CN114605785B - High-wear-resistance and high-toughness PBT (polybutylene terephthalate) material for automobile stay cables and preparation method thereof - Google Patents
High-wear-resistance and high-toughness PBT (polybutylene terephthalate) material for automobile stay cables and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-wear-resistance and toughened PBT material for an automobile cable, which comprises the following raw materials in parts by weight: 70-90 parts of PBT, 5-20 parts of wear-resistant agent, 5-10 parts of toughening agent, 0.2-2 parts of compatibilizer, 0.4-2.0 parts of antioxidant, 0.2-1.0 part of lubricant, 0.1-0.5 part of graphene composite modified polyimide fiber and 0.1-0.3 part of ionic liquid composite rare earth liquid. The PBT material is used as a matrix, and is processed and granulated by a double-screw extruder with the diameter of phi 30mm through the optimized combination and proportion of the wear-resisting agent, the toughening agent and the compatibilizer to prepare the high-wear-resisting and toughened PBT material.
Description
Technical Field
The invention relates to the technical field of automobile cable PBT materials, in particular to a high-wear-resistance and high-toughness PBT material for an automobile cable and a preparation method thereof.
Background
Polybutylene terephthalate (hereinafter abbreviated as PBT) is a crystalline high-molecular polymer, has excellent properties such as high heat resistance, fatigue resistance, weather resistance and low water absorption, and is widely used in automobile parts, electronic and electric appliances, household goods and the like. In the application of the automobile inhaul cable, the pure PBT material can not meet the requirements on wear resistance and toughness. Because the PBT material has low surface hardness and large surface friction coefficient, and simultaneously needs certain toughness to meet the requirement of low temperature resistance, and the wear resistance and the toughness are just contradictory. In recent years, domestic modified plastic factories do a lot of work on the aspects of developing high-wear-resistance and toughened PBT materials, but the modification results can not meet the requirements.
The research on the improvement of the nylon material in the prior art is found through retrieval, the technology is different from the main research of the invention, the nylon mainly takes fiber, the PBT material is thermoplastic polyester substance, the common effect between the two product raw materials is different, and the comparison treatment can not be carried out.
Based on the background, the invention develops the PBT material with high wear resistance and toughness, and can be widely used for manufacturing and producing the automobile inhaul cable.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-wear-resistance and high-toughness PBT material for an automobile cable and a preparation method thereof, so as to solve the problems in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a high-wear-resistance and toughened PBT material for an automobile cable, which comprises the following raw materials in parts by weight:
70-90 parts of PBT, 5-20 parts of wear-resistant agent, 5-10 parts of toughening agent, 0.2-2 parts of compatibilizer, 0.4-2.0 parts of antioxidant, 0.2-1.0 part of lubricant, 0.1-0.5 part of graphene composite modified polyimide fiber and 0.1-0.3 part of ionic liquid composite rare earth liquid.
Preferably, the preparation method of the graphene composite modified polyimide fiber comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5-10% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin in a weight ratio of 1:7 into an ethanol solvent to obtain a vanillin solution, then mixing the vanillin solution and the chitosan solution in a weight ratio of 3:5, stirring at 40-50 ℃ and a rotation speed of 200-500r/min for 25-35min, and obtaining an active medium agent after stirring;
s2, compounding and feeding the graphene and the polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 1-4um, the pulse width is 20-50ns, and the laser impact power density is 2-5GW/cm 2 And the energy is 10-20J, so that the modified material of the graphene and polyimide fibers is obtained;
s3, mixing the interface organism with an active medium agent according to the weight ratio of 1:3 to obtain mixed liquid; and then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 4-6 times that of the graphene and polyimide fiber modified material, then adding divinylbenzene accounting for 1-3% of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 500-1000r/min for 20-30min, wherein the stirring temperature is 80-110 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber.
Preferably, the interfacial organism is prepared by the method comprising: adding a silane coupling agent into a reaction kettle, adding dibutyltin dilaurate accounting for 1-5% of the total amount of the silane coupling agent, reacting at 60-100 ℃ for 15-25min at the reaction speed of 200-500r/min, then adding hexadecyl trimethoxy silane accounting for 2-6% of the total amount of the silane coupling agent, continuing to react for 25-35min, and obtaining an interface organism after the reaction is finished.
Preferably, the preparation method of the ionic liquid composite rare earth liquid comprises the following steps: mixing 1-hexyl-3-methylimidazole tetrafluoroborate and 1-5 mass percent lanthanum chloride solution according to a weight ratio of 1:3, stirring at a rotating speed of 100-200r/min for 20-30min, and obtaining the ionic liquid composite rare earth liquid after stirring.
Preferably, the viscosity of the PBT is 0.68 to 1.30dl/g; the wear-resisting agent is Polytetrafluoroethylene (PTFE), silicon compound, glass microsphere, inorganic whisker compound, molybdenum disulfide (MoS) 2 ) And one or more of graphite.
Preferably, the silicon compound comprises nano silicon dioxide and tetraethoxysilane.
Preferably, the toughening agent comprises POE grafted maleic anhydride, POE grafted glycidyl acrylate, EPDM grafted maleic anhydride, EPDM grafted glycidyl acrylate, ethylene-acrylic ester-glycidyl acrylate, and polyester elastomer containing one or more of MAH, GMA or epoxy group;
the compatibilizer comprises one or more of silane coupling agent, titanate coupling agent, epoxy resin and isocyanate.
Preferably, the antioxidant comprises pentaerythritol tetrakis [ methyl- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide ], N-octadecyl 3,5-di-tert-butyl-4-hydroxyphenyl propionate, N-octadecyl 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) trione, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 3434 zxft 34' -methylenebis (4-methyl-6-tert-butylphenol), tris (3825-di-tert-butylphenyl) phosphite, bis (36zxft-butyl-4-hydroxyphenyl) propionate, bis (di-tert-butyl-4-hydroxyphenyl) bis (4-butylphenyl) phosphite, tetrakis (3824-butyl-4-hydroxyphenyl) propionate, and tetrakis (3724-butyl-3-4-hydroxyphenyl) propionate, or more pentaerythritol tetrakis (3824-butyl-4-dodecyl) phosphite.
Preferably, the lubricant comprises one or more of polyethylene wax, N '-ethylene bis-stearamide, organic silicon oil, oleamide, ethylene bis-oleamide, N' -ethylene bis-stearamide-grafted maleic anhydride, silicone powder and fluorine-containing lubricant.
The invention also provides a preparation method of the high-wear-resistance and toughened PBT material for the automobile guy cable, which comprises the following steps:
s1, weighing raw materials according to the mixture ratio of claim 1;
s2, adding the raw materials into a high-speed mixer for mixing;
s3, continuously and uniformly adding the mixed materials into a main machine cylinder of a double-screw extruder with the screw diameter of 30mm and the length-diameter ratio of L/D =40 by using a double-screw feeder, wherein the temperature of each section of the main machine cylinder is controlled in a segmented mode, and the temperature is 200 ℃, 220 ℃,230 ℃,230 ℃,230 ℃,235 ℃ in sequence from a feed inlet to a machine head outlet, and the rotating speed of double screws is 350 revolutions per minute;
and S4, cooling the extruded material strips through a cooling water tank, and then cutting into particles to obtain the high-wear-resistance and toughened PBT material.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the graphene composite modified polyimide fiber comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5-10% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin 1:7 in weight ratio into ethanol solvent to obtain vanillin solution, mixing vanillin solution and chitosan solution in weight ratio of 3:5, stirring at 40-50 deg.C and 200-500r/min for 25-35min, and stirring to obtain active medium agent;
s2, compounding and feeding the graphene and polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 1-4um, the pulse width is 20-50ns, the laser impact power density is 2-5GW/cm, and the energy is 10-20J, so as to obtain a graphene and polyimide fiber modified material;
s3, mixing the interface organism with an active medium agent according to a weight ratio of 1:3 to obtain a mixed solution; and then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 4-6 times that of the graphene and polyimide fiber modified material, then adding divinylbenzene accounting for 1-3% of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 500-1000r/min for 20-30min, wherein the stirring temperature is 80-110 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber.
Preferably, the interfacial organism is prepared by the method comprising: adding a silane coupling agent into a reaction kettle, then adding dibutyltin dilaurate accounting for 1-5% of the total amount of the silane coupling agent, reacting for 15-25min at 60-100 ℃ at a reaction rotating speed of 200-500r/min, then adding hexadecyl trimethoxy silane accounting for 2-6% of the total amount of the silane coupling agent, continuing to react for 25-35min, and obtaining an interface organism after the reaction is finished.
Preferably, the preparation method of the ionic liquid composite rare earth liquid comprises the following steps: mixing 1-hexyl-3-methylimidazolium tetrafluoroborate and 1-5 mass percent lanthanum chloride solution according to the weight ratio of 1:3, stirring at the rotating speed of 100-200r/min for 20-30min, and obtaining the ionic liquid composite rare earth liquid after the stirring is finished
The PBT material is used as a matrix, and is processed and granulated by a double-screw extruder with the diameter phi of 30mm through the optimized combination proportion of a wear-resistant agent, a toughening agent and a compatibilizer to prepare the high-wear-resistant toughened PBT material. The technical indexes of the technical scheme are as follows:
1) Surface hardness (rockwell M): not less than 60
2) Surface friction coefficient: less than or equal to 0.15
3) Tensile strength: not less than 55MPa
4) Bending strength: not less than 80MPa
5) Notched impact strength: not less than 8kJ/m 2 ；
The graphene composite modified polyimide fiber and the ionic liquid composite rare earth liquid which are also added in the invention can further improve the performance of the product, the graphene and polyimide fibers are adopted in the preparation of the graphene composite modified polyimide fiber and are treated by a laser, the activity of the prepared modified material is high, the organic degree of the product is improved by matching the raw materials such as a silane coupling agent, dibutyltin dilaurate and the like in an interface organism, the reaction is carried out in a vanillin and chitosan solution, the graphene and polyimide fibers are subjected to interface treatment by matching a multi-active group in an active medium agent, and the graphene and polyimide fibers are subjected to graft reaction with other raw materials in the product, so that the graphene composite modified polyimide fiber is introduced, and the performances such as wear resistance, strength and the like in the product can be improved;
the ionic liquid added into the ionic liquid composite rare earth liquid is matched with the rare earth liquid, the rare earth liquid has an amphoteric effect and can improve the bonding strength between organic and inorganic products, so that the performance of the products is improved, and the ionic liquid is added to assist the rare earth liquid, so that the performance condition of the products in a low-temperature environment can be enhanced, and the improvement effect of the products is improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The raw materials used in the examples: the base material PBT is 1100-211M (Changchun China Taiwan), the wear-resisting agent tetrafluoroethylene (PTFE) is produced by Japan gold, the inorganic whisker compound is produced by Shanghai flos Pelargonii Hortori composite new material, and the molybdenum disulfide (MoS) 2 ) For Dow Corning production, the toughening agent ethylene-acrylate-acrylic acidGlycidyl ester (E-MA-GMA) is produced by Akoma, polyester elastomer (TPEE) DuPont, compatibilizer silane coupling agent (KH 560) is produced by Nanjing eosin photochemical engineering, epoxy resin (YD-012) is produced by Country, antioxidant 1790 is produced by Korean pine, 626 is produced by Taiwan double bond, 412S is produced by Kogyo, lubricant silicone oil is produced by Shanghai resin factory, and TAF (sold in market).
Example 1
The embodiment 1 of the invention discloses a high-wear-resistance and toughened PBT material for an automobile cable, which adopts the following technical scheme:
the specific weight fraction ratio of each component is 1100-211M:81.4 parts; PTFE:10 parts of (A); E-MA-GMA:7 parts; KH560:0.3 part; 1790:0.3 part; 626:0.3 part; 412S:0.2 part; silicone oil: 0.5 part; adding the mixture into a high-speed mixer according to the proportion, mixing for 3min, extruding and granulating the uniformly mixed materials through a double-screw extruder, feeding glass fibers laterally, and preparing modified particles, wherein the set temperature of each section of the extruder is as follows: 200 ℃, 220 ℃,230 ℃,230 ℃,235 ℃ (handpiece), and the rotating speed of the twin screw is 350 r/min.
The injection molding temperature was 245 ℃, 240 ℃,230 ℃, 210 ℃, and ISO specimen test was made.
Example 2
The embodiment 2 of the invention discloses a high-wear-resistance and toughened PBT material for an automobile cable, which adopts the following technical scheme:
the specific weight fraction ratio of each component is 1100-211M:80.7 parts of a mixture; inorganic whisker compound: 10 parts of (A); TPEE:7 parts; YD-012:1 part; 1790:0.3 part; 626:0.3 part; 412S:0.2 part; TAF:0.5 part; adding the mixture into a high-speed mixer according to the proportion, mixing for 3min, extruding and granulating the uniformly mixed materials through a double-screw extruder, feeding glass fibers laterally, and preparing modified particles, wherein the set temperature of each section of the extruder is as follows: 200 ℃, 220 ℃,230 ℃,230 ℃,235 ℃ (handpiece), and the rotating speed of the twin screw is 350 r/min.
The injection molding temperature is 245 ℃, 240 ℃,230 ℃ and 210 ℃, and ISO sample bars are prepared for testing. Example 3
The embodiment 3 of the invention discloses a high wear-resistant and toughened PBT material for an automobile inhaul cable, which adopts the following technical scheme:
the specific weight fraction ratio of each component is 1100-211M:86.4 parts of a mixture; moS 2 :5 parts of a mixture; E-MA-GMA:7 parts; KH560:0.3 part; 1790:0.3 part; 626:0.3 part; 412S:0.2 part; silicone oil: 0.5 part; adding the mixture into a high-speed mixer according to the proportion, mixing for 3min, then extruding and granulating the uniformly mixed materials through a double-screw extruder, feeding glass fibers laterally, and preparing to obtain modified particles, wherein the set temperature of each section of the extruder is as follows: 200 ℃, 220 ℃,230 ℃,230 ℃,235 ℃ (handpiece), and the rotating speed of the twin screw is 350 r/min.
The injection molding temperature was 245 ℃, 240 ℃,230 ℃, 210 ℃, and ISO specimen test was made.
Example 4
The embodiment 4 of the invention discloses a high wear-resistant and toughened PBT material for an automobile cable, which adopts the following technical scheme:
the specific weight fraction ratio of each component is 1100-211M:76.7 parts of; PTFE:10 parts of a binder; moS 2 :5 parts of a mixture; E-MA-GMA:7 parts; KH560:0.3 part; 1790:0.3 part; 626:0.3 part; 412S:0.2 part; silicone oil: 0.5 part; adding the mixture into a high-speed mixer according to the proportion, mixing for 3min, extruding and granulating the uniformly mixed materials through a double-screw extruder, feeding glass fibers laterally, and preparing modified particles, wherein the set temperature of each section of the extruder is as follows: 200 ℃, 220 ℃,230 ℃,230 ℃,230 ℃,235 ℃ (handpiece), and the rotating speed of the twin screw is 350 r/min.
The injection molding temperature was 245 ℃, 240 ℃,230 ℃, 210 ℃, and ISO specimen test was made.
Example 5
The embodiment 5 of the invention discloses a high-wear-resistance and toughened PBT material for an automobile cable, which adopts the following technical scheme:
the specific weight fraction ratio of each component is 1100-211M:75.4 parts of; inorganic whisker compound: 10 portions of；MoS 2 :5 parts of a mixture; TPEE:7 parts; KH560:0.3 part; YD-012:1 part; 1790:0.3 part; 626:0.3 part; 412S:0.2 part; silicone oil: 0.5 part; adding the mixture into a high-speed mixer according to the proportion, mixing for 3min, extruding and granulating the uniformly mixed materials through a double-screw extruder, feeding glass fibers laterally, and preparing modified particles, wherein the set temperature of each section of the extruder is as follows: 200 ℃, 220 ℃,230 ℃,230 ℃,230 ℃,235 ℃ (handpiece), and the rotating speed of the twin screw is 350 r/min.
The injection molding temperature is 245 ℃, 240 ℃,230 ℃ and 210 ℃, and ISO sample bars are prepared for testing.
To further illustrate the beneficial effects of the technical scheme of the invention, the samples obtained in examples 1-5 were subjected to performance testing. The test results are shown in table 1 below, in which the test standards are ISO standards.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Surface hardness (Rockwell M) | 58 | 72 | 68 | 61 | 70 |
| Coefficient of surface friction | 0.23 | 0.18 | 0.16 | 0.20 | 0.14 |
| Tensile Strength (MPa) | 56 | 57.5 | 58.5 | 56.6 | 57 |
| Flexural Strength (MPa) | 75 | 81 | 85 | 78 | 83 |
| Notched impact strength (kJ/m 2) | 15 | 12 | 11 | 12 | 11 |
Comparative examples 1, 2 and 3 effects of different anti-wear Agents, abrasion resistance PTFE < inorganic whisker Compound < MoS 2 Are sequentially increased, wherein MoS 2 The addition of (b) was the smallest, i.e., the wear resistance effect of example 3 was the best, but the requirement was still not satisfied. Through mixing the antiwear agent,After the compatibilizer is optimized and combined and proportioned, the friction coefficient meets the requirement, and the principle is as follows: inorganic whisker compound and MoS 2 The wear-resistant agent has small particle size and high surface hardness, the silane coupling agent and the epoxy resin are matched, so that the wear-resistant agent has excellent compatibility with matrix resin, and the unique dispersibility of the silicone oil enables the wear-resistant agent to be uniformly dispersed in the material.
Example 6.
The invention is further improved and processed on the basis of the embodiment 3;
0.1 part of graphene composite modified polyimide fiber and 0.1 part of ionic liquid composite rare earth liquid are also added.
The preparation method of the graphene composite modified polyimide fiber comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin in a weight ratio of 1:7 into an ethanol solvent to obtain a vanillin solution, then mixing the vanillin solution and the chitosan solution in a weight ratio of 3:5, stirring at 40 ℃ and a rotation speed of 200r/min for 25min, and obtaining an active medium agent after stirring;
s2, compounding and feeding the graphene and polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 1um, the pulse width is 20ns, the laser impact power density is 2GW/cm, and the energy is 10J, so as to obtain the graphene and polyimide fiber modified material;
s3, mixing the interface organism with an active medium agent according to the weight ratio of 1:3 to obtain mixed liquid; and then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 4 times that of the mixed solution, then adding divinylbenzene accounting for 1 percent of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 500r/min for 20min, wherein the stirring temperature is 80 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber.
The preparation method of the interfacial organism of this example is: adding a silane coupling agent into a reaction kettle, then adding dibutyltin dilaurate accounting for 1% of the total amount of the silane coupling agent, reacting for 15min at 60 ℃ at a reaction rotating speed of 200r/min, then adding hexadecyl trimethoxy silane accounting for 2% of the total amount of the silane coupling agent, continuing to react for 25min, and obtaining an interface organism after the reaction is finished.
The preparation method of the ionic liquid composite rare earth liquid comprises the following steps: mixing 1-hexyl-3-methylimidazole tetrafluoroborate and 1-5 mass percent lanthanum chloride solution according to a weight ratio of 1:3, stirring at a rotating speed of 100-200r/min for 20-30min, and obtaining the ionic liquid composite rare earth liquid after stirring.
Example 7.
The invention is further improved and processed on the basis of the embodiment 3;
0.5 part of graphene composite modified polyimide fiber and 0.3 part of ionic liquid composite rare earth liquid are also added.
The preparation method of the graphene composite modified polyimide fiber of the embodiment comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin in a weight ratio of 1:7 into an ethanol solvent to obtain a vanillin solution, then mixing the vanillin solution and the chitosan solution in a weight ratio of 3:5, stirring at 40 ℃ and a rotation speed of 200r/min for 25min, and obtaining an active medium agent after stirring;
s2, compositely feeding the graphene and polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 1um, the pulse width is 20ns, the laser impact power density is 2GW/cm, and the energy is 10J, so as to obtain a graphene and polyimide fiber modified material;
s3, mixing the interface organism with an active medium agent according to a weight ratio of 1:3 to obtain a mixed solution; and then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 4 times that of the mixed solution, then adding divinylbenzene accounting for 1 percent of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 500r/min for 20min, wherein the stirring temperature is 80 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber.
The preparation method of the interfacial organism of this example was: adding a silane coupling agent into a reaction kettle, adding dibutyltin dilaurate accounting for 1% of the total amount of the silane coupling agent, reacting at 60 ℃ for 15min at a reaction speed of 200r/min, then adding hexadecyl trimethoxy silane accounting for 2% of the total amount of the silane coupling agent, continuing to react for 25min, and obtaining an interface organism after the reaction is finished.
The preparation method of the ionic liquid composite rare earth liquid comprises the following steps: mixing 1-hexyl-3-methylimidazole tetrafluoroborate and a lanthanum chloride solution with the mass fraction of 1% according to the weight ratio of 1:3, stirring at the rotating speed of 100r/min for 20min, and obtaining the ionic liquid composite rare earth liquid after the stirring is finished.
Example 8.
The invention is further improved and processed on the basis of the embodiment 3;
0.5 part of graphene composite modified polyimide fiber and 0.2 part of ionic liquid composite rare earth liquid are also added.
The preparation method of the graphene composite modified polyimide fiber comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5-10% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin in a weight ratio of 1:7 into an ethanol solvent to obtain a vanillin solution, then mixing the vanillin solution and the chitosan solution in a weight ratio of 3:5, stirring at the rotation speed of 350r/min at 45 ℃ for 30min, and obtaining an active medium agent after stirring;
s2, compounding and feeding the graphene and polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 2.5um, the pulse width is 35ns, the laser impact power density is 3.5GW/cm, and the energy is 15J, so as to obtain a graphene and polyimide fiber modified material;
s3, mixing the interface organism with an active medium agent according to a weight ratio of 1:3 to obtain a mixed solution; and then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 5 times that of the graphene and polyimide fiber modified material, adding divinylbenzene accounting for 2 percent of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 750r/min for 25min, wherein the stirring temperature is 95 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber.
The preparation method of the interfacial organism of this example was: adding a silane coupling agent into a reaction kettle, adding dibutyltin dilaurate accounting for 3% of the total amount of the silane coupling agent, reacting at 80 ℃ for 20min at the reaction speed of 350r/min, then adding hexadecyl trimethoxy silane accounting for 4% of the total amount of the silane coupling agent, continuing to react for 30min, and obtaining an interface organism after the reaction is finished.
The preparation method of the ionic liquid composite rare earth liquid in the embodiment comprises the following steps: mixing 1-hexyl-3-methylimidazole tetrafluoroborate and lanthanum chloride solution with the mass fraction of 3% according to the weight ratio of 1:3, stirring at the rotating speed of 150r/min for 25min, and obtaining the ionic liquid composite rare earth liquid after the stirring is finished.
TABLE 2
| Example 6 | Example 7 | Example 8 | |
| Surface hardness (Rockwell M) | 72 | 72 | 73 |
| Coefficient of surface friction | 0.14 | 0.13 | 0.12 |
| Tensile Strength (MPa) | 60 | 60.5 | 61.5 |
| Flexural Strength (MPa) | 88 | 88 | 89 |
| Notched impact strength (kJ/m 2) | 15 | 15 | 16 |
In summary, the PBT material with high wear resistance and toughness for the automobile guy cable and the preparation method thereof provided by the embodiment of the invention are characterized in that the PBT material with high wear resistance and toughness is prepared by the optimized combination and proportion of the wear-resistant agent, the toughening agent and the compatibilizer.
The strength performances such as wear resistance, notch impact strength and the like can be improved obviously by adding the graphene composite modified polyimide fiber and the ionic liquid composite rare earth liquid.
The invention further explores the graphene composite modified polyimide fiber, and realizes the performance improvement treatment of the product by changing the reaction factors in the graphene composite modified polyimide fiber.
Experimental example 1:
based on example 8, except that no interfacial organisms were added.
Experimental example 2:
on the basis of example 8, except that no laser shock treatment was employed.
Experimental example 3:
on the basis of example 8, except that no active mediator was added.
TABLE 3
| Experimental example 1 | Experimental example 2 | Experimental example 3 | |
| Surface hardness (Rockwell M) | 71 | 71 | 72 |
| Coefficient of surface friction | 0.15 | 0.14 | 0.14 |
| Notched impact strength (kJ/m 2) | 13 | 14 | 13 |
From experimental examples 1-3, it can be seen that parameters such as interface organisms in the graphene composite modified polyimide fibers in the product of the invention are changed, and the parameters have certain influence on the wear resistance and the notch impact strength of the product.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. The high-wear-resistance and toughening PBT material for the automobile guy cable is characterized by comprising the following raw materials in parts by weight:
70-90 parts of PBT, 5-20 parts of wear-resistant agent, 5-10 parts of toughening agent, 0.2-2 parts of compatibilizer, 0.4-2.0 parts of antioxidant, 0.2-1.0 part of lubricant, 0.1-0.5 part of graphene composite modified polyimide fiber and 0.1-0.3 part of ionic liquid composite rare earth liquid;
the preparation method of the graphene composite modified polyimide fiber comprises the following steps:
s1, mixing chitosan and acetone according to a weight ratio of 1:5, and then adding glacial acetic acid accounting for 5-10% of the total amount of the chitosan to obtain a chitosan solution; adding vanillin 1:7 in weight ratio into ethanol solvent to obtain vanillin solution, mixing vanillin solution and chitosan solution in weight ratio of 3:5, stirring at 40-50 deg.C and 200-500r/min for 25-35min, and stirring to obtain active medium agent;
s2, compounding and feeding the graphene and the polyimide fibers into a laser according to a weight ratio of 2:5 for irradiation treatment, wherein the wavelength of the laser is 1-4um, the pulse width is 20-50ns, and the laser impact power density is 2-5GW/cm 2 And the energy is 10-20J, so that the modified material of the graphene and polyimide fibers is obtained;
s3, mixing the interface organism with an active medium agent according to a weight ratio of 1:3 to obtain a mixed solution; then adding the graphene and polyimide fiber modified material into the mixed solution of which the amount is 4-6 times that of the graphene and polyimide fiber modified material, then adding divinylbenzene accounting for 1-3% of the total amount of the graphene and polyimide fiber modified material, stirring at the rotating speed of 500-1000r/min for 20-30min, wherein the stirring temperature is 80-110 ℃, and after stirring, washing and drying to obtain the graphene composite modified polyimide fiber; the preparation method of the ionic liquid composite rare earth liquid comprises the following steps: mixing 1-hexyl-3-methylimidazole tetrafluoroborate and 1-5 mass percent lanthanum chloride solution according to a weight ratio of 1:3, stirring at a rotating speed of 100-200r/min for 20-30min, and obtaining ionic liquid composite rare earth liquid after stirring; the preparation method of the interfacial organism comprises the following steps: adding a silane coupling agent into a reaction kettle, adding dibutyltin dilaurate accounting for 1-5% of the total amount of the silane coupling agent, reacting at 60-100 ℃ for 15-25min at the reaction speed of 200-500r/min, then adding hexadecyl trimethoxy silane accounting for 2-6% of the total amount of the silane coupling agent, continuing to react for 25-35min, and obtaining an interface organism after the reaction is finished.
2. The high-wear-resistance and toughening PBT material for the automobile guy cable according to claim 1, wherein the viscosity of the PBT is 0.68 to 1.30dl/g; the wear-resisting agent is formed by compounding one or more of Polytetrafluoroethylene (PTFE), silicon compounds, glass microspheres, inorganic whisker compounds, molybdenum disulfide (MoS 2) and graphite.
3. The highly wear-resistant and toughened PBT material for the automobile guy cable as claimed in claim 2, wherein the silicon compound comprises nano silica and tetraethoxysilane.
4. The highly wear-resistant and toughened PBT material for the automobile guy cable according to claim 1, wherein the toughening agent comprises one or more of POE grafted maleic anhydride, POE grafted glycidyl acrylate, EPDM grafted maleic anhydride, EPDM grafted glycidyl acrylate, ethylene-acrylate-glycidyl acrylate, and a polyester elastomer containing MAH, GMA or epoxy groups;
the compatibilizer comprises one or more of silane coupling agent, titanate coupling agent, epoxy resin and isocyanate.
5. The PBT material with high wear resistance and toughness for the automobile guy cable as claimed in claim 1, wherein the antioxidant comprises pentaerythritol tetrakis [ methyl- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-1,6-hexylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide ], N-octadecyl-3- (3856 zxft 3883-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-3282 zxft 82- (1H, 3H, 5H) trione, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 3434 x34' -methylenebis (4-methyl-6-tert-butylphenol), tris (3825-tert-butyl-4-hydroxyphenyl) propionate, or bis- (3824-tert-butyl-4-hydroxyphenyl) propionate, or bis (3724-butyl-3-hydroxy-4-hydroxyphenyl) bis (3838-3224-dichlorophenyl) phosphite, and further comprises pentaerythritol tetrakis (3724-butyl-3-tert-butyl-4-hydroxyphenyl) propionate.
6. The PBT material with high wear resistance and toughness for the automobile guy cable according to claim 1, wherein the lubricant comprises one or more of polyethylene wax, N '-ethylene bis-stearamide, organic silicone oil, oleamide, ethylene bis-oleamide, N' -ethylene bis-stearamide-grafted maleic anhydride, silicone powder and fluorine-containing lubricant.
7. A preparation method of the PBT material with high wear resistance and toughness for the automobile guy cable according to any one of claims 1 to 6, which is characterized by comprising the following steps:
s1, weighing raw materials according to the mixture ratio of claim 1;
s2, adding the raw materials into a high-speed mixer for mixing;
s3, continuously and uniformly adding the mixed materials into a main machine cylinder of a double-screw extruder with the screw diameter of 30mm and the length-diameter ratio of L/D =40 by using a double-screw feeder, wherein the temperature of each section of the main machine cylinder is controlled in a segmented mode, and the temperature is 200 ℃, 220 ℃,230 ℃,230 ℃,230 ℃,235 ℃ in sequence from a feed inlet to a machine head outlet, and the rotating speed of double screws is 350 revolutions per minute;
and S4, cooling the extruded material strips through a cooling water tank, and then cutting into particles to obtain the high-wear-resistance and toughened PBT material.
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