, cooling, concentrating, and washing with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0038] (6) adding 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde to a mixed solvent of 65 ml of toluene and 70 ml of 1,4-dioxane, wherein the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde is 1:2.5:4.2, and performing a cyclization reaction. After the reaction, the mixture is distilled under reduced pressure, washed with distilled water and methanol in turn, and the crude product is recrystallized with dichloromethane to obtain a modified benzoxazine;

[0039] (7) 60 parts by weight of polyphenylene sulfide, 7 parts by weight of a silicon-containing flame retardant, 12 parts by weight of a phenol-based polyphenylene sulfide, and 3 parts by weight of an antioxidant 1035 were mixed, melted, and stirred for 9 minutes, and then fed into a twin-screw extruder at a blending temperature of 195° C. and an extrusion temperature of 180° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0040] Example 3

[0041] (1) Adding cardanol and 2,2-bis(bromomethyl)-1,3-propylene glycol to 70 ml of acetone solvent and stirring evenly, wherein the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:0.95, then dropping a sodium hydroxide solution with a molar concentration of 5.5 mol / L, reacting at 70° C. for 11 h, and then dropping a dilute hydrochloric acid with a molar concentration of 3 mol / L to neutralize, concentrating, filtering, washing and drying to obtain an intermediate 1;

[0042] (2) Add 60 ml of acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, wherein the mass ratio of intermediate 1 to phosphorus oxychloride is 1.4:1, react for 6.5 hours at 35 minutes, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2;

[0043] (3) adding intermediate 2 and pentaerythritol methyl silicate to 72.5 ml of N,N-dimethylformamide solvent, stirring and dissolving, wherein the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:2.95, reacting at 95° C. for 9 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain a silicon-containing flame retardant;

[0044] (4) adding 7.5 parts by weight of polyphenylene sulfide to 1.5 parts by weight of chloromethyl ether and 0.75 parts by weight of tin tetrachloride, stirring and mixing, reacting at 82.5° C. for 11.5 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0045] (5) Add chloromethylated polyphenylene sulfide and p-aminophenol to 90 ml of N,N-dimethylformamide solvent, stir for 27.5 min, add sodium acetate, wherein the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate is 1.35:1:3, heat to 72.5° C., reflux for 4 h, cool, concentrate, and wash with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0046] (6) adding 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde to a mixed solvent of 52.5 ml of toluene and 60 ml of 1,4-dioxane, wherein the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde is 1:2.3:3.65, and performing a cyclization reaction. After the reaction, the mixture is distilled under reduced pressure, washed with distilled water and methanol in turn, and the crude product is recrystallized with dichloromethane to obtain a modified benzoxazine;

[0047] (7) 50 parts by weight of polyphenylene sulfide, 6 parts by weight of a silicon-containing flame retardant, 10 parts by weight of a phenol-based polyphenylene sulfide, and 2 parts by weight of an antioxidant 1035 were mixed and melted and stirred for 7.5 minutes, and then fed into a twin-screw extruder at a blending temperature of 187.5° C. and an extrusion temperature of 175° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0048] Example 4

[0049] (1) Adding cardanol and 2,2-bis(bromomethyl)-1,3-propylene glycol to 60 ml of acetone solvent and stirring evenly, wherein the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:0.8, then dropping a sodium hydroxide solution with a molar concentration of 4 mol / L, reacting at 6° C. for 7 h, and then dropping a dilute hydrochloric acid with a molar concentration of 2 mol / L to neutralize, concentrating, filtering, washing and drying to obtain an intermediate 1;

[0050] (2) Add 50 ml of acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, wherein the mass ratio of intermediate 1 to phosphorus oxychloride is 1.3:1, react for 5 hours at 30 minutes, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2;

[0051] (3) adding intermediate 2 and pentaerythritol methyl silicate to 80 ml of N,N-dimethylformamide solvent, stirring and dissolving, wherein the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:3.4, reacting at 110° C. for 12 h, and then removing the solvent by reduced pressure distillation, filtering and drying to obtain a silicon-containing flame retardant;

[0052] (4) adding 10 parts by weight of polyphenylene sulfide to 2 parts by weight of chloromethyl ether and 1 part by weight of tin tetrachloride, stirring and mixing, reacting at 90° C. for 13 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0053] (5) adding chloromethylated polyphenylene sulfide and p-aminophenol to 90 ml of N,N-dimethylformamide solvent, stirring for 27.5 min, adding sodium acetate, wherein the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate is 1.5:1:4, heating to 72.5° C. and reflux reaction for 4 h, cooling, concentrating, and washing with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0054] (6) adding 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde to a mixed solvent of 52.5 ml of toluene and 60 ml of 1,4-dioxane, wherein the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde is 1:2.3:3.65, and performing a cyclization reaction. After the reaction, the mixture is distilled under reduced pressure, washed with distilled water and methanol in turn, and the crude product is recrystallized with dichloromethane to obtain a modified benzoxazine;

[0055] (7) 50 parts by weight of polyphenylene sulfide, 6 parts by weight of a silicon-containing flame retardant, 10 parts by weight of a phenol-based polyphenylene sulfide, and 2 parts by weight of an antioxidant 1035 were mixed and melted and stirred for 7.5 minutes, and then fed into a twin-screw extruder at a blending temperature of 187.5° C. and an extrusion temperature of 175° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0056] Example 5

[0057] (1) Adding cardanol and 2,2-bis(bromomethyl)-1,3-propylene glycol to 80 ml of acetone solvent and stirring evenly, wherein the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:1.1, then dropping a sodium hydroxide solution with a molar concentration of 7 mol / L, reacting at 80° C. for 15 h, and then dropping a dilute hydrochloric acid with a molar concentration of 3 mol / L for neutralization, concentrating, filtering, washing and drying to obtain an intermediate 1;

[0058] (2) Add 70 ml of acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, wherein the mass ratio of intermediate 1 to phosphorus oxychloride is 1.5:1, react for 8 hours at 40 min, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2;

[0059] (3) adding intermediate 2 and pentaerythritol methyl silicate to 72.5 ml of N,N-dimethylformamide solvent, stirring and dissolving, wherein the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:2.95, reacting at 95° C. for 9 h, and then removing the solvent by reduced pressure distillation after the reaction, filtering and drying to obtain a silicon-containing flame retardant;

[0060] (4) adding 7.5 parts by weight of polyphenylene sulfide to 1.5 parts by weight of chloromethyl ether and 0.75 parts by weight of tin tetrachloride, stirring and mixing, reacting at 82.5° C. for 11.5 hours, filtering after the reaction, washing and drying to obtain chloromethylated polyphenylene sulfide;

[0061] (5) adding chloromethylated polyphenylene sulfide and p-aminophenol to 80 ml of N,N-dimethylformamide solvent, stirring for 20 min, adding sodium acetate, wherein the mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate is 1.35:1:3, heating to 60° C. and reflux reaction for 3 h, cooling, concentrating, and washing with petroleum ether to obtain phenol-based polyphenylene sulfide;

[0062] (6) adding 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde to a mixed solvent of 40 ml of toluene and 50 ml of 1,4-dioxane, wherein the mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide, and formaldehyde is 1:2.1:3.1, and performing a cyclization reaction. After the reaction, the mixture is distilled under reduced pressure, washed with distilled water and methanol in turn, and the crude product is recrystallized with dichloromethane to obtain a modified benzoxazine;

[0063] (7) 40 parts by weight of polyphenylene sulfide, 5 parts by weight of a silicon-containing flame retardant, 8 parts by weight of a phenol-based polyphenylene sulfide, and 1 part by weight of an antioxidant 1035 were mixed and melted and stirred for 6 minutes, and then fed into a twin-screw extruder at a blending temperature of 180° C. and an extrusion temperature of 170° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0064] Comparative Example 1

[0065] (1) 40 parts by weight of polyphenylene sulfide, 8 parts by weight of modified benzoxazine, and 1 part by weight of antioxidant 1035 were mixed and melted and stirred for 6 minutes, and then fed into a twin-screw extruder at a blending temperature of 180° C. and an extrusion temperature of 170° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0066] Comparative Example 2

[0067] (1) 40 parts by weight of polyphenylene sulfide, 5 parts by weight of a silicon-containing flame retardant, and 1 part by weight of an antioxidant 1035 were mixed and melted and stirred for 6 minutes, and then fed into a twin-screw extruder at a blending temperature of 180° C. and an extrusion temperature of 170° C. to obtain a highly oil-resistant polyphenylene sulfide flame retardant material for a vehicle charging system.

[0068] Use an oxygen index tester to test the oxygen index of the material.

[0069] The combustion level of the material is tested using a horizontal vertical combustion tester.

[0070] Table 1: Flame retardancy tests.

[0071] project Oxygen index (%) UL-94 Example 1 28.4 V-0 Example 2 30.1 V-0 Example 3 29.6 V-0 Example 4 283 V-0 Example 5 29.2 V-0 Comparative Example 1 22.4 V-1 Comparative Example 2 22.1 V-1

[0072] It can be seen from Table 1 that Examples 1-5 of the present invention have better flame retardant effects than Comparative Examples 1-2.

[0073] The oil resistance was tested according to ASTM D471 standard, and the tensile strength was measured using an electronic universal testing machine.

[0074] Table 2: Oil resistance and tensile testing.

[0075] project Oil resistance (%) Tensile strength(MPa) Example 1 5.3 161 Example 2 5.1 164 Example 3 5.2 163 Example 4 5.2 162 Example 5 5.1 161 Comparative Example 1 6.7 153 Comparative Example 2 6.9 141

[0076] It can be seen from Table 2 that Examples 1-5 of the present invention have better oil resistance and tensile properties than Comparative Examples 1-2.

[0077] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0078] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A highly oil-resistant polyphenylene sulfide flame retardant material for automobile charging system, characterized in that: The invention comprises the following components by weight: 40-60 parts by weight of polyphenylene sulfide, 5-7 parts by weight of a silicon-containing flame retardant, 8-12 parts by weight of a modified benzoxazine, and 1-3 parts by weight of an antioxidant 1035; The preparation method of the silicon-containing flame retardant is: (1) Add cardanol and 2,2-di(bromomethyl)-1,3-propylene glycol to an acetone solvent and stir evenly, then dropwise add a sodium hydroxide solution with a molar concentration of 4-7 mol / L, react at 60-80°C for 7-15 hours, and then dropwise add dilute hydrochloric acid with a molar concentration of 2-4 mol / L to neutralize, concentrate, filter, wash and dry to obtain intermediate 1; (2) Add acetone solvent to the reactor, pass nitrogen protection, add intermediate 1 and phosphorus oxychloride, react for 5-8 hours at 30-40 minutes, add ice water after the reaction, concentrate, add ethyl acetate for extraction, dry the organic phase over anhydrous magnesium sulfate, concentrate the filtrate, wash with ether, and then recrystallize with ethyl acetate to obtain intermediate 2; (3) adding intermediate 2 and pentaerythritol methyl silicate to N,N-dimethylformamide solvent, stirring to dissolve, reacting at 80-110° C. for 6-12 hours, and then removing the solvent by vacuum distillation, filtering and drying to obtain a silicon-containing flame retardant; In (1), the mass ratio of cardanol to 2,2-bis(bromomethyl)-1,3-propylene glycol is 1:0.8-1.1; In (2), the mass ratio of intermediate 1 to phosphorus oxychloride is 1.3-1.5:1; In said (3), the mass ratio of intermediate 2 to pentaerythritol methyl silicate is 1:2.5-3.4; The preparation method of the modified benzoxazine is: S1. 5-10 parts by weight of polyphenylene sulfide are added to 1-2 parts by weight of chloromethyl ether and 0.5-1 parts by weight of tin tetrachloride, stirred and mixed, reacted at 75-90 ° C for 10-13h, filtered after the reaction, washed and dried to obtain chloromethylated polyphenylene sulfide; S2. Add chloromethylated polyphenylene sulfide and p-aminophenol to N,N-dimethylformamide solvent, stir for 20-35 min, add sodium acetate, heat to 60-85 ° C, reflux for 3-5 h, cool, concentrate, and wash with petroleum ether to obtain phenol-based polyphenylene sulfide; S3. Add 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide and formaldehyde to a mixed solvent of toluene and 1,4-dioxane to carry out a cyclization reaction, and distill under reduced pressure after the reaction, wash with distilled water and methanol in turn, and recrystallize the crude product with dichloromethane to obtain a modified benzoxazine; The mass ratio of chloromethylated polyphenylene sulfide, p-aminophenol and sodium acetate in S2 is 1.2-1.5:1:2-4; The mass ratio of 4,4-diaminodiphenyl sulfone, phenol-based polyphenylene sulfide and formaldehyde in S3 is 1:2.1-2.5:3.1-4.

2.

2. A highly oil-resistant polyphenylene sulfide flame retardant material for an automobile charging system as claimed in claim 1, characterized in that: The preparation method of the highly oil-resistant polyphenylene sulfide flame retardant material for the automobile charging system is as follows: polyphenylene sulfide, a silicon-containing flame retardant, a modified benzoxazine, and an antioxidant 1035 are mixed, melted, and stirred for 6-9 minutes, and then fed into a twin-screw extruder, with a blending temperature of 180-195° C. and an extrusion temperature of 170-180° C. to obtain the highly oil-resistant polyphenylene sulfide flame retardant material for the automobile charging system.