Antistatic PPE composite material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses an antistatic PPE composite material and a preparation method thereof. According to the PPE composite material disclosed by the invention, the polyphenyl ether resin and the modified polystyrene are taken as matrix resin, and functional aids such as the filler reinforcing filler, the antioxidant, the compatilizer and the lubricant are used, so that the antistatic property and the light resistance of the composite material are comprehensively improved; wherein the modified polystyrene takes chloromethyl polystyrene resin as a matrix, a cationic quaternary ammonium salt structure and a sulfonic acid group are grafted on the side chain of the modified polystyrene, the antistatic performance of the surface of the composite material is remarkably improved, and the reinforcing filler takes titanium dioxide as a matrix and is loaded with quantum dots, so that the light resistance of the composite material is improved, and the antistatic performance of the surface of the composite material is improved. And the antistatic agent also can cooperate with modified polystyrene, so that the antistatic performance of the material is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an antistatic PPE composite material and a preparation method thereof. Background Art

[0002] Polyphenylene ether (PPE) is a non-polar linear polymer obtained by oxidative condensation reaction of 2,6-dimethylphenol with oxygen in the presence of copper-amine catalyst. It is one of the world's top five general-purpose engineering plastics. Due to its advantages such as good dielectric properties, high heat resistance, good mechanical properties and stable dimensional properties, it is widely used in electronics, intelligent manufacturing, printed circuits, aviation and military industries.

[0003] However, PPE resin still has some disadvantages, such as: (1) poor antistatic performance, which will lead to static electricity accumulation on the surface of the material, making it susceptible to static damage and lacking safety, thus limiting its application in electronic appliances, medical equipment and other products; (2) relatively poor light resistance, after being exposed to light or ultraviolet light for a long time, it will cause the material to crack, discolor, powder and other phenomena. Therefore, researchers need to develop a PPE composite material with excellent antistatic performance and good light resistance to meet practical application needs. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antistatic PPE composite material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antistatic PPE composite material comprises the following raw materials in parts by weight: 40-60 parts of polyphenylene ether resin, 15-25 parts of modified polystyrene, 10-20 parts of reinforcing filler, 0.5-1.5 parts of antioxidant, 1-3 parts of compatibilizer, and 1-3 parts of lubricant;

[0007] The antioxidant is antioxidant 1010, the compatibilizer is maleic anhydride-styrene copolymer, and the lubricant is zinc stearate;

[0008] The modified polystyrene is prepared by the following steps:

[0009] Step A1, dispersing sodium benzaldehyde-4-sulfonate evenly in ethanol, recorded as mixed solution 1; mixing diethylenetriamine in ethanol and stirring evenly, and adjusting the pH to 5-6, then slowly adding mixed solution 1 dropwise using a constant pressure dropping funnel, and heating to 60-80° C., stirring to react for 3-4 hours, and distilling to obtain an intermediate product;

[0010] Further, in step A1, the dosage ratio of diethylenetriamine, ethanol and mixed solution 1 is 0.01-0.02 mol: 100 mL: 20 mL;

[0011] Further, the dosage ratio of sodium benzaldehyde-4-sulfonate and ethanol in the mixed solution 1 of step A1 is 0.021-0.42 mol: 20 mL;

[0012] Step A2, washing and drying the chloromethyl polystyrene resin (Cl-PS), which is recorded as pre-treated Cl-PS; mixing the pre-treated Cl-PS, the intermediate product and isopropanol, stirring evenly, heating to 55-75° C., stirring for reaction for 4-8 hours, filtering under reduced pressure, washing and drying, to obtain sulfonated polystyrene;

[0013] Further, in step A2, the ratio of the pre-treated Cl-PS, the intermediate product and isopropanol is 10 g: 1-2 g: 30 mL;

[0014] Step A3, adding sulfonated polystyrene to N,N-dimethylformamide, heating to 45-55°C and stirring evenly, then slowly adding 1-chlorobutane dropwise using a constant pressure separatory funnel, stirring and reacting for 8-12 hours, and performing reduced pressure distillation, rotary evaporation, and drying to obtain modified polystyrene;

[0015] Furthermore, in step A3, the usage ratio of sulfonated polystyrene, N,N-dimethylformamide and 1-chlorobutane is 10 g:50 mL:0.2-1 g.

[0016] The reinforcing filler is prepared by the following steps:

[0017] Step B1, mix and grind the MXene powder and ethanol, place it on a 1000 mesh sieve for sieving, collect the product, and evenly mix the product and titanium dioxide nanosheets in a 0.5 mol / L sodium hydroxide ethanol solution, then transfer it to an autoclave, react at 100°C for 3-4h, ultrasonicate in a water bath for 2-3h, centrifuge, wash, and dry to obtain MXene QDs / TiO2 nanomaterials (MXene quantum dots loaded with titanium dioxide nanomaterials);

[0018] Further, in step B1, the usage ratio of MXene powder, ethanol, titanium dioxide nanosheets and sodium hydroxide ethanol solution is 2-4 g: 5-8 mL: 0.5-2 g: 50 mL;

[0019] Step B2, stirring the MXene QDs / TiO2 nanomaterial in a mixture of ethanol and deionized water, adding hexadecyltrimethylammonium bromide and stirring for 10-30 minutes, then ultrasonically treating for 2-3 hours, filtering, washing and drying to obtain a reinforced filler;

[0020] Furthermore, in step B2, the usage ratio of MXene QDs / TiO2 nanomaterial, deionized water, ethanol and hexadecyltrimethylammonium bromide is 5g:30mL:20mL:0.4-0.8g.

[0021] A method for preparing an antistatic PPE composite material comprises the following steps:

[0022] The raw materials are weighed in parts by weight, and the polyphenylene ether resin, modified polystyrene, reinforcing filler, antioxidant, compatibilizer and lubricant are mixed and stirred uniformly to obtain a mixture, and then the mixture is put into a twin-screw extruder, and the antistatic PPE composite material is obtained through extrusion and granulation.

[0023] Beneficial effects of the present invention:

[0024] The PPE composite material of the present invention is based on polyphenylene ether resin and modified polystyrene as matrix resins, and includes filler reinforcing filler, antioxidant, compatibilizer, lubricant and other functional additives, which comprehensively improve the antistatic performance and light resistance of the composite material; wherein the modified polystyrene is based on chloromethyl polystyrene resin, and cationic quaternary ammonium salt structure and sulfonic acid group are grafted on the side chain of the modified polystyrene, which significantly improves the antistatic performance of the composite material surface, and the reinforcing filler is based on titanium dioxide and loaded with quantum dots, which not only improves the light resistance of the composite material, but also can synergize with the modified polystyrene to further improve the antistatic performance of the material.

[0025] In the modified polystyrene, the aldehyde group in sodium benzaldehyde-4-sulfonate and the amino group in diethylenetriamine are first reacted to obtain an intermediate product; the intermediate product is then reacted with pre-treated Cl-PS to obtain sulfonated polystyrene; finally, 1-chlorobutane is reacted with the tertiary amine of the side chain of sulfonated polystyrene to obtain modified polystyrene. The modified polystyrene plays a plasticizing role in the matrix, making the composite material easier to shape during processing, and improving the flexibility and antistatic properties of the composite material; the modified polystyrene is made of Cl-PS as a raw material, and the Cl of the resin side chain is used for grafting, thereby introducing a quaternary ammonium salt structure and a sulfonic acid group into the side chain of polystyrene, wherein the cationic quaternary ammonium salt structure can neutralize the surface charge of the matrix, eliminate or reduce the electrostatic charge, and the sulfonic acid group has excellent hydrophilicity, can adsorb water molecules in the environment, form a conductive water film, so that the charge on the surface of the composite material can be quickly removed from the surface, and the synergistic effect between the two improves the antistatic effect of the matrix. In addition, by introducing antistatic components into the side chains of polystyrene and utilizing the good compatibility between polystyrene and polyphenylene ether, the composite material can have a long-lasting antistatic effect.

[0026] In the reinforcing filler, MXene powder is used as raw material, and MXene QDs are loaded on the surface of titanium dioxide to obtain MXeneQDs / TiO2 nanomaterials; then the surface of MXene QDs / TiO2 nanomaterials is treated with surfactant hexadecyltrimethylammonium bromide to obtain reinforcing fillers. After the reinforcing filler is introduced, it can not only improve the light resistance of the composite material, but also improve the conductivity, and further improve the antistatic performance of the matrix; the titanium dioxide nanosheet substrate in the reinforcing filler has a strong ability to absorb ultraviolet rays, which can effectively protect the composite material from damage by ultraviolet rays, improve the light resistance of the matrix, and extend the service life of the plastic. At the same time, the quantum dots loaded on its surface can also inhibit the photocatalytic ability of titanium dioxide and avoid catalytic degradation of the matrix resin; and MXene quantum dots have good conductivity and can synergize with modified polystyrene to improve the antistatic performance of the composite material. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.

[0028] Example 1: Modified polystyrene is prepared by the following steps:

[0029] Step A1, 0.02 mol of sodium benzaldehyde-4-sulfonate is dispersed evenly in 20 mL of ethanol, recorded as mixed solution 1; 0.01 mol of diethylenetriamine is mixed and stirred evenly in 100 mL of ethanol, and the pH is adjusted to 5, and then 20 mL of mixed solution 1 is slowly added dropwise using a constant pressure dropping funnel, and the temperature is raised to 60° C., stirred for reaction for 3 hours, and distilled to obtain an intermediate product;

[0030] Step A2, washing and drying the chloromethyl polystyrene resin, recorded as pre-treated Cl-PS; 10g of pre-treated Cl-PS, 1g of the intermediate product and 30mL of isopropanol were mixed and stirred evenly, heated to 55°C, stirred and reacted for 4h, filtered under reduced pressure, washed and dried to obtain sulfonated polystyrene;

[0031] Step A3, add 10 g of sulfonated polystyrene to 50 mL of N,N-dimethylformamide, heat to 45 °C and stir evenly, then slowly drop 0.2 g of 1-chlorobutane using a constant pressure separatory funnel, stir and react for 8 h, distill under reduced pressure, rotary evaporate and dry to obtain modified polystyrene.

[0032] The reinforcing filler is prepared by the following steps:

[0033] Step B1, 2 g of MXene powder and 5 mL of ethanol were mixed and ground, placed in a 1000 mesh sieve for sieving, the product was collected, and the product and 0.5 g of titanium dioxide nanosheets were mixed evenly in 50 mL of 0.5 mol / L sodium hydroxide ethanol solution, and then transferred to an autoclave, reacted at 100 ° C for 3 h, water bath ultrasonic for 2 h, centrifuged, washed, and dried to obtain MXene QDs / TiO2 nanomaterials;

[0034] Step B2: Evenly stir 5 g of MXene QDs / TiO2 nanomaterial in a mixture of 30 mL of ethanol and 20 mL of deionized water, add 0.4 g of hexadecyltrimethylammonium bromide and stir for 10 min, then ultrasonically treat for 2 h, filter, wash and dry to obtain a reinforced filler.

[0035] Example 2: Modified polystyrene is prepared by the following steps:

[0036] Step A1, 0.032 mol of sodium benzaldehyde-4-sulfonate was dispersed evenly in 20 mL of ethanol, recorded as mixed solution 1; 0.015 mol of diethylenetriamine was mixed and stirred evenly in 100 mL of ethanol, and the pH was adjusted to 5.5, and then 20 mL of mixed solution 1 was slowly added dropwise using a constant pressure dropping funnel, and the temperature was raised to 70° C., stirred for reaction for 3.5 hours, and distilled to obtain an intermediate product;

[0037] Step A2, washing and drying the chloromethyl polystyrene resin, recorded as pre-treated Cl-PS; 10g of pre-treated Cl-PS, 1.5g of the intermediate product and 30mL of isopropanol were mixed and stirred evenly, heated to 65°C, stirred and reacted for 6h, filtered under reduced pressure, washed and dried to obtain sulfonated polystyrene;

[0038] Step A3, add 10 g of sulfonated polystyrene to 50 mL of N,N-dimethylformamide, heat to 50°C and stir evenly, then slowly drop 0.5 g of 1-chlorobutane using a constant pressure separatory funnel, stir to react for 10 hours, distill under reduced pressure, rotary evaporate, and dry to obtain modified polystyrene.

[0039] The reinforcing filler is prepared by the following steps:

[0040] Step B1, 3 g of MXene powder and 6.5 mL of ethanol were mixed and ground, placed in a 1000 mesh sieve, the product was collected, and the product and 1 g of titanium dioxide nanosheets were mixed evenly in 50 mL of 0.5 mol / L sodium hydroxide ethanol solution, and then transferred to an autoclave, reacted at 100 ° C for 3.5 h, water bath ultrasonic for 2.5 h, centrifuged, washed, and dried to obtain MXene QDs / TiO2 nanomaterials;

[0041] Step B2: Evenly stir 5 g of MXene QDs / TiO2 nanomaterial in a mixture of 30 mL of ethanol and 20 mL of deionized water, add 0.6 g of hexadecyltrimethylammonium bromide and stir for 20 min, then ultrasonically treat for 2.5 h, filter, wash and dry to obtain a reinforced filler.

[0042] Example 3: Modified polystyrene is prepared by the following steps:

[0043] Step A1, 0.42 mol of sodium benzaldehyde-4-sulfonate is dispersed evenly in 20 mL of ethanol, recorded as mixed solution 1; 0.02 mol of diethylenetriamine is mixed and stirred evenly in 100 mL of ethanol, and the pH is adjusted to 6, and then 20 mL of mixed solution 1 is slowly added dropwise using a constant pressure dropping funnel, and the temperature is raised to 80° C., stirred for reaction for 4 hours, and distilled to obtain an intermediate product;

[0044] Step A2, washing and drying the chloromethyl polystyrene resin, recorded as pre-treated Cl-PS; 10g of pre-treated Cl-PS, 2g of the intermediate product and 30mL of isopropanol were mixed and stirred evenly, heated to 75°C, stirred and reacted for 8h, filtered under reduced pressure, washed and dried to obtain sulfonated polystyrene;

[0045] Step A3, add 10g of sulfonated polystyrene to 50mL of N,N-dimethylformamide, heat to 55°C and stir evenly, then slowly drop 1g of 1-chlorobutane using a constant pressure separatory funnel, stir and react for 12h, distill under reduced pressure, rotary evaporate and dry to obtain modified polystyrene.

[0046] The reinforcing filler is prepared by the following steps:

[0047] Step B1, 4 g of MXene powder and 8 mL of ethanol were mixed and ground, placed in a 1000 mesh sieve, the product was collected, and the product and 2 g of titanium dioxide nanosheets were mixed evenly in 50 mL of 0.5 mol / L sodium hydroxide ethanol solution, and then transferred to an autoclave, reacted at 100 ° C for 4 h, water bath ultrasonic for 3 h, centrifuged, washed, and dried to obtain MXene QDs / TiO2 nanomaterials;

[0048] Step B2: Evenly stir 5 g of MXene QDs / TiO2 nanomaterial in a mixture of 30 mL of ethanol and 20 mL of deionized water, add 0.8 g of hexadecyltrimethylammonium bromide and stir for 30 min, then ultrasonically treat for 3 h, filter, wash and dry to obtain a reinforced filler.

[0049] Embodiment 4: A method for preparing an antistatic PPE composite material comprises the following steps:

[0050] 40 parts of polyphenylene ether resin, 15 parts of modified polystyrene prepared in Example 1, 10 parts of reinforcing filler prepared in Example 1, 0.5 parts of antioxidant 1010, 1 part of maleic anhydride-styrene copolymer, and 1 part of zinc stearate;

[0051] The raw materials were weighed in parts by weight, and the polyphenylene ether resin, the modified polystyrene prepared in Example 1, the reinforcing filler prepared in Example 1, the antioxidant 1010, the maleic anhydride-styrene copolymer and the zinc stearate were mixed and stirred uniformly to obtain a mixture, and then the mixture was put into a twin-screw extruder, and the antistatic PPE composite material was obtained by extrusion and granulation.

[0052] Embodiment 5: A method for preparing an antistatic PPE composite material comprises the following steps:

[0053] 50 parts of polyphenylene ether resin, 20 parts of modified polystyrene prepared in Example 2, 15 parts of reinforcing filler prepared in Example 2, 10101 parts of antioxidant, 2 parts of maleic anhydride-styrene copolymer, and 2 parts of zinc stearate;

[0054] The raw materials were weighed in parts by weight, and the polyphenylene ether resin, the modified polystyrene prepared in Example 2, the reinforcing filler prepared in Example 2, the antioxidant 1010, the maleic anhydride-styrene copolymer and the zinc stearate were mixed and stirred uniformly to obtain a mixture, and then the mixture was put into a twin-screw extruder, and the antistatic PPE composite material was obtained by extrusion and granulation.

[0055] Embodiment 6: A method for preparing an antistatic PPE composite material comprises the following steps:

[0056] 60 parts of polyphenylene ether resin, 25 parts of modified polystyrene prepared in Example 3, 20 parts of reinforcing filler prepared in Example 3, 1.5 parts of antioxidant 1010, 3 parts of maleic anhydride-styrene copolymer, and 3 parts of zinc stearate;

[0057] The raw materials were weighed in parts by weight, and the polyphenylene ether resin, the modified polystyrene prepared in Example 3, the reinforcing filler prepared in Example 3, the antioxidant 1010, the maleic anhydride-styrene copolymer and the zinc stearate were mixed and stirred uniformly to obtain a mixture, and then the mixture was put into a twin-screw extruder, and the antistatic PPE composite material was obtained by extrusion and granulation.

[0058] Comparative Example 1: This comparative example is a PPE composite material, which is different from Example 6 in that polystyrene replaces the modified polystyrene prepared in Example 3, and the rest are the same.

[0059] Comparative Example 2: This comparative example is a PPE composite material, which differs from Example 6 in that titanium dioxide nanosheets are used instead of the reinforcing filler prepared in Example 3, and the rest are the same.

[0060] The PPE composite materials prepared in Examples 4-6 and Comparative Examples 1-2 were subjected to performance tests:

[0061] Antistatic performance test: Test the surface resistivity of PPE composite materials under IEC60093 standard conditions;

[0062] Lightfastness test: Test the xenon lamp aging color difference △E of the sample according to ISO 4892-2cycle 1 and ASTM D2244 standards, and observe whether the surface of the sample is cracked or powdered;

[0063] The test results are shown in Table 1:

[0064] Table 1: Performance test results

[0065] <![CDATA[Resistivity (Ω / m 2 )]]> Color difference ΔE Surface state Example 4 <![CDATA[2.6×10 5 ]]> 2.3 No cracking, no powdering Example 5 <![CDATA[8.7×10 4 ]]> 2.2 No cracking, no powdering Example 6 <![CDATA[3.2×10 4 ]]> 2.0 No cracking, no powdering Comparative Example 1 <![CDATA[5.8×10 8 ]]> 2.4 No cracking, no powdering Comparative Example 2 6.1×106 6.7 Slight cracking, no powdering

[0066] It can be seen from Table 1 that after the surface resistivity test, the surface resistivity of the PPE composite material prepared by the present invention is (3.2×10 4 -2.6×10 5 )Ω / m 2 , indicating that it has excellent antistatic properties; after weather resistance test, the color difference ΔE is in the range of 2.0-2.3, and the surface of the sample is not cracked or powdered, indicating that it has good weather resistance.

[0067] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field 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 scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An antistatic PPE composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 40-60 parts of polyphenylene ether resin, 15-25 parts of modified polystyrene, 10-20 parts of reinforcing filler, 0.5-1.5 parts of antioxidant, 1-3 parts of compatibilizer and 1-3 parts of lubricant; The modified polystyrene is prepared by the following steps: Step A1, dispersing sodium benzaldehyde-4-sulfonate evenly in ethanol, recorded as mixed solution 1; mixing diethylenetriamine in ethanol and stirring evenly, and adjusting the pH to 5-6, then slowly adding mixed solution 1 dropwise using a constant pressure dropping funnel, and heating to 60-80° C., stirring to react for 3-4 hours, and distilling to obtain an intermediate product; Step A2, washing and drying the chloromethyl polystyrene resin, recorded as pre-treated Cl-PS; mixing the pre-treated Cl-PS, the intermediate product and isopropanol uniformly, heating to 55-75° C., stirring for reaction for 4-8 hours, filtering under reduced pressure, washing and drying to obtain sulfonated polystyrene; Step A3, add sulfonated polystyrene to N,N-dimethylformamide, raise the temperature to 45-55°C and stir evenly, then slowly add 1-chlorobutane dropwise using a constant pressure separatory funnel, stir and react for 8-12 hours, and perform vacuum distillation, rotary evaporation, and drying to obtain modified polystyrene.

2. An antistatic PPE composite material according to claim 1, characterized in that: In step A1, the usage ratio of diethylenetriamine, ethanol and mixed solution 1 is 0.01-0.02 mol:100 mL:20 mL, and the usage ratio of sodium benzaldehyde-4-sulfonate and ethanol in mixed solution 1 is 0.021-0.42 mol:20 mL.

3. An antistatic PPE composite material according to claim 1, characterized in that: In step A2, the usage ratio of pre-treated Cl-PS, intermediate product and isopropanol is 10 g: 1-2 g: 30 mL.

4. The antistatic PPE composite material according to claim 1, characterized in that: In step A3, the usage ratio of sulfonated polystyrene, N,N-dimethylformamide and 1-chlorobutane is 10 g:50 mL:0.2-1 g.

5. The antistatic PPE composite material according to claim 1, characterized in that: The reinforcing filler is prepared by the following steps: Step B1, mix and grind MXene powder and ethanol, place on a 1000 mesh sieve for sieving, collect the product, and mix the product and titanium dioxide nanosheets evenly in a 0.5 mol / L sodium hydroxide ethanol solution, then transfer to an autoclave, react at 100°C for 3-4 hours, ultrasonicate in a water bath for 2-3 hours, centrifuge, wash, and dry to obtain MXene QDs / TiO2 nanomaterials; Step B2, stir the MXene QDs / TiO2 nanomaterial in a mixture of ethanol and deionized water, add hexadecyltrimethylammonium bromide and stir for 10-30 minutes, then ultrasonically treat for 2-3 hours, filter, wash and dry to obtain a reinforced filler.

6. An antistatic PPE composite material according to claim 5, characterized in that: In step B1, the dosage ratio of MXene powder, ethanol, titanium dioxide nanosheets and sodium hydroxide ethanol solution is 2-4 g: 5-8 mL: 0.5-2 g: 50 mL.

7. The antistatic PPE composite material according to claim 5, characterized in that: In step B2, the usage ratio of MXene QDs / TiO2 nanomaterial, deionized water, ethanol and hexadecyltrimethylammonium bromide is 5g:30mL:20mL:0.4-0.8g.

8. The antistatic PPE composite material according to claim 1, characterized in that: The antioxidant is antioxidant 1010, the compatibilizer is maleic anhydride-styrene copolymer, and the lubricant is zinc stearate.

9. A method for preparing the antistatic PPE composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The raw materials are weighed in parts by weight, and the polyphenylene ether resin, modified polystyrene, reinforcing filler, antioxidant, compatibilizer and lubricant are mixed and stirred uniformly to obtain a mixture, and then the mixture is put into a twin-screw extruder, and the antistatic PPE composite material is obtained through extrusion and granulation.