Antistatic polyester composite and method for producing the same

Abstract

The application relates to the technical field of polyester materials, and discloses an antistatic polyester composite material and a preparation method thereof. The polyester composite material comprises the following raw materials in parts by weight: 70-90 parts of PET resin, 2-4 parts of a borate antistatic agent, 3-6 parts of modified carbon black, 0.5-1 part of an antioxidant, and 0.2-0.5 part of a lubricant; the composite material takes the PET resin as a main matrix material, and the antistatic performance of the composite material is improved by the synergistic effect of the modified carbon black and the borate antistatic agent which have the electric conduction effect, so that the composite material has excellent antistatic performance and can be widely applied to the electronic, electric, communication, aerospace, petrochemical, medicine and food industries.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyester materials, in particular to an antistatic polyester composite material and a preparation method thereof. BACKGROUND

[0002] Polyethylene terephthalate (PET) is prepared by polycondensation reaction of terephthalic acid and ethylene glycol. As a hydrophobic material, PET is prone to accumulate electric charge on the surface, which can cause potential harm in industries such as papermaking, printing, textile and plastic processing. For static electricity, it not only can adsorb dust, but also can cause a certain degree of discharge, which can cause fire accidents. In order to avoid the occurrence of static electricity, the accumulated static electricity can be eliminated in the first time, and appropriate measures can effectively prevent the harm caused by static electricity. In order to accelerate the dissipation process of static electricity, the conductivity of the material can be improved by modifying the material.

[0003] The common solution is to select conductive fillers, antistatic agents and coating technology, etc. These methods can promote the rapid discharge of static electricity by increasing the conductivity or hydrophilicity of the material, thereby reducing the risk of static electricity accumulation. However, these methods have some disadvantages, for example: (1) a large amount of conductive filler is needed to achieve the desired antistatic effect, and too much filler will accumulate in the material, damaging the mechanical properties of the material; (2) when using antistatic agents, due to their small molecular weight, they are prone to migrate in the material, which can cause the antistatic performance of the material to decrease over time and lack of long-term performance; (3) the antistatic components coated on the surface of the material will decrease in antistatic effect over time. Therefore, in view of the antistatic performance defects of the polyester composite material in the prior art, a polyester composite material with excellent antistatic effect is developed. SUMMARY

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

[0005] The object of the present application can be achieved by the following technical solutions:

[0006] An antistatic polyester composite material comprises the following raw materials by weight: 70-90 parts of PET resin, 2-4 parts of borate antistatic agent, 3-6 parts of modified carbon black, 0.5-1 part of antioxidant, and 0.2-0.5 part of lubricant.

[0007] Further, the antioxidant is one of antioxidant 1010 or antioxidant 168;

[0008] Further, the lubricant is one of calcium stearate or zinc stearate;

[0009] The borate antistatic agent is prepared by the following steps:

[0010] Step A1, under the condition of nitrogen, diethylene glycol amine and boric acid are mixed uniformly in toluene, heated to 110℃, constant temperature reflux reaction for 6-10h, rotary evaporation, to obtain the end amino borate ester;

[0011] Further, in step A1, the molar ratio of diethylene glycol amine and boric acid is 3-3.02:1;

[0012] Step A2, the end amino borate ester is stirred uniformly in N,N-dimethylformamide (DMF), denoted as solution 1; 4-hydroxy phthalic anhydride is stirred uniformly in DMF, slowly added dropwise into solution 1, stirred at room temperature for 2h, then anhydrous sodium acetate, hydroquinone and acetic anhydride are added, and the temperature is raised to 50-60℃ for 2h, then the reaction liquid is poured into ice water mixture and placed for 5min, filtered, washed and dried, to obtain the borate antistatic agent;

[0013] Further, in step A2, the molar ratio of end amino borate ester and 4-hydroxy phthalic anhydride is 1:1-1.1;

[0014] Further, in step A2, the amount of anhydrous sodium acetate, hydroquinone and acetic anhydride accounts for 2wt%-4wt%, 5wt%-8wt% and 45wt%-55wt% of the total amount of reactants, respectively;

[0015] Further, in step A2, the mass ratio of ice and water in the ice water mixture is 7:3, and the mass of the ice water mixture is 10 times the mass of the reaction liquid.

[0016] The modified carbon black is prepared by the following steps:

[0017] Step B1, carbon black powder is uniformly dispersed in ethanol and water by ultrasonic, silane coupling agent KH-550 is added, and the temperature is raised to 50℃ for stirring for 5-8h, then filtered, washed and dried, to obtain aminated carbon black;

[0018] Further, in step B1, the mass ratio of carbon black and silane coupling agent KH-550 is 5-10:1-3;

[0019] Further, in step B1, the volume ratio of ethanol and water is 9:1;

[0020] Step B2, the aminated carbon black is uniformly dispersed in methanol, methyl acrylate is added, and the reaction is carried out under the condition of nitrogen at 30-40℃ for 48h, then centrifuged, washed, and the product 1 is collected; then the product 1 is dispersed in an equal amount of methanol, and ethylenediamine is added, and the reaction is carried out at 30-40℃ for 48h, then centrifuged, washed and dried, to obtain the modified carbon black precursor;

[0021] Further, in step B2, the amount ratio of aminated carbon black, methanol, methyl acrylate and ethylenediamine is 0.5-1.5g:20mL:8-24mL:6-18mL;

[0022] In step B3, the modified carbon black precursor is uniformly dispersed in methanol, methyl acrylate is added, and the reaction is carried out under the conditions of nitrogen and 30-40℃ for 48h, and then the product 2 is collected after centrifugation, washing and drying; the product 2 is dispersed in an equal amount of methanol, and ethylenediamine is added, and the reaction is carried out under the conditions of 30-40℃ for 48h, and then the product is collected after centrifugation, washing and drying, thereby obtaining the modified carbon black.

[0023] Further, in step B3, the amount ratio of the modified carbon black precursor, methanol, methyl acrylate and ethylenediamine is 0.4-1.2g:20mL:8-24mL:8-24mL.

[0024] A preparation method of an antistatic polyester composite material comprises the following steps:

[0025] The raw materials are weighed by weight parts, the PET resin, the borate antistatic agent, the modified carbon black, the antioxidant and the lubricant are uniformly mixed and stirred in a stirring machine, and then transferred to a double-screw extruder for fully melting, plasticizing, kneading, mixing, extruding and granulating, thereby obtaining the antistatic polyester composite material.

[0026] The polyester composite material in the application is prepared by using the modified carbon black and the borate antistatic agent, and the use of the conductive filler and the antistatic agent in the polyester composite material is reduced, but the antistatic performance is still significantly improved.

[0027] The polyester composite material in the application is prepared by using the modified carbon black and the borate antistatic agent, and the use of the conductive filler and the antistatic agent in the polyester composite material is reduced, but the antistatic performance is still significantly improved.

[0028] The borate antistatic agent prepared in the application has a polar borate group and a hydrophilic ether bond, which helps to absorb and retain moisture in the environment, forms a conductive water film on the surface of the polyester composite material, helps to balance the electric charge, and thus has an antistatic effect. The borate antistatic agent not only has good antistatic effect, but also has less impact on the environment, and is more in line with the current environmental protection requirements (different from the traditional quaternary ammonium salt antistatic agent which has certain toxicity and irritation). At the same time, the introduction of the imide ring and the benzene ring with excellent heat resistance improves the heat resistance of the borate antistatic agent, so that the borate antistatic agent can still maintain excellent antistatic performance and good thermal stability at high temperature. In addition, the borate antistatic agent also has a terminal hydroxyl group, which can form a chemical bond with the polyester in the matrix, reduce the loss of the antistatic agent due to migration, and make the polyester composite material maintain the antistatic performance for a long time.

[0029] The modified carbon black prepared by the method has the following advantages: the carbon black is used as a conductive base material, and the surface thereof is treated to graft an amide segment to the surface, the amide group can form a hydrogen bond with water molecules, the hydrophilicity of the surface of the polyester composite material is increased, the material surface is easier to adsorb water, and thus the volume resistivity of the material is reduced, the release and dissipation of static electricity are promoted, the material has a certain conductivity due to the presence of the amide group, and the accumulated static electricity can be discharged in time to prevent the harm caused by static electricity accumulation. In addition, the amide molecular chain on the surface of the modified carbon black also has a certain lubricating effect, which can reduce the internal friction of the base body, and thus reduce the generation of internal static electricity. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0031] Embodiment 1: The borate antistatic agent is prepared by the following steps:

[0032] Step A1, under the condition of nitrogen, 0.3 mol of diglycolamine and 0.1 mol of boric acid are uniformly mixed in 200 mL of toluene, heated to 110℃, and refluxed for 6 h, and then rotary evaporation is performed to obtain an amino-terminated borate ester;

[0033] Step A2, 0.1 mol of the amino-terminated borate ester is uniformly stirred in 200 mL of DMF to obtain solution 1; 0.1 mol of 4-hydroxyphthalic anhydride is uniformly stirred in 200 mL of DMF, and solution 1 is slowly added dropwise, stirred at room temperature for 2 h, and then anhydrous sodium acetate, hydroquinone and acetic anhydride are added, and the temperature is increased to 50℃ and reacted for 2 h, then the reaction liquid is poured into an ice-water mixture and left to stand for 5 min, and then filtration, washing and drying are performed to obtain the borate antistatic agent, the amount of anhydrous sodium acetate, hydroquinone and acetic anhydride accounts for 2 wt%, 5 wt% and 45 wt% of the total amount of the reactants respectively, and the mass ratio of ice to water in the ice-water mixture is 7:3, and the mass of the ice-water mixture is 10 times the mass of the reaction liquid.

[0034] The modified carbon black is prepared by the following steps:

[0035] Step B1, 5 g of carbon black powder is uniformly dispersed in 45 mL of ethanol and 5 mL of water by ultrasonic dispersion, 1 g of silane coupling agent KH-550 is added, and the temperature is increased to 50℃ and stirred for 5 h, and then filtration, washing and drying are performed to obtain amino-modified carbon black;

[0036] Step B2, 0.5 g of aminated carbon black was uniformly dispersed in 10 mL of methanol, 8 mL of methyl acrylate was added, and the reaction was carried out at 30°C for 48 h under nitrogen. The product 1 was collected by centrifugation, washing, and drying; then the product 1 was dispersed in 10 mL of methanol, and 6 mL of ethylenediamine was added. The reaction was carried out at 30°C for 48 h, and the product was collected by centrifugation, washing, and drying to obtain the modified carbon black precursor.

[0037] Step B3, 0.4 g of the modified carbon black precursor was uniformly dispersed in 10 mL of methanol, and 8 mL of methyl acrylate was added. The reaction was carried out at 30°C for 48 h under nitrogen. The product 2 was collected by centrifugation, washing, and drying; then the product 2 was dispersed in 10 mL of methanol, and 8 mL of ethylenediamine was added. The reaction was carried out at 30°C for 48 h, and the product was collected by centrifugation, washing, and drying to obtain the modified carbon black.

[0038] Example 2: Borate antistatic agent was prepared by the following steps:

[0039] Step A1, under nitrogen, 0.301 mol of diethyleneglycol amine and 0.1 mol of boric acid were uniformly mixed in 200 mL of toluene, heated to 110°C, and refluxed for 8 h. The product was collected by rotary evaporation to obtain an amino-terminated borate ester.

[0040] Step A2, 0.1 mol of the amino-terminated borate ester was uniformly stirred in 200 mL of DMF to obtain solution 1; 0.105 mol of 4-hydroxyphthalic anhydride was uniformly stirred in 200 mL of DMF, and solution 1 was slowly added dropwise. The mixture was stirred at room temperature for 2 h, and then anhydrous sodium acetate, hydroquinone, and acetic anhydride were added. The reaction was carried out at 55°C for 2 h. The reaction solution was then poured into an ice-water mixture and allowed to stand for 5 min. The product was collected by filtration, washing, and drying to obtain the borate antistatic agent. The amounts of anhydrous sodium acetate, hydroquinone, and acetic anhydride accounted for 3 wt%, 6.5 wt%, and 50 wt% of the total amount of reactants, respectively. The mass ratio of ice to water in the ice-water mixture was 7:3, and the mass of the ice-water mixture was 10 times the mass of the reaction solution.

[0041] The modified carbon black was prepared by the following steps:

[0042] Step B1, 7.5 g of carbon black powder was uniformly dispersed in 45 mL of ethanol and 5 mL of water by ultrasonic dispersion, and 2 g of silane coupling agent KH-550 was added. The mixture was heated to 50°C and stirred for 6.5 h. The product was collected by filtration, washing, and drying to obtain aminated carbon black.

[0043] Step B2, 1 g of aminated carbon black was uniformly dispersed in 10 mL of methanol, and 16 mL of methyl acrylate was added. The reaction was carried out at 35°C for 48 h under nitrogen. The product 1 was collected by centrifugation, washing, and drying; then the product 1 was dispersed in 10 mL of methanol, and 12 mL of ethylenediamine was added. The reaction was carried out at 35°C for 48 h, and the product was collected by centrifugation, washing, and drying to obtain the modified carbon black precursor.

[0044] Step B3, 0.8 g of modified carbon black precursor was uniformly dispersed in 10 mL of methanol, 16 mL of methyl acrylate was added, and the reaction was carried out at 35°C under nitrogen for 48 h, centrifuged, washed, and the product 2 was collected; then the product 2 was dispersed in 10 mL of methanol, and 16 mL of ethylenediamine was added, and the reaction was carried out at 35°C for 48 h, centrifuged, washed, and dried to obtain the modified carbon black.

[0045] Example 3: The borate antistatic agent was prepared by the following steps:

[0046] Step A1, under the condition of nitrogen, 0.302 mol of diethylene glycol amine and 0.1 mol of boric acid were uniformly mixed in 200 mL of toluene, heated to 110°C, and refluxed for 6-10 h, and then rotary evaporated to obtain an amino-terminated borate ester;

[0047] Step A2, 0.1 mol of the amino-terminated borate ester was uniformly stirred in 200 mL of DMF, and was recorded as solution 1; 0.11 mol of 4-hydroxyphthalic anhydride was uniformly stirred in 200 mL of DMF, and was slowly added dropwise into solution 1, and was stirred at room temperature for 2 h, and then anhydrous sodium acetate, hydroquinone and acetic anhydride were added, and the reaction was carried out at 60°C for 2 h, and then the reaction solution was poured into an ice-water mixture and was allowed to stand for 5 min, and then was filtered, washed and dried to obtain the borate antistatic agent, the amount of anhydrous sodium acetate, hydroquinone and acetic anhydride accounted for 4 wt%, 8 wt% and 55 wt% of the total amount of the reactants respectively, and the mass ratio of ice to water in the ice-water mixture was 7:3, and the mass of the ice-water mixture was 10 times the mass of the reaction solution.

[0048] The modified carbon black was prepared by the following steps:

[0049] Step B1, 10 g of carbon black powder was uniformly dispersed in 45 mL of ethanol and 5 mL of water by ultrasonic dispersion, 3 g of silane coupling agent KH-550 was added, and the temperature was raised to 50°C and stirred for 8 h, and then filtered, washed and dried to obtain an aminated carbon black;

[0050] Step B2, 1.5 g of the aminated carbon black was uniformly dispersed in 10 mL of methanol, 24 mL of methyl acrylate was added, and the reaction was carried out at 40°C under nitrogen for 48 h, and then centrifuged, washed, and the product 1 was collected; then the product 1 was dispersed in 10 mL of methanol, and 18 mL of ethylenediamine was added, and the reaction was carried out at 40°C for 48 h, and then centrifuged, washed and dried to obtain a modified carbon black precursor;

[0051] Step B3, 1.2 g of the modified carbon black precursor was uniformly dispersed in 10 mL of methanol, 24 mL of methyl acrylate was added, and the reaction was carried out at 40°C under nitrogen for 48 h, and then centrifuged, washed, and the product 2 was collected; then the product 2 was dispersed in 10 mL of methanol, and 24 mL of ethylenediamine was added, and the reaction was carried out at 40°C for 48 h, and then centrifuged, washed and dried to obtain the modified carbon black.

[0052] Example 4: A method for preparing an antistatic polyester composite material comprises the following steps:

[0053] The raw materials are weighed by parts by weight, 70 parts of PET resin, 2 parts of the borate antistatic agent prepared in Example 1, 3 parts of the modified carbon black prepared in Example 1, 0.5 parts of antioxidant 1010 and 0.2 parts of calcium stearate are uniformly mixed and stirred in a blender, then transferred to a twin-screw extruder for sufficient melting, plasticizing, kneading and mixing, then extruded and granulated to obtain the antistatic polyester composite material.

[0054] Example 5: A method for preparing an antistatic polyester composite material comprises the following steps:

[0055] The raw materials are weighed by parts by weight, 80 parts of PET resin, 3 parts of the borate antistatic agent prepared in Example 2, 4.5 parts of the modified carbon black prepared in Example 2, 0.7 parts of antioxidant 168 and 0.35 parts of zinc stearate are uniformly mixed and stirred in a blender, then transferred to a twin-screw extruder for sufficient melting, plasticizing, kneading and mixing, then extruded and granulated to obtain the antistatic polyester composite material.

[0056] Example 6: A method for preparing an antistatic polyester composite material comprises the following steps:

[0057] The raw materials are weighed by parts by weight, 90 parts of PET resin, 4 parts of the borate antistatic agent prepared in Example 3, 6 parts of the modified carbon black prepared in Example 3, 1 part of antioxidant 168 and 0.5 parts of zinc stearate are uniformly mixed and stirred in a blender, then transferred to a twin-screw extruder for sufficient melting, plasticizing, kneading and mixing, then extruded and granulated to obtain the antistatic polyester composite material.

[0058] Comparative Example 1: This comparative example is a polyester composite material, which is different from Example 6 in that the commercially available quaternary ammonium salt antistatic agent SH-105 is used instead of the borate antistatic agent prepared in Example 3, and the rest are the same.

[0059] Comparative Example 2: This comparative example is a polyester composite material, which is different from Example 6 in that carbon black powder is used instead of the modified carbon black prepared in Example 3, and the rest are the same.

[0060] Comparative Example 3: This comparative example is a polyester composite material, which is different from Example 6 in that the commercially available quaternary ammonium salt antistatic agent SH-105 is used instead of the borate antistatic agent prepared in Example 3, and the carbon black powder is used instead of the modified carbon black prepared in Example 3, and the rest are the same.

[0061] The polyester composite materials prepared in Examples 4-6 and Comparative Examples 1-3 were pressed into sheets with a thickness of 2 mm by a flat vulcanizing machine, 5 cm x 5 cm samples were cut from the sheets, and the sheets were tested for resistivity by a high insulation resistance measuring instrument; the test results are shown in Table 1:

[0062] Table 1: Test results

[0063]

[0064] As can be seen from Table 1, the polyester composite material prepared in the application has a low surface resistivity after resistivity testing, indicating that the material has excellent antistatic properties.

[0065] The above is merely an example and description of the concept of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the scope defined by the concept of the application, which shall belong to the protection scope of the application.

Claims

1. An antistatic polyester composite material, characterized in that, The raw materials include the following components by weight: PET resin 70-90 parts, borate antistatic agent 2-4 parts, modified carbon black 3-6 parts, antioxidant 0.5-1 part, lubricant 0.2-0.5 part; The borate antistatic agent is prepared by the following steps: Step A1, under the condition of nitrogen, diethyleneglycolamine and boric acid are mixed uniformly in toluene, heated to 110℃, constant temperature reflux reaction for 6-10h, rotary evaporation, to obtain the terminal amino borate ester, wherein the molar ratio of diethyleneglycolamine and boric acid is 3-3.02:1; Step A2, the terminal amino borate ester is stirred uniformly in DMF, denoted as solution 1; 4-hydroxyphthalic anhydride is stirred uniformly in DMF, slowly added dropwise into solution 1, stirred at room temperature for 2h, then added anhydrous sodium acetate, hydroquinone and acetic anhydride, heated to 50-60℃ for 2h, then the reaction liquid is poured into ice water mixture and stand for 5min, filtered, washed and dried, to obtain the borate antistatic agent, wherein the molar ratio of terminal amino borate ester and 4-hydroxyphthalic anhydride is 1:1-1.1; The modified carbon black is prepared by the following steps: Step B1, carbon black powder is ultrasonically dispersed uniformly in ethanol and water, then silane coupling agent KH-550 is added, heated to 50℃ and stirred for 5-8h, filtered, washed and dried, to obtain aminated carbon black; Step B2, the aminated carbon black is uniformly dispersed in methanol, then methyl acrylate is added, reacted under the condition of nitrogen at 30-40℃ for 48h, centrifuged, washed, and the product 1 is collected; then the product 1 is dispersed in equal amount of methanol, and ethylenediamine is added, reacted at 30-40℃ for 48h, centrifuged, washed and dried, to obtain the modified carbon black precursor; Step B3, the modified carbon black precursor is uniformly dispersed in methanol, then methyl acrylate is added, reacted under the condition of nitrogen at 30-40℃ for 48h, centrifuged, washed, and the product 2 is collected; then the product 2 is dispersed in equal amount of methanol, and ethylenediamine is added, reacted at 30-40℃ for 48h, centrifuged, washed and dried, to obtain the modified carbon black.

2. The antistatic polyester composite material according to claim 1, characterized in that, In step A2, the amount of anhydrous sodium acetate, hydroquinone and acetic anhydride accounts for 2wt%-4wt%, 5wt%-8wt% and 45wt%-55wt% of the total amount of reactants respectively, the mass ratio of ice and water in the ice water mixture is 7:3, and the mass of the ice water mixture is 10 times of the mass of the reaction liquid.

3. The antistatic polyester composite material according to claim 1, characterized in that, In step B1, the mass ratio of carbon black and silane coupling agent KH-550 is 5-10:1-3, and the volume ratio of ethanol and water is 9:

1.

4. The antistatic polyester composite material according to claim 1, wherein In step B2, the amount ratio of aminated carbon black, methanol, methyl acrylate and ethylenediamine is 0.5-1.5g:20mL:8-24mL:6-18mL.

5. The antistatic polyester composite material according to claim 1, wherein In step B3, the amount ratio of modified carbon black precursor, methanol, methyl acrylate and ethylenediamine is 0.4-1.2g:20mL:8-24mL:8-24mL.

6. The antistatic polyester composite material according to claim 1, wherein The antioxidant is one of antioxidant 1010 or antioxidant 168, and the lubricant is one of calcium stearate or zinc stearate.

7. A process for the production of the antistatic polyester composite material according to any one of claims 1 to 6, characterized in that The method comprises the following steps: The raw materials are weighed by weight parts, the PET resin, the borate antistatic agent, the modified carbon black, the antioxidant and the lubricant are mixed and stirred uniformly in a stirrer, then are transferred into a double screw extruder for sufficient melting, plasticizing, kneading and mixing, and then are extruded and granulated to obtain the antistatic polyester composite material.

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