PBT / PPO alloy material suitable for online spraying and preparation method of PBT / PPO alloy material

Abstract

The invention provides a PBT / PPO alloy material suitable for online spraying and a preparation method of the PBT / PPO alloy material. The alloy material is prepared from the following raw material components in parts by weight: 50 to 60 parts of PBT (Polybutylene Terephthalate), 15 to 25 parts of PPO (Polyphenylene Oxide), 8 to 12 parts of a toughening agent, 0.5 to 2 parts of a lubricating agent, 0.2 to 1.0 part of an antioxidant and 1 to 2 parts of conductive carbon black, wherein the conductive carbon black is obtained by modifying carbon black, the iodine absorption value of the carbon black is 1000-1400 mg / g, the oil absorption value of the carbon black is 300-340 mL / 100 g, and the finally prepared PBT / PPO composite material has high flowability, high impact, high heat resistance and good spraying performance and can be used for manufacturing parts with high weather resistance requirements such as automobile charging port covers and door handle decoration covers.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material modification, and relates to a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. Background Art

[0002] Polybutylene terephthalate (PBT) is a crystalline thermoplastic polyester resin containing a carbonyl group (-COO-) in its main chain. PBT exhibits excellent properties, including high-temperature resistance, moisture resistance, oil resistance, excellent electrical insulation, chemical resistance, rapid molding, low moisture absorption, and ease of processing. After appropriate modification, it is widely used in electronics, automotive, mechanical equipment, and optical fiber cable and fiber optic coating. Polyphenylene oxide (PPO or PPE) is one of the world's five most common engineering plastics. With a density of only approximately 1.05 g / cm³, the lowest among engineering plastics, it offers advantages such as high rigidity, heat resistance, flame retardancy, high strength, and excellent electrical properties. Furthermore, PPE is wear-resistant, non-toxic, and resistant to contamination. PPO has one of the lowest dielectric constants and dielectric loss among engineering plastics, being virtually unaffected by temperature and humidity, making it suitable for applications in low, medium, and high-frequency electric fields.

[0003] Fuel filler cap panels, charging port panels, and concealed door handle trims on gasoline, hybrid, and electric vehicles are often made from a high-temperature, spray-coated PA / PPO alloy. However, with the increasing frequency of extreme weather in recent years, particularly hot and rainy summers, PA / PPO alloys are susceptible to high temperatures and high humidity. Rapid moisture absorption can cause dimensional changes and warping in parts, further impacting their performance. To address this hygroscopicity, we propose replacing PA / PPO with PBT / PPO. By interacting with other components, we have developed a PBT / PPO alloy suitable for online spray coating. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention adopts the following technical solutions: In a first aspect, a PBT / PPO alloy material suitable for online spraying is provided, wherein the alloy material comprises the following raw material components by weight: 50-60 parts of PBT, 15-25 parts of PPO, 8-12 parts of a toughening agent, 0.5-2 parts of a lubricant, 0.2-1.0 parts of an antioxidant, and 1-2 parts of conductive carbon black; the conductive carbon black is obtained by modifying carbon black, and the carbon black has an iodine absorption value of 1000-1400 mg / g and an oil absorption value of 300-340 mL / 100g.

[0005] As a preferred embodiment of the present invention, the relative viscosity of the polybutylene terephthalate is 0.8-1.2 dl / g.

[0006] As a preferred embodiment of the present invention, the intrinsic viscosity of the polyphenylene ether is 0.43-0.46 dl / g.

[0007] As a preferred embodiment of the present invention, the styrene content in the toughening agent is 10-20%.

[0008] As a preferred embodiment of the present invention, the lubricant is selected from one or a combination of silicone masterbatch, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer.

[0009] As a preferred embodiment of the present invention, the antioxidant is selected from one or a combination of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(2,4-di-tert-butylphenyl)phosphite, pentaerythritol distearyl diphosphite, pentaerythritol stearate, and aromatic phosphites.

[0010] As a preferred embodiment of the present invention, the alloy material further includes a compatibilizer, and the mass ratio of the compatibilizer to the conductive carbon black is (5-6):1.

[0011] As a preferred embodiment of the present invention, the preparation process of the conductive carbon black is as follows: carbon black is dispersed in an oxidant solution and oxidized to obtain oxidized carbon black, the oxidized carbon black and a silane compound are refluxed in a solvent to obtain modified carbon black, and then the modified carbon black is reacted with an ionic liquid in the presence of a catalyst, and the conductive carbon black is obtained after drying.

[0012] In a second aspect, the present invention provides a method for preparing the aforementioned PBT / PPO alloy material, the method comprising the following steps: The formulated amount of PPO, toughening agent, lubricant, antioxidant, conductive carbon black and compatibilizer are mixed in a high-speed mixer to obtain a mixture, and the mixture is fed from the main feeding port of a twin-screw extruder, and PBT is fed from the side to perform extrusion granulation.

[0013] As a preferred embodiment of the present invention, the mixing time is 3-7 minutes; the ratio of the screw length to the screw diameter of the twin-screw extruder is 30-48; the control temperature of each section of the twin-screw extruder is 250-290°C, and the rotation speed is 350-450 rpm.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The present invention adopts low-viscosity PBT as the first matrix resin and PPO as the second matrix resin, and interacts with the toughening agent, conductive carbon black, compatibilizer, etc. in the system to balance the rigidity, toughness and processing performance of the material. The final prepared PBT / PPO composite material has high flow, high impact, high heat resistance and good spraying performance. It can be used to manufacture components with high weather resistance requirements such as automobile charging port covers and door handle decorative covers. DETAILED DESCRIPTION

[0015] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, the present invention is further described in detail below. However, the following embodiments are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0016] The specific embodiment of the present invention provides a PBT / PPO alloy material suitable for online spraying, wherein the alloy material comprises the following raw material components by weight: 50-60 parts of PBT, 15-25 parts of PPO, 8-12 parts of toughening agent, 0.5-2 parts of lubricant, 0.2-1.0 parts of antioxidant, and 1-2 parts of conductive carbon black.

[0017] As a more preferred embodiment of the present invention, the relative viscosity of the polybutylene terephthalate is 0.8-1.2 dl / g, and the relative viscosity is measured according to GB / T 14190-2017.

[0018] As a more preferred embodiment of the present invention, the intrinsic viscosity of the polyphenylene ether is 0.43-0.46 dl / g, and the intrinsic viscosity is measured according to ISO 1628.

[0019] Among them, the amount of PBT can be 50 parts, 52 parts, 54 parts, 56 parts, 58 parts or 60 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the amount of PPO can be 15 parts, 17 parts, 19 parts, 21 parts, 23 parts or 25 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the amount of toughening agent can be 8 parts, 9 parts, 10 parts, 11 parts or 12 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the amount of lubricant can be 15 parts, 17 parts, 19 parts, 21 parts, 23 parts or 25 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; The dosage can be 0.5 parts, 0.8 parts, 1.1 parts, 1.4 parts, 1.7 parts or 2 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are equally applicable; the dosage of the antioxidant can be 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts or 1 part, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are equally applicable; the dosage of the conductive carbon black can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are equally applicable.

[0020] As a preferred embodiment of the present invention, the styrene content in the toughening agent is 10-20%; as a more preferred embodiment of the present invention, the styrene content in the toughening agent is 13%.

[0021] As a preferred embodiment of the present invention, the lubricant is selected from one or a combination of silicone masterbatch, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer. As a preferred embodiment of the present invention, the lubricant is silicone masterbatch.

[0022] As a preferred embodiment of the present invention, the antioxidant is selected from one or a combination of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(2,4-di-tert-butylphenyl)phosphite, pentaerythritol distearyl diphosphite, pentaerythritol stearate, and aryl phosphite; as a preferred embodiment of the present invention, the antioxidant is an aryl phosphite.

[0023] As a preferred embodiment of the present invention, the preparation process of the conductive carbon black is as follows: carbon black is dispersed in an oxidant solution and oxidized to obtain oxidized carbon black, the oxidized carbon black and a silane compound are refluxed in a solvent to obtain modified carbon black, and then the modified carbon black is reacted with an ionic liquid in the presence of a catalyst, and the conductive carbon black is obtained after drying.

[0024] As a preferred embodiment of the present invention, the preparation process of the conductive carbon black is as follows: carbon black is dispersed in a 5-10wt% hydrogen peroxide solution, ultrasonically treated at 40-60°C for 1-3h for mild oxidation, centrifuged, washed and dried after oxidation to obtain oxidized carbon black, then the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 80-90°C for 3-5h, centrifuged, washed and dried to obtain modified carbon black, the modified carbon black is reacted with an ionic liquid at 50-70°C for 5-7h under the action of a catalyst, washed with ethanol, and dried to obtain the conductive carbon black.

[0025] As a preferred embodiment of the present invention, the catalyst is diisopropylcarbodiimide; the amount of the catalyst used is 5-20% of the mass of the ionic liquid.

[0026] As a preferred embodiment of the present invention, the carbon black has an iodine absorption value of 1000-1400 mg / g and an oil absorption value of 300-340 mL / 100 g. As a preferred embodiment of the present invention, the carbon black has an iodine absorption value of 1360 mg / g and an oil absorption value of 320 mL / 100 g. The iodine absorption value is measured using ASTM D-1510, and the oil absorption value is measured using ASTM D-2414.

[0027] As a preferred embodiment of the present invention, the mass ratio of the silane compound to the oxidized carbon black is (0.1-0.5):1; as a preferred embodiment of the present invention, the mass ratio of the silane compound to the oxidized carbon black is 0.3:1.

[0028] As a preferred embodiment of the present invention, the mass ratio of the ionic liquid to the modified carbon black is (0.5-5):1; as a preferred embodiment of the present invention, the mass ratio of the ionic liquid to the modified carbon black is 3:1.

[0029] As a preferred embodiment of the present invention, the silane compound is γ-aminoethylaminopropyltrimethoxysilane.

[0030] As a preferred embodiment of the present invention, the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0031] As a preferred embodiment of the present invention, the alloy material further includes a compatibilizer, and the mass ratio of the compatibilizer to the conductive carbon black is (5-6):1.

[0032] As a preferred embodiment of the present invention, the compatibilizer is poly(1,4-cyclohexane dimethyl terephthalate) having an intrinsic viscosity of 0.7-1 dl / g, which is measured according to ISO 1628.

[0033] The specific embodiments of the present invention also provide a method for preparing the aforementioned PBT / PPO alloy material, the method comprising the following steps:

[0034] The formulated amount of PPO, toughening agent, lubricant, antioxidant, conductive carbon black and compatibilizer are mixed in a high-speed mixer to obtain a mixture, and the mixture is fed from the main feeding port of a twin-screw extruder, and PBT is fed from the side to perform extrusion granulation.

[0035] As a preferred embodiment of the present invention, the mixing processing time is 3 min-7 min, such as 3 min, 4 min, 5 min, 6 min or 7 min, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] As a preferred embodiment of the present invention, the ratio of the screw length to the screw diameter of the twin-screw extruder is 30-48, for example, 30, 32, 34, 36, 38, 40, 42, 44, 46 or 48, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] As a preferred embodiment of the present invention, the control temperature of each section of the twin-screw extruder is 250°C-290°C, for example, 250°C, 260°C, 270°C, 280°C or 290°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the screw speed of the twin-screw extruder is 350rpm-450rpm, for example, 350 rpm, 370rpm, 390 rpm, 410rpm, 430 rpm or 450 rpm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0038] As a preferred embodiment of the present invention, after extrusion granulation, the obtained particles are dried and then injection molded into standard specimens for testing using an injection molding machine; wherein the drying temperature is 110-130°C, for example, 110°C, 115°C, 120°C, 125°C or 130°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the drying time is 4-6h, for example, 4h, 5h or 6h, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; injection molding The control temperature of each section of the machine is 270°C-300°C, for example, 270°C, 280°C, 290°C or 300°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable; the screw speed is set to 120rpm-180rpm, for example, 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm or 180rpm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0039] The following are typical but non-limiting examples of the present invention: The following examples include PBT (brand TH6100, Bluestar Tunhe); PPO (brand LXN045, Bluestar); toughening agent (brand G1657, Kraton); antioxidant (P-EPQ, Clariant); lubricant (silicone additive, Evonik Specialty Chemicals, the functional group of the silicone additive is primary hydroxyl group with a functionality of 2); and compatibilizer (brand 0502, SK, South Korea).

[0040] Example 1: This embodiment provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 8 parts of a compatibilizer.

[0041] The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an 8wt% hydrogen peroxide solution, ultrasonically treated at 50°C for 2h for mild oxidation, and then centrifuged, washed, and dried to obtain oxidized carbon black. The oxidized carbon black and a silane compound are then refluxed in anhydrous ethanol at 85°C for 4h, centrifuged, washed, and dried to obtain modified carbon black. The modified carbon black is reacted with an ionic liquid at 60°C for 6h under the action of diisopropylcarbodiimide, washed with ethanol, and dried to obtain conductive carbon black. The mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black brand is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt.

[0042] The preparation method of the PBT / PPO alloy material is as follows: The formulated amounts of PPO, toughening agent, lubricant, antioxidant, conductive carbon black and compatibilizer were mixed evenly in a high-speed mixer for 4 minutes and then fed from the main feeding port of a twin-screw extruder, and PBT was fed from the side feeding port of the twin-screw extruder. The temperature settings of each section of the twin-screw extruder were: 260°C, 285°C, 285°C, 285°C, 255°C, 255°C, 255°C, 255°C, 285°C, the screw speed was set to 400 rpm, and the ratio of screw length L to screw diameter D was 44. Extrusion granulation was carried out to obtain a PBT / PPO alloy material.

[0043] Example 2: This embodiment provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 55 parts of PBT, 22 parts of PPO, 10 parts of a toughening agent, 1.2 parts of a lubricant, 0.8 parts of an antioxidant, 1.7 parts of conductive carbon black, and 9.3 parts of a compatibilizer.

[0044] The preparation process of the conductive carbon black is the same as that in Example 1.

[0045] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0046] Comparative Example 1: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 47.5 parts of PBT, 30 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 8 parts of a compatibilizer.

[0047] The preparation process of the conductive carbon black is the same as that in Example 1.

[0048] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0049] Comparative Example 2: This comparative example provides a PBT / PPO alloy suitable for online spray coating and its preparation method. The alloy comprises the following raw materials, by weight: 57.5 parts PBT, 20 parts PPO, 12 parts toughening agent, 0.5 parts lubricant, 0.5 parts antioxidant, 1.5 parts conductive carbon black, and 8 parts compatibilizer. The toughening agent, containing 37% styrene, was purchased from Kraton's G1701.

[0050] The preparation process of the conductive carbon black is the same as that in Example 1.

[0051] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0052] Comparative Example 3: This comparative example provides a PBT / PPO alloy material suitable for online spray coating and a preparation method thereof. The alloy material comprises the following raw materials, by weight: 57.5 parts PBT, 20 parts PPO, 12 parts toughening agent, 0.5 parts lubricant, 0.5 parts antioxidant, 1.5 parts conductive carbon black, and 0 parts compatibilizer. The preparation process of the conductive carbon black is the same as that in Example 1.

[0053] The preparation process of the conductive carbon black is the same as that in Example 1.

[0054] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0055] Comparative Example 4: This comparative example provides a PBT / PPO alloy material suitable for online spray coating and a preparation method thereof. The alloy material comprises the following raw materials, by weight: 57.5 parts PBT, 20 parts PPO, 12 parts toughening agent, 0.5 parts lubricant, 0.5 parts antioxidant, 1.5 parts conductive carbon black, and 12 parts compatibilizer. The compatibilizer is polyethylene oxide grafted with maleic anhydride.

[0056] The preparation process of the conductive carbon black is the same as that in Example 1.

[0057] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0058] Comparative Example 5: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 4 parts of a compatibilizer.

[0059] The preparation process of the conductive carbon black is the same as that in Example 1.

[0060] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0061] Comparative Example 6: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0062] The preparation process of the conductive carbon black is the same as that in Example 1.

[0063] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0064] Comparative Example 7: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0065] The conductive carbon black was prepared as follows: the carbon black was dispersed in an 8 wt % hydrogen peroxide solution, subjected to ultrasonic treatment at 50° C. for 2 h for mild oxidation, and then centrifuged, washed, and dried to obtain the conductive carbon black; the carbon black was XCMAX22, purchased from Cabot Corporation.

[0066] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0067] Comparative Example 8: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0068] The preparation process of the conductive carbon black is as follows: dispersing carbon black in an 8wt% hydrogen peroxide solution, ultrasonically treating at 50°C for 2h for mild oxidation, centrifugally washing and drying after oxidation to obtain oxidized carbon black, then reflux-reacting the oxidized carbon black with a silane compound in anhydrous ethanol at 85°C for 4h, centrifugally washing and drying to obtain the conductive carbon black; the mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the carbon black is XCMAX22, purchased from Cabot Corporation; and the silane compound is γ-aminoethylaminopropyltrimethoxysilane.

[0069] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0070] Comparative Example 9: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0071] The conductive carbon black is prepared as follows: carbon black is dispersed in an 8wt% hydrogen peroxide solution, subjected to ultrasonic treatment at 50°C for 2h for mild oxidation, and then centrifuged, washed, and dried to obtain oxidized carbon black. The oxidized carbon black is then reacted with an ionic liquid at 60°C for 6h under the action of diisopropylcarbodiimide, washed with ethanol, and dried to obtain the conductive carbon black. The mass ratio of the ionic liquid to the oxidized carbon black is 3:1. The carbon black is XCMAX22, purchased from Cabot Corporation. The ionic liquid is 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt.

[0072] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0073] Comparative Example 10: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0074] The preparation process of the conductive carbon black is as follows: carbon black and a silane compound are refluxed in anhydrous ethanol at 85°C for 4 hours, centrifuged, washed, and dried to obtain modified carbon black, the modified carbon black is reacted with an ionic liquid at 60°C for 6 hours under the action of diisopropylcarbodiimide, washed with ethanol, and dried to obtain conductive carbon black; the mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black brand is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt.

[0075] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0076] Comparative Example 11: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0077] The preparation process of the conductive carbon black is as follows: dispersing carbon black in an 8wt% hydrogen peroxide solution, ultrasonically treating at 50°C for 2h for mild oxidation, centrifugally washing and drying after oxidation to obtain oxidized carbon black, then reflux reacting the oxidized carbon black with a silane compound in anhydrous ethanol at 85°C for 4h, centrifugally washing and drying to obtain modified carbon black, reacting the modified carbon black with an ionic liquid at 60°C for 6h under the action of diisopropylcarbodiimide, washing with ethanol, and drying to obtain conductive carbon black; the mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black brand is XCMAX22, purchased from Cabot Corporation; the silane compound is KH-550; and the ionic liquid is 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide salt.

[0078] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0079] Comparative Example 12: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0080] The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an 8wt% hydrogen peroxide solution, ultrasonically treated at 50°C for 2h for mild oxidation, and then centrifuged, washed, and dried to obtain oxidized carbon black. The oxidized carbon black and a silane compound are then refluxed in anhydrous ethanol at 85°C for 4h, centrifuged, washed, and dried to obtain modified carbon black. The modified carbon black is reacted with an ionic liquid at 60°C for 6h under the action of diisopropylcarbodiimide, washed with ethanol, and dried to obtain conductive carbon black. The mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black brand is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-ethyl-3-methylimidazole phosphate.

[0081] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0082] Comparative Example 13: This comparative example provides a PBT / PPO alloy material suitable for online spraying and a preparation method thereof. The alloy material comprises the following raw material components by weight: 57.5 parts of PBT, 20 parts of PPO, 12 parts of a toughening agent, 0.5 parts of a lubricant, 0.5 parts of an antioxidant, 1.5 parts of conductive carbon black, and 12 parts of a compatibilizer.

[0083] The conductive carbon black is prepared as follows: dispersing carbon black in an 8wt% hydrogen peroxide solution, ultrasonically treating at 50°C for 2h for mild oxidation, centrifugally washing and drying after oxidation to obtain oxidized carbon black, then reflux-reacting the oxidized carbon black with a silane compound in anhydrous ethanol at 85°C for 4h, centrifugally washing and drying to obtain modified carbon black, reacting the modified carbon black with an ionic liquid at 60°C for 6h under the action of diisopropylcarbodiimide, washing with ethanol, and drying to obtain the conductive carbon black; the mass ratio of the silane compound to the oxidized carbon black is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black has an iodine absorption value of 253 mg / g and an oil absorption value of 174 mL / 100g, is brand XC72, and is purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazole bis(trifluoromethanesulfonyl)imide.

[0084] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0085] The performance of the PBT / PPO alloy materials in Examples 1-2 and Comparative Examples 1-13 was tested using ISO and IEC standards. The test results are shown in Tables 1 and 2 below.

[0086] Table 1: Alloy performance test results of Examples 1-2 and Comparative Examples 1-5

[0087] Table 2: Alloy performance test results of Comparative Examples 6-13

[0088] From the comparison in the above table, it can be seen that in Example 1 and Comparative Example 1, when the amount of PPO added increases, the toughness of the alloy material deteriorates and the resistivity increases. In Comparative Example 2, when the styrene content in the toughening agent increases from 13% to 37%, no compatibilizer is added in Comparative Example 3, maleic anhydride-grafted polyethylene oxide is used as a compatibilizer in Comparative Example 4, and the amount of compatibilizer added is reduced in Comparative Example 5. All of these have an impact on the mechanical properties and heat distortion temperature of the alloy material. This further illustrates that in the system of the present invention, the selection of a specific amount of poly(1,4-cyclohexanedimethyl terephthalate) as a compatibilizer and the control of the styrene content in the toughening agent can achieve a balance between rigidity, toughness, and heat resistance in the alloy material. In particular, the absence of a compatibilizer has a significant impact on the resistivity. This may be because the lack of a compatibilizer makes PBT / PPO more prone to phase separation, resulting in uneven dispersion of the conductive carbon black.

[0089] In Comparative Example 6, the carbon black was not modified, and the volume resistivity increased significantly, and the tensile strength also decreased. In Comparative Example 7, the carbon black was only oxidized. In Comparative Example 8, the carbon black was only modified with a silane compound after oxidation. In Comparative Example 9, the carbon black was only modified with an ionic liquid after oxidation. In Comparative Example 10, the carbon black was not oxidized and only modified with a silane compound and an ionic liquid. In this case, the conductivity was slightly improved, and other properties were relatively poor. This may be because the surface of the oxidized carbon black generates functional groups such as hydroxyl and carboxyl groups, which provide reaction sites for the subsequent modification treatment, thereby weakening the effect of the carbon black that has not been pre-oxidized in the system. In other words, the applicant unexpectedly discovered that in the system of the present invention, only by first oxidizing the carbon black and then modifying it with a silane compound and an ionic liquid in sequence can the conductive carbon black interact better with other components in the matrix, resulting in an alloy material with excellent comprehensive properties.

[0090] In Comparative Example 11, the silane compound is replaced by KH550, in Comparative Example 12, the ionic liquid is replaced by 1-ethyl-3-methylimidazole phosphate, and in Comparative Example 13, the carbon black selected has an iodine absorption value of 253 mg / g and an oil absorption value of 174 mL / 100 g, all of which will affect the conductivity and mechanical properties of the alloy. This further illustrates that in the modification treatment of carbon black of the present invention, specific carbon black, γ-aminoethylaminopropyltrimethoxysilane, and 1-butyl-3-methylimidazole bistrifluoromethanesulfonyl imide salt are selected as modifiers. In the system of the present invention, not only can the interface bonding between carbon black and PBT / PPO matrix be improved and the compliance rate of volume resistivity be increased, but also the mechanical properties of the material, such as tensile strength and impact strength, are also good.

[0091] In summary, the present invention uses low-viscosity PBT as the first matrix resin and PPO as the second matrix resin, and interacts with the toughening agent, conductive carbon black, compatibilizer, etc. in the system to balance the rigidity, toughness and processing performance of the material. The final prepared PBT / PPO composite material has high flow, high impact, high heat resistance and good spraying performance. It can be used to manufacture components with high weather resistance requirements such as automotive charging port covers and door handle trim covers.

[0092] While the present invention uses the above-described embodiments to illustrate the detailed process equipment and process flow of the present invention, the present invention is not limited to the above-described detailed process equipment and process flow, and does not necessarily rely on the above-described detailed process equipment and process flow for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent replacements for raw materials in the products of the present invention, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A PBT / PPO alloy material suitable for online spraying, characterized in that: The alloy material includes the following raw material components by weight: 50-60 parts of PBT, 15-25 parts of PPO, 8-12 parts of toughening agent, 0.5-2 parts of lubricant, 0.2-1.0 parts of antioxidant, and 1-2 parts of conductive carbon black; the conductive carbon black is obtained by modifying carbon black, and the iodine absorption value of the carbon black is 1000-1400 mg / g and the oil absorption value is 300-340 mL / 100g.

2. The PBT / PPO alloy material according to claim 1, characterized in that: The relative viscosity of PBT is 0.8-1.2 dl / g.

3. The PBT / PPO alloy material according to claim 1, characterized in that: The intrinsic viscosity of PPO is 0.43-0.46 dl / g.

4. The PBT / PPO alloy material according to claim 1, characterized in that: The styrene content in the toughening agent is 10-20%.

5. The PBT / PPO alloy material according to claim 1, characterized in that: The lubricant is selected from one or a combination of silicone masterbatch, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer.

6. The PBT / PPO alloy material according to claim 1, characterized in that: The antioxidant is selected from one or a combination of β (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3 tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 trimethyl 2,4,6 tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-tert-butylphenyl) phosphite, dioctadecyl pentaerythritol diphosphite, pentaerythritol stearate, and aromatic phosphite antioxidants.

7. The PBT / PPO alloy material according to claim 1, characterized in that: The alloy material further includes a compatibilizer, and the mass ratio of the compatibilizer to the conductive carbon black is (5-6):

1.

8. The PBT / PPO alloy material according to claim 1, characterized in that: The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an oxidant solution and oxidized to obtain oxidized carbon black, the oxidized carbon black and a silane compound are refluxed in a solvent to obtain modified carbon black, and the modified carbon black is reacted with an ionic liquid under the action of a catalyst, and the conductive carbon black is obtained after drying.

9. A method for preparing the PBT / PPO alloy material according to any one of claims 1 to 8, characterized in that: The preparation method comprises: The formulated amount of PPO, toughening agent, lubricant, antioxidant, conductive carbon black and compatibilizer are mixed in a high-speed mixer to obtain a mixture, and the mixture is fed from the main feeding port of a twin-screw extruder, and PBT is fed from the side to perform extrusion granulation.

10. The preparation method according to claim 9, characterized in that The mixing time is 3 min-7 min; the ratio of the screw length to the screw diameter of the twin-screw extruder is 30-48; the control temperature of each section of the twin-screw extruder is 250° C.-290° C., and the rotation speed is 350 rpm-450 rpm.

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