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

Abstract

This invention provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components by weight: 50-60 parts PBT, 15-25 parts PPO, 8-12 parts toughening agent, 0.5-2 parts lubricant, 0.2-1.0 parts antioxidant, and 1-2 parts 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. The final PBT / PPO composite material possesses high flowability, high impact resistance, high heat resistance, and good spraying performance, and can be used to manufacture components with high weather resistance requirements, such as automotive charging port covers and door handle trim covers.

Description

Technical Field

[0001] This invention belongs to the field of polymer material modification technology, and relates to a PBT / PPO alloy material suitable for online spraying and its preparation method. Background Technology

[0002] Polybutylene terephthalate (PBT) is a crystalline thermoplastic polyester resin containing carbonyl groups (-COO-) in its main chain. PBT possesses excellent properties such as high temperature resistance, moisture resistance, oil resistance, good electrical insulation, chemical corrosion resistance, fast molding, low moisture absorption, and ease of molding and processing. After proper modification, it is widely used in many fields including electronics, automobiles, machinery, and optical fiber sheathing. Polyphenylene oxide (PPO or PPE) is one of the world's five major general-purpose engineering plastics. With a density of only about 1.05 g / cm³, it has the lowest density among engineering plastics. It possesses advantages such as high rigidity, high heat resistance, flame retardancy, high strength, and excellent electrical properties. In addition, PPO also has advantages such as wear resistance, non-toxicity, and pollution resistance. PPO has one of the lowest dielectric constants and dielectric losses among engineering plastics, almost unaffected by temperature and humidity, and can be used in low, medium, and high frequency electric field applications.

[0003] Fuel filler caps, charging port covers, and concealed door handle covers in gasoline, hybrid, and electric vehicles often utilize high-temperature resistant PA / PPO alloys that can be sprayed online. However, with the increasing frequency of extreme weather events in recent years, especially the hot and rainy summers, PA / PPO alloys are susceptible to dimensional changes and warping after rapid moisture absorption, further affecting their normal use. To address the moisture absorption problem of PA / PPO alloys, we propose replacing them with PBT / PPO alloys. Through interactions with other components, a PBT / PPO alloy material suitable for online spraying can be prepared. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention adopts the following technical solution:

[0005] 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 PBT, 15-25 parts PPO, 8-12 parts toughening agent, 0.5-2 parts lubricant, 0.2-1.0 parts antioxidant, and 1-2 parts conductive carbon black; wherein 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.

[0006] As a preferred embodiment of the present invention, the relative viscosity of the polybutylene terephthalate is 0.8-1.2 dl / g.

[0007] As a preferred embodiment of the present invention, the intrinsic viscosity of the polyphenylene ether is 0.43-0.46 dl / g.

[0008] As a preferred embodiment of the present invention, the toughening agent contains 10-20% styrene.

[0009] 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.

[0010] As a preferred embodiment of the present invention, the antioxidant is selected from one or a combination of several of the following: 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 dioctadecanol diphosphite, pentaerythritol stearate, and aryl phosphite.

[0011] As a preferred embodiment of the present invention, the alloy material further includes a compatibilizer, wherein the mass ratio of the compatibilizer to the conductive carbon black is (5-6):1.

[0012] 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 carbon oxide black; carbon oxide black and silane compound are refluxed in a solvent to obtain modified carbon black; then the modified carbon black is reacted with an ionic liquid under the action of a catalyst, and after drying, conductive carbon black is obtained.

[0013] Secondly, the present invention provides a method for preparing the aforementioned PBT / PPO alloy material, the method comprising the following steps:

[0014] The formulated amounts of PPO, toughening agent, lubricant, antioxidant, conductive carbon black, and compatibilizer are mixed in a high-speed mixer to obtain a mixture. The mixture is fed from the main feed port of a twin-screw extruder, while PBT is fed from the side feed port for extrusion granulation.

[0015] As a preferred embodiment of the present invention, 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 controlled temperature of each section of the twin-screw extruder is 250℃-290℃, and the rotation speed is 350 rpm-450 rpm.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] This invention uses low-viscosity PBT as the first matrix resin and PPO as the second matrix resin. Through interaction with toughening agents, conductive carbon black, compatibilizers, etc. in the system, the rigidity, toughness and processing performance of the materials are balanced, so that the final PBT / PPO composite material has high flow, high impact, high heat resistance and good spraying performance. It can be used to manufacture parts with high weather resistance requirements, such as car charging port covers and door handle covers. Detailed Implementation

[0018] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention will be 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 is determined by the claims.

[0019] The specific embodiments of this invention provide a PBT / PPO alloy material suitable for online spraying. The alloy material comprises the following raw material components by weight: 50-60 parts PBT, 15-25 parts PPO, 8-12 parts toughening agent, 0.5-2 parts lubricant, 0.2-1.0 parts antioxidant, and 1-2 parts conductive carbon black.

[0020] As a more preferred embodiment of the present invention, the relative viscosity of the polybutylene terephthalate is 0.8-1.2 dl / g, which is obtained by measurement according to GB / T 14190-2017.

[0021] As a more preferred embodiment of the present invention, the intrinsic viscosity of the polyphenylene ether is 0.43-0.46 dl / g, which is obtained by measuring according to ISO 1628.

[0022] The dosage of PBT can be 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, or 60 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The dosage of PPO can be 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, or 25 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The dosage of toughening agent can be 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. The lubricant... 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; other unlisted values ​​within this range are also applicable. The dosage of 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; other unlisted values ​​within this range are also applicable. The dosage of 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; other unlisted values ​​within this range are also applicable.

[0023] In a preferred embodiment of the present invention, the toughening agent contains 10-20% styrene; in a more preferred embodiment of the present invention, the toughening agent contains 13% styrene.

[0024] In a preferred embodiment of the present invention, the lubricant is selected from one or a combination of several of silicone masterbatch, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer. In a preferred embodiment of the present invention, the lubricant is silicone masterbatch.

[0025] As a preferred embodiment of the present invention, the antioxidant is selected from one or a combination of several of the following: 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 dioctadecanol diphosphite, pentaerythritol stearate, and aryl phosphites; as a preferred embodiment of the present invention, the antioxidant is an aryl phosphite.

[0026] 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 carbon oxide black; carbon oxide black and silane compound are refluxed in a solvent to obtain modified carbon black; then the modified carbon black is reacted with an ionic liquid under the action of a catalyst, and after drying, conductive carbon black is obtained.

[0027] 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 5-10 wt% hydrogen peroxide solution and subjected to ultrasonic treatment at 40-60℃ for 1-3 hours for mild oxidation. After oxidation, the carbon black is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 80-90℃ for 3-5 hours. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 50-70℃ for 5-7 hours under the action of a catalyst. After washing with ethanol and drying, conductive carbon black is obtained.

[0028] As a preferred embodiment of the present invention, the catalyst is diisopropylcarbodiimide; the amount of the catalyst is 5-20% of the mass of the ionic liquid.

[0029] In 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 / 100g; in another preferred embodiment, the carbon black has an iodine absorption value of 1360 mg / g and an oil absorption value of 320 mL / 100g. The iodine absorption value is measured using ASTM D-1510; the oil absorption value is measured using ASTM D-2414.

[0030] In a preferred embodiment of the present invention, the mass ratio of the silane compound to carbon black oxide is (0.1-0.5):1; in a preferred embodiment of the present invention, the mass ratio of the silane compound to carbon black oxide is 0.3:1.

[0031] 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.

[0032] As a preferred embodiment of the present invention, the silane compound is γ-aminoethylaminopropyltrimethoxysilane.

[0033] As a preferred embodiment of the present invention, the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0034] As a preferred embodiment of the present invention, the alloy material further includes a compatibilizer, wherein the mass ratio of the compatibilizer to the conductive carbon black is (5-6):1.

[0035] As a preferred embodiment of the present invention, the compatibilizer is poly(1,4-cyclohexanedimethyl terephthalate) with an intrinsic viscosity of 0.7-1 dl / g, which is measured by ISO 1628.

[0036] The specific embodiments of this invention also provide a method for preparing the aforementioned PBT / PPO alloy material, the method comprising the following steps:

[0037] The formulated amounts of PPO, toughening agent, lubricant, antioxidant, conductive carbon black, and compatibilizer are mixed in a high-speed mixer to obtain a mixture. The mixture is fed from the main feed port of a twin-screw extruder, while PBT is fed from the side feed port for extrusion granulation.

[0038] As a preferred embodiment of the present invention, the mixing and processing time is 3 min to 7 min, such as 3 min, 4 min, 5 min, 6 min or 7 min, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0039] 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, such as 30, 32, 34, 36, 38, 40, 42, 44, 46 or 48, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0040] As a preferred embodiment of the present invention, the controlled temperature of each section of the twin-screw extruder is 250℃-290℃, such as 250℃, 260℃, 270℃, 280℃ or 290℃, etc., but not limited to the listed values, other unlisted values ​​within this range are also applicable; the screw speed of the twin-screw extruder is 350rpm-450rpm, such as 350 rpm, 370rpm, 390 rpm, 410rpm, 430 rpm or 450 rpm, etc., but not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0041] In a preferred embodiment of the present invention, after extrusion granulation, the obtained particles are dried and then injection molded into standard test strips using an injection molding machine. The drying temperature is 110-130℃, such as 110℃, 115℃, 120℃, 125℃, or 130℃, but not limited to the listed values; other unlisted values ​​within this range are also applicable. The drying time is 4-6 hours, such as 4 hours, 5 hours, or 6 hours, but not limited to the listed values; other unlisted values ​​within this range are also applicable. Injection molding... The controlled temperature of each section of the machine is 270℃-300℃, such as 270℃, 280℃, 290℃ or 300℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable. The screw speed is set to 120rpm-180rpm, such as 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 170rpm or 180rpm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0042] The following are typical but non-limiting embodiments of the present invention:

[0043] The following examples use PBT (TH6100, Lanshan Tunhe); PPO (LXN045, Lanxing); toughening agent (G1657, Keteng); antioxidant (P-EPQ, Clariant); lubricant (silicone additive, Evonik Specialty Chemicals, the functional group of which is a primary alcohol hydroxyl group with a functionality of 2); and compatibilizer (0502, SK Korea).

[0044] Example 1:

[0045] This embodiment provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0046] The preparation process of the conductive carbon black is as follows: Carbon black is dispersed in an 8 wt% hydrogen peroxide solution and gently oxidized by ultrasonic treatment at 50°C for 2 h. After oxidation, it is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 85°C for 4 h. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 60°C for 6 h under the action of diisopropylcarbodiimide. After washing with ethanol and drying, conductive carbon black is obtained. 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 grade is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0047] The preparation method of the PBT / PPO alloy material is as follows:

[0048] The formulated amounts of PPO, toughening agent, lubricant, antioxidant, conductive carbon black, and compatibilizer are mixed uniformly in a high-speed mixer for 4 minutes and then fed into the main feed port of a twin-screw extruder. PBT is fed into the side feed port of the twin-screw extruder. The temperature settings for each section of the twin-screw extruder are: 260℃, 285℃, 285℃, 285℃, 255℃, 255℃, 255℃, 255℃, 285℃. The screw speed is set to 400 rpm, and the ratio of screw length L to screw diameter D is 44. Extrusion granulation is performed to obtain PBT / PPO alloy material.

[0049] Example 2:

[0050] This embodiment provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components by weight: 55 parts PBT, 22 parts PPO, 10 parts toughening agent, 1.2 parts lubricant, 0.8 parts antioxidant, 1.7 parts conductive carbon black, and 9.3 parts compatibilizer.

[0051] The preparation process of the conductive carbon black is the same as that in Example 1.

[0052] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0053] Comparative Example 1:

[0054] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components by weight: 47.5 parts PBT, 30 parts PPO, 12 parts toughening agent, 0.5 parts lubricant, 0.5 parts antioxidant, 1.5 parts conductive carbon black, and 8 parts compatibilizer.

[0055] The preparation process of the conductive carbon black is the same as that in Example 1.

[0056] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0057] Comparative Example 2:

[0058] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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 has a styrene content of 37% and is purchased from Kraton G1701.

[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 3:

[0062] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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 in Example 1.

[0063] The preparation process of the conductive carbon black is the same as that in Example 1.

[0064] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0065] Comparative Example 4:

[0066] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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 maleic anhydride-grafted polyethylene oxide.

[0067] The preparation process of the conductive carbon black is the same as that in Example 1.

[0068] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0069] Comparative Example 5:

[0070] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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 4 parts compatibilizer.

[0071] The preparation process of the conductive carbon black is the same as that in Example 1.

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

[0073] Comparative Example 6:

[0074] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0075] The preparation process of the conductive carbon black is the same as that in Example 1.

[0076] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0077] Comparative Example 7:

[0078] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0079] The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an 8 wt% hydrogen peroxide solution, and mildly oxidized by ultrasonic treatment at 50°C for 2 h. After oxidation, it is centrifuged, washed and dried to obtain conductive carbon black. The carbon black grade is XCMAX22, which was purchased from Cabot Corporation.

[0080] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0081] Comparative Example 8:

[0082] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0083] The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an 8 wt% hydrogen peroxide solution and subjected to mild oxidation by ultrasonic treatment at 50°C for 2 h. After oxidation, the carbon black is obtained by centrifugation, washing and drying. Then, the carbon black oxide is reacted with a silane compound in anhydrous ethanol under reflux at 85°C for 4 h. After centrifugation, washing and drying, the conductive carbon black is obtained. The mass ratio of the silane compound to the carbon black oxide is 0.3:1. The carbon black grade is XCMAX22, purchased from Cabot Corporation. The silane compound is γ-aminoethylaminopropyltrimethoxysilane.

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

[0085] Comparative Example 9:

[0086] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0087] The preparation process of the conductive carbon black is as follows: carbon black is dispersed in an 8 wt% hydrogen peroxide solution and subjected to mild oxidation by ultrasonic treatment at 50°C for 2 h. After oxidation, the carbon black is centrifuged, washed, and dried to obtain carbon oxide. Then, the carbon oxide reacts with an ionic liquid at 60°C for 6 h under the action of diisopropylcarbodiimide. After washing with ethanol and drying, the conductive carbon black is obtained. The mass ratio of the ionic liquid to the carbon oxide is 3:1. The carbon black grade is XCMAX22, purchased from Cabot Corporation. The ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0088] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0089] Comparative Example 10:

[0090] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0091] 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. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black is reacted with an ionic liquid at 60°C for 6 hours under the action of diisopropylcarbodiimide. After washing with ethanol and drying, conductive carbon black is obtained. The mass ratio of the silane compound to carbon black oxide is 0.3:1; the mass ratio of the ionic liquid to the modified carbon black is 3:1; the carbon black grade is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0092] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0093] Comparative Example 11:

[0094] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0095] The preparation process of the conductive carbon black is as follows: Carbon black is dispersed in an 8 wt% hydrogen peroxide solution and gently oxidized by ultrasonic treatment at 50°C for 2 h. After oxidation, it is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 85°C for 4 h. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 60°C for 6 h under the action of diisopropylcarbodiimide. After washing with ethanol and drying, conductive carbon black is obtained. 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 grade is XCMAX22, purchased from Cabot Corporation; the silane compound is KH-550; and the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0096] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0097] Comparative Example 12:

[0098] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0099] The preparation process of the conductive carbon black is as follows: Carbon black is dispersed in an 8 wt% hydrogen peroxide solution and gently oxidized by ultrasonic treatment at 50°C for 2 h. After oxidation, it is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 85°C for 4 h. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 60°C for 6 h under the action of diisopropylcarbodiimide. After washing with ethanol and drying, conductive carbon black is obtained. 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 grade is XCMAX22, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-ethyl-3-methylimidazolium phosphate.

[0100] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0101] Comparative Example 13:

[0102] This comparative example provides a PBT / PPO alloy material suitable for online spraying and its preparation method. The alloy material comprises the following raw material components 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.

[0103] The preparation process of the conductive carbon black is as follows: Carbon black is dispersed in an 8 wt% hydrogen peroxide solution and gently oxidized by ultrasonic treatment at 50°C for 2 h. After oxidation, it is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 85°C for 4 h. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 60°C for 6 h under the action of diisopropylcarbodiimide. After washing with ethanol and drying, conductive carbon black is obtained. 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, and its grade is XC72, purchased from Cabot Corporation; the silane compound is γ-aminoethylaminopropyltrimethoxysilane; and the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt.

[0104] The preparation method of the PBT / PPO alloy material is the same as that in Example 1.

[0105] 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.

[0106] Table 1: Alloy property test results of Examples 1-2 and Comparative Examples 1-5

[0107]

[0108] Table 2: Alloy property test results of Comparative Example 6-13

[0109]

[0110] The comparison in the table above shows that in Example 1 and Comparative Example 1, the toughness of the alloy material deteriorates and the resistivity increases when the amount of PPO added increases. In Comparative Example 2, the styrene content in the toughening agent increases from 13% to 37%. In Comparative Example 3, no compatibilizer is added. In Comparative Example 4, maleic anhydride-grafted polyethylene oxide is used as a compatibilizer. In Comparative Example 5, the amount of compatibilizer added is reduced. All of these situations affect the mechanical properties and heat distortion temperature of the alloy material. This further illustrates that by selecting a specific amount of poly(1,4-cyclohexanedimethyl terephthalate) as a compatibilizer and controlling the styrene content in the toughening agent, a balance can be achieved between the rigidity, toughness, and heat resistance of the alloy material in the system of this invention. 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 prone to phase separation, resulting in uneven dispersion of the conductive carbon black.

[0111] In Comparative Example 6, the carbon black was not modified, resulting in a significant increase in volume resistivity and a decrease in tensile strength. In Comparative Example 7, the carbon black underwent only oxidation treatment. In Comparative Example 8, the oxidized carbon black was modified only with silane compounds. In Comparative Example 9, the oxidized carbon black was modified only with ionic liquids. In Comparative Example 10, the carbon black was not oxidized and only modified with silane compounds and ionic liquids. In this case, the improvement in conductivity was small, and other properties were relatively poor. This may be because oxidized carbon black forms functional groups such as hydroxyl and carboxyl groups on its surface, providing reaction sites for subsequent modification treatments, thus weakening the role of the unoxidized carbon black in the system. In other words, the applicant unexpectedly discovered that in the system of this invention, only by first oxidizing the carbon black and then sequentially modifying it with silane compounds and ionic liquids can the conductive carbon black interact better with other components in the matrix, resulting in an alloy material with excellent comprehensive performance.

[0112] In Comparative Example 11, the silane compound was replaced with KH550; in Comparative Example 12, the ionic liquid was replaced with 1-ethyl-3-methylimidazolium phosphate; and in Comparative Example 13, the carbon black used had an iodine absorption value of 253 mg / g and an oil absorption value of 174 mL / 100g. All of these factors affect the conductivity and mechanical properties of the alloy. This further illustrates that the specific carbon black, γ-aminoethylaminopropyltrimethoxysilane, and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt were selected as modifiers in the carbon black modification treatment of this invention. In the system of this invention, not only can the interfacial bonding between carbon black and PBT / PPO matrix be improved and the volume resistivity compliance rate be increased, but the tensile strength, impact strength, and other mechanical properties of the material are also better.

[0113] In summary, this invention uses low-viscosity PBT as the first matrix resin and PPO as the second matrix resin. Through interaction with toughening agents, conductive carbon black, compatibilizers, etc. in the system, the rigidity, toughness, and processing performance of the materials are balanced, so that the final PBT / PPO composite material has high flow, high impact, high heat resistance and good spraying performance. It can be used to manufacture parts with high weather resistance requirements, such as car charging port covers and door handle covers.

[0114] This invention illustrates the detailed process equipment and process flow through the above embodiments. However, this invention is not limited to the detailed process equipment and process flow described above, meaning that this invention does not necessarily depend on the detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, all fall within the protection scope and disclosure scope of this invention.

Claims

1. A PBT / PPO alloy material suitable for online spraying, characterized in that, The alloy material comprises the following raw material components by weight: 50-60 parts PBT, 15-25 parts PPO, 8-12 parts toughening agent, 0.5-2 parts lubricant, 0.2-1.0 parts antioxidant, and 1-2 parts 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 mg / g. mL / 100g; The preparation process of the conductive carbon black is as follows: Carbon black is dispersed in a 5-10wt% hydrogen peroxide solution, and mildly oxidized by ultrasonic treatment at 40-60℃ for 1-3h. After oxidation, it is centrifuged, washed, and dried to obtain oxidized carbon black. Then, the oxidized carbon black and a silane compound are refluxed in anhydrous ethanol at 80-90℃ for 3-5h. After centrifugation, washing, and drying, modified carbon black is obtained. The modified carbon black and an ionic liquid are reacted at 50-70℃ for 5-7h under the action of a catalyst. After washing with ethanol and drying, conductive carbon black is obtained. The silane compound is γ-aminoethylaminopropyltrimethoxysilane; the ionic liquid is 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt; the alloy material also includes a compatibilizer, and the mass ratio of the compatibilizer to the conductive carbon black is (5-6):1; the compatibilizer is poly(1,4-cyclohexanedimethyl terephthalate) with an intrinsic viscosity of 0.7-1 dl / g; the toughening agent is Kronen G1657.

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 lubricant is selected from one or a combination of silicone masterbatch, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer.

5. The PBT / PPO alloy material according to claim 1, characterized in that, The antioxidant is selected from one or a combination of several of the following: 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 dioctadecanol diphosphite, pentaerythritol stearate, and aryl phosphite antioxidants.

6. A method for preparing the PBT / PPO alloy material as described in any one of claims 1-5, characterized in that, The preparation method includes: The formulated amounts of PPO, toughening agent, lubricant, antioxidant, conductive carbon black, and compatibilizer are mixed in a high-speed mixer to obtain a mixture. The mixture is fed from the main feed port of a twin-screw extruder, while PBT is fed from the side feed port for extrusion granulation.

7. The preparation method according to claim 6, characterized in that, The mixing time is 3-7 minutes; the ratio of screw length to screw diameter of the twin-screw extruder is 30-48; the controlled temperature of each section of the twin-screw extruder is 250℃-290℃, and the rotation speed is 350rpm-450rpm.

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