A high and low temperature resistant polyamide cable tie and preparation method thereof

Abstract

The present invention discloses a high and low temperature resistant polyamide cable tie and a preparation method thereof, and relates to the technical field of polyamide cable ties. The high and low temperature resistant polyamide cable tie comprises the following components: by weight, 40 to 60 parts of polyamide 6, 12 to 15 parts of modifier, 5 to 15 parts of polyetheretherketone, 15 to 20 parts of modified glass fiber, 5 to 10 parts of toughening agent, 0.5 to 1 part of antioxidant, and 0.3 to 0.6 part of lubricant. By controlling the reaction conditions, lignin dissolution is avoided, and modified grafting is performed on the surface of lignin. While introducing sulfonate groups, polyetheretherketone segments, polydimethylsiloxane segments, and acid anhydride structures, the rigid structure of lignin is maintained, and then a modifier is prepared. The modifier can further cooperate with polyetheretherketone, modified glass fiber, and toughening agent to achieve effective improvement of the mechanical properties and high and low temperature resistance of polyamide 6.

Description

Technical Field

[0001] The present invention relates to the technical field of polyamide cable ties, in particular to a high and low temperature resistant polyamide cable tie and a preparation method thereof. Background Art

[0002] Polyamide materials are widely used in cable ties, electronic connectors, automotive parts, and other fields due to their excellent mechanical properties, chemical corrosion resistance, and ease of processing. However, traditional polyamide cable ties (such as polyamide-6 and polyamide-66) have significant performance defects in extreme temperature environments (such as high temperatures > 120°C or low temperatures < -40°C): they are prone to softening and deformation at high temperatures, resulting in a decrease in tensile strength and dimensional stability; at low temperatures, the movement of molecular segments is restricted, causing brittle fracture and a sharp drop in impact strength.

[0003] In order to enhance the applicability of cable ties, the present invention will prepare a high and low temperature resistant polyamide cable tie, which can well solve the defects of traditional polyamide cable ties and has practical significance. Summary of the Invention

[0004] The object of the present invention is to provide a high and low temperature resistant polyamide cable tie and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A method for preparing a high and low temperature resistant polyamide cable tie comprises the following steps:

[0007] S1: Preparation of modifier:

[0008] S11: maleic anhydride and lignin undergo esterification reaction to obtain maleic anhydride-modified lignin;

[0009] S12: Maleic anhydride-modified lignin undergoes amidation reaction with p-aminobenzenesulfonic acid to obtain sulfonated modified lignin;

[0010] S13: reducing the polyetheretherketone with sodium borohydride to obtain a hydroxylated polyetheretherketone;

[0011] S14: Sulfonated modified lignin reacts with hydroxylated polyetheretherketone to produce lignin-modified polyetheretherketone;

[0012] S15: Lignin-modified polyetheretherketone is polymerized with vinyl-terminated polydimethylsiloxane and maleic anhydride to obtain a modifier;

[0013] S2: Preparation of modified glass fiber:

[0014] S21: Modifying glass fiber with γ-aminopropyltriethoxysilane to obtain modified glass fiber;

[0015] S3: Preparation of high and low temperature resistant polyamide cable ties:

[0016] S31: adding polyamide-6, a modifier, polyetheretherketone, modified glass fiber, a toughening agent, an antioxidant, and a lubricant into a twin-screw extruder, and performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material;

[0017] S32: adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, heating and melting it, and injection molding it to obtain the high and low temperature resistant polyamide cable tie.

[0018] More optimally, the preparation method of the modifier is as follows: (1) under nitrogen protection, maleic anhydride, lignin, and acetic acid are added to a reaction vessel, stirred at 30-40°C for 1-6 hours, the reaction is terminated, and the maleic anhydride-modified lignin is obtained through separation and purification; (2) under nitrogen protection, maleic anhydride-modified lignin, p-aminobenzenesulfonic acid, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and deionized water are added to a reaction vessel, stirred at 50-60°C for 1-6 hours, the reaction is terminated, and the sulfonated modified lignin is obtained through separation and purification; (3) polyetheretherketone, sodium borohydride, and dimethyl sulfoxide are added to a reaction vessel, stirred at 115-125°C for 3-9 hours, the reaction is terminated, and the sulfonated modified lignin is obtained through separation and purification. h, terminate the reaction, and obtain hydroxylated polyether ether ketone through separation and purification; (4) under nitrogen protection, add sulfonated modified lignin, hydroxylated polyether ether ketone, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and N-methylpyrrolidone into a reaction vessel, stir and react at 50-60°C for 3-9h, terminate the reaction, and obtain lignin-modified polyether ether ketone through separation and purification; (5) under nitrogen protection, add lignin-modified polyether ether ketone, vinyl-terminated polydimethylsiloxane, and maleic anhydride into a reaction vessel, stir and mix evenly, add benzoyl peroxide dropwise into the reaction solution at 50-70°C while stirring, and after the addition is complete, continue stirring and reacting for 1-3h to obtain a modifier.

[0019] More optimally, the mass ratio of maleic anhydride, lignin and acetic acid is (0.5-1):(4-4.5):20.

[0020] More optimally, the lignin is alkali lignin.

[0021] More optimally, the mass ratio of the maleic anhydride-modified lignin, p-aminobenzenesulfonic acid, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and deionized water is 2:(1-2):(2-3):1:20.

[0022] More optimally, the mass ratio of the polyetheretherketone, sodium borohydride and dimethyl sulfoxide is 1:(0.1-0.2):10.

[0023] More optimally, the mass ratio of the sulfonated modified lignin, hydroxylated polyetheretherketone, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and N-methylpyrrolidone is (1-3):(14-16):(16-18):2:100.

[0024] More optimally, the mass ratio of the lignin-modified polyetheretherketone, vinyl-terminated polydimethylsiloxane, maleic anhydride, and benzoyl peroxide is 2:(0.1-0.3):(0.05-0.1):(0.03-0.05).

[0025] Lignin has excellent thermal stability, and its introduction into resins can improve the resin's high-temperature resistance. Furthermore, lignin has a rigid structure, and improving its compatibility can enhance the mechanical properties of the resin. Based on this, the present invention controls the reaction conditions to prevent lignin dissolution, maintains the modified grafting treatment on the lignin surface, and maintains its rigid structure while introducing other beneficial segments or groups, ultimately producing a modifier. The specific preparation process is as follows: in the present invention, acetic acid is first used as a solvent and a catalyst to react the anhydride of maleic anhydride with the phenolic hydroxyl group on the lignin to perform an esterification reaction, thereby obtaining maleic anhydride-modified lignin having unsaturated double bonds and carboxyl groups; then, the double bonds on the maleic anhydride-modified lignin are reacted with the amino groups on sodium p-aminobenzenesulfonate to perform an amidation reaction, thereby obtaining a sulfonated modified lignin still having unsaturated bonds; then, after hydroxylating the polyetheretherketone, the hydroxyl groups on the hydroxylated polyetheretherketone are reacted with the sulfonic acid groups on the sulfonated modified lignin to perform a sulfonate esterification reaction, thereby obtaining a lignin-modified polyetheretherketone having an unsaturated bond; finally, the unsaturated bonds on the lignin-modified polyetheretherketone are polymerized with the unsaturated bonds on the vinyl-terminated polydimethylsiloxane and the maleic anhydride to obtain a modifier. Among them, the reason why acetic acid solvent is used in the preparation process of maleic anhydride modified lignin is that: maleic anhydride has higher reactivity than acetic acid, so maleic anhydride will react first; and since there is no water in acetic acid, maleic anhydride will not be hydrolyzed, so that no side reactions will occur during the reaction process and a rapid esterification rate can be maintained continuously; in addition, the reaction is carried out at 30-40°C, at which temperature the solubility of lignin is extremely low, and maleic anhydride can finally undergo a rapid esterification reaction with the phenolic hydroxyl groups on the surface or shallow pores of the lignin; and in the subsequent preparation of sulfonated modified lignin, lignin modified polyetheretherketone, and modifiers, the reaction process is promoted by a catalyst, which effectively reduces the reaction temperature, avoids the increase in the solubility of lignin, and ensures the rigid structure of the lignin.

[0026] The obtained modifier is added to polyamide-6. Since the modifier contains lignin rigid structure, sulfonate group, polyetheretherketone segment, polydimethylsiloxane segment and acid anhydride structure, firstly, the presence of acid anhydride structure can form a stable chemical bond with the amide group in polyamide-6, that is, the modifier has good compatibility with polyamide-6; secondly, under the action of lignin rigid structure, the modifier plays a role in improving the mechanical properties and high temperature resistance of polyamide-6; furthermore, the polyetheretherketone segment can improve the compatibility between polyamide-6 and polyetheretherketone, so it can be used in polyamide-6. Polyamide-6 is further partially introduced with polyetheretherketone. Under the action of the modifier, polyetheretherketone and polyamide-6 also have good compatibility, which can further enhance the mechanical properties and high-temperature resistance of polyamide-6. The sulfonate group and the amide group can form hydrogen bonds, which can also enhance the compatibility of the modifier and polyamide-6 to a certain extent. At the same time, due to the hydrogen bonding, the mechanical properties and high-temperature resistance of polyamide-6 are also enhanced. Finally, the polydimethylsiloxane chain end is a flexible chain end, which helps to enhance the toughness and low-temperature resistance of polyamide-6. That is, the present invention prepares a modifier with good compatibility with polyamide-6. Due to the good compatibility of the modifier with polyetheretherketone, it can also be used as a compatibilizer for polyetheretherketone and polyamide-6. Ultimately, under the synergistic effect of the modifier and polyetheretherketone, the mechanical properties and high-temperature resistance of polyamide-6 are effectively improved.

[0027] More optimally, the preparation method of the modified glass fiber is as follows: (1) adding γ-aminopropyltriethoxysilane, deionized water, anhydrous ethanol, and acetic acid into a reaction vessel, stirring and mixing for 10 to 30 minutes to obtain a silane hydrolyzate; (2) adding glass fiber to the silane hydrolyzate, stirring and mixing at 50 to 60° C. for 2 to 12 hours, filtering, washing, and drying to obtain the modified glass fiber.

[0028] More optimally, the raw materials required for preparing the modified glass fiber include the following components: 20 parts of glass fiber, 1-2 parts of γ-aminopropyltriethoxysilane, 0.3-0.6 parts of acetic acid, 10-15 parts of deionized water, and 30-40 parts of anhydrous ethanol, calculated by weight.

[0029] More optimally, the glass fiber is chopped glass fiber, and the diameter of the single fiber is 10 μm.

[0030] To further enhance the heat resistance of polyamide-6, the present invention modifies glass fiber with γ-aminopropyltriethoxysilane to produce modified glass fiber. The modified glass fiber contains amino groups that can form hydrogen bonds with the amide groups on polyamide-6, enhancing the dispersibility and compatibility of the glass fiber in polyamide-6. The introduction of glass fiber forms a reinforcing network within polyamide-6, thereby enhancing the mechanical properties of polyamide-6 at both high and low temperatures.

[0031] More preferably, the toughening agent includes but is not limited to one or a combination of maleic anhydride grafted EPDM rubber, maleic anhydride grafted ethylene-octene copolymer, and maleic anhydride grafted ethylene-acrylate copolymer.

[0032] In the present invention, a toughening agent is further added to further modify the polyamide-6 in coordination with the modifier, polyetheretherketone and modified glass fiber, so that the temperature resistance and mechanical properties of the polyamide-6 are balanced.

[0033] More optimally, the high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: by weight, 0-60 parts of polyamide-64, 12-15 parts of modifier, 5-15 parts of polyetheretherketone, 15-20 parts of modified glass fiber, 5-10 parts of toughening agent, 0.5-1 part of antioxidant, and 0.3-0.6 part of lubricant.

[0034] More optimally, the twin-screw extruder is divided into seven heating zones, and the temperature of the heating zones is 210-280°C; the temperature of the first heating zone is 210-240°C, the temperature of the second heating zone is 230-250°C, the temperature of the third heating zone is 240-250°C, the temperature of the fourth heating zone is 250-260°C, the temperature of the fifth heating zone is 260-280°C, the temperature of the sixth heating zone is 260-270°C, and the temperature of the seventh heating zone is 260-270; the extrusion temperature is 260-270°C, and the screw speed is 300-500r / min.

[0035] More optimally, the heating and melting temperature is 250-280° C.; the injection molding parameters are: pressure 50-100 MPa, and time 10-20 s.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The modifier prepared by the present invention can improve the mechanical properties and high and low temperature resistance of polyamide-6, and has good compatibility with polyamide-6 and polyetheretherketone. It can also be used as a compatibilizer to promote the compatibility of polyetheretherketone and polyamide-6;

[0038] (2) The present invention further introduces toughening agents and modified glass fibers to improve polyamide-6 in coordination with polyetheretherketone and modifiers, and each component is evenly dispersed and has good compatibility, thereby achieving effective improvement in the mechanical properties and high and low temperature resistance of polyamide-6. DETAILED DESCRIPTION

[0039] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0040] It should be noted that the following parts are calculated by weight, and the purchasers of all raw materials involved in the present invention include, without any special restrictions, the following examples:

[0041] In the following examples,

[0042] Polyamide-6, purity 99.5%, product number 25038-54-4, alkali lignin, purity 99.5%, product number 9005-53-2, γ-aminopropyltriethoxysilane, purity 99%, N,N-dicyclohexylcarbodiimide, purity 99%, 4-dimethylaminopyridine, purity 99%, sodium borohydride, purity 99%, dimethyl sulfoxide, purity 99%, N-methylpyrrolidone, purity 99%, were purchased from Hubei Guangao Biotechnology Co., Ltd.

[0043] Polyetheretherketone (PEEK) with a purity of 99% and a product number of JSPL-PEEK-001 was purchased from Jiangsu Puli New Materials Co., Ltd.

[0044] Maleic anhydride grafted ethylene-octene copolymer, with a purity of 99% and a maleic anhydride grafting rate of 0.5-1 wt% of the mass of the ethylene-octene copolymer, product number N216, purchased from Ningbo Yikun Import and Export Co., Ltd.

[0045] Chopped glass fibers, with a purity of 99%, a monofilament diameter of 10 μm, and a length of 3–6 mm, were purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0046] Antioxidant 703, purity 99%, was purchased from Shandong Tianhong Biopharmaceutical Co., Ltd.;

[0047] Lubricant, model Licocare RBW 300VITA, purchased from Guangzhou Rongda Chemical Co., Ltd.

[0048] Maleic anhydride, purity 99%, purchased from Shanghai Bangcheng Chemical Co., Ltd.;

[0049] p-Aminobenzenesulfonic acid, 99% purity, was purchased from Shanghai Dingmiao Chemical Technology Co., Ltd.;

[0050] Vinyl-terminated polydimethylsiloxane, with a purity of 99% and a molecular weight of 1000, was purchased from Hubei Shixing Chemical Co., Ltd.

[0051] Each weight portion below is 100 g.

[0052] Example 1: A method for preparing a high and low temperature resistant polyamide cable tie:

[0053] S1: Preparation of modifier: (1) Under nitrogen protection, 0.8 parts of maleic anhydride, 4.2 parts of alkali lignin, and 20 parts of acetic acid were added to a reaction vessel, stirred at 35°C for 3 hours, and the reaction was terminated. After separation and purification, maleic anhydride-modified lignin was obtained; (2) Under nitrogen protection, 4 parts of maleic anhydride-modified lignin, 3 parts of p-aminobenzenesulfonic acid, 5 parts of N,N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine, and 40 parts of deionized water were added to a reaction vessel, stirred at 55°C for 3 hours, and the reaction was terminated. After separation and purification, sulfonated modified lignin was obtained; (3) 10 parts of polyetheretherketone, 1.5 parts of sodium borohydride, and 100 parts of dimethyl sulfoxide were added to a reaction vessel, stirred at 120°C for 6 hours, and the reaction was terminated. (4) under nitrogen protection, 2 parts of sulfonated modified lignin, 15 parts of hydroxylated polyether ether ketone, 17 parts of N, N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine and 100 parts of N-methylpyrrolidone were added into a reaction vessel, stirred and reacted at 55°C for 6 hours, and the reaction was terminated. After separation and purification, lignin-modified polyether ether ketone was obtained; (5) under nitrogen protection, 15 parts of lignin-modified polyether ether ketone, 1.5 parts of vinyl-terminated polydimethylsiloxane and 0.6 parts of maleic anhydride were added into a reaction vessel, stirred and mixed uniformly, and 0.3 parts of benzoyl peroxide was added dropwise to the reaction solution at 60°C while stirring. After the addition was completed, the reaction was continued with stirring for 2 hours to obtain a modifier;

[0054] S2: Preparation of modified glass fiber: (1) Add 1.5 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of anhydrous ethanol, and 0.5 parts of acetic acid into a reaction vessel, and stir and mix for 20 minutes to obtain a silane hydrolyzate; (2) Add 20 parts of chopped glass fibers into the silane hydrolyzate, stir and mix at 55°C for 6 hours, filter, wash, and dry to obtain a modified glass fiber;

[0055] S3: Preparing a high and low temperature resistant polyamide cable tie: S31: Adding polyamide-6, a modifier, polyetheretherketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and a lubricant into a twin-screw extruder, performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, performing heating and melting, and injection molding to obtain a high and low temperature resistant polyamide cable tie;

[0056] The high and low temperature resistant polyamide cable tie composite material comprises the following components and raw materials: by weight: 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant;

[0057] The twin-screw extruder is divided into seven heating zones, the temperatures of which are: the first heating zone temperature is 230°C, the second heating zone temperature is 240°C, the third heating zone temperature range is 245°C, the fourth heating zone temperature range is 255°C, the fifth heating zone temperature range is 270°C, the sixth heating zone temperature range is 265°C, and the seventh heating zone temperature range is 265; the extrusion temperature is 265°C and the screw speed is 400r / min;

[0058] The heating and melting temperature is 270° C.; the injection molding parameters are: pressure 80 MPa, time 15 s.

[0059] Example 2: A method for preparing a high and low temperature resistant polyamide cable tie:

[0060] S1: Preparation of modifier: (1) Under nitrogen protection, 0.5 parts of maleic anhydride, 4.5 parts of alkali lignin, and 20 parts of acetic acid were added to a reaction vessel, stirred at 35°C for 1 hour, and the reaction was terminated. After separation and purification, maleic anhydride-modified lignin was obtained; (2) Under nitrogen protection, 4 parts of maleic anhydride-modified lignin, 2 parts of p-aminobenzenesulfonic acid, 5 parts of N,N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine, and 40 parts of deionized water were added to a reaction vessel, stirred at 55°C for 1 hour, and the reaction was terminated. After separation and purification, sulfonated modified lignin was obtained; (3) 10 parts of polyetheretherketone, 1 part of sodium borohydride, and 100 parts of dimethyl sulfoxide were added to a reaction vessel, stirred at 120°C for 3 hours, and the reaction was terminated. After separation and purification, hydroxylated polyether ether ketone was obtained; (4) under nitrogen protection, 1 part of sulfonated modified lignin, 16 parts of hydroxylated polyether ether ketone, 17 parts of N,N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine, and 100 parts of N-methylpyrrolidone were added to a reaction vessel, stirred at 55°C for 3 hours, and the reaction was terminated. After separation and purification, lignin-modified polyether ether ketone was obtained; (5) under nitrogen protection, 15 parts of lignin-modified polyether ether ketone, 0.75 parts of vinyl-terminated polydimethylsiloxane, and 0.375 parts of maleic anhydride were added to a reaction vessel, stirred and mixed uniformly, and 0.3 parts of benzoyl peroxide was added dropwise to the reaction solution at 60°C while stirring. After the addition was completed, the stirring reaction was continued for 2 hours to obtain a modifier;

[0061] S2: Preparation of modified glass fiber: (1) Add 1 part of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of anhydrous ethanol, and 0.5 parts of acetic acid into a reaction vessel, and stir and mix for 10 minutes to obtain a silane hydrolyzate; (2) Add 20 parts of chopped glass fibers into the silane hydrolyzate, stir and mix at 55°C for 2 hours, filter, wash, and dry to obtain a modified glass fiber;

[0062] S3: Preparing a high and low temperature resistant polyamide cable tie: S31: Adding polyamide-6, a modifier, polyetheretherketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and a lubricant into a twin-screw extruder, performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, performing heating and melting, and injection molding to obtain a high and low temperature resistant polyamide cable tie;

[0063] The high and low temperature resistant polyamide cable tie composite material comprises the following components and raw materials: by weight: 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant;

[0064] The twin-screw extruder is divided into seven heating zones, the temperatures of which are: the first heating zone temperature is 230°C, the second heating zone temperature is 240°C, the third heating zone temperature range is 245°C, the fourth heating zone temperature range is 255°C, the fifth heating zone temperature range is 270°C, the sixth heating zone temperature range is 265°C, and the seventh heating zone temperature range is 265; the extrusion temperature is 265°C and the screw speed is 400r / min;

[0065] The heating and melting temperature is 270° C.; the injection molding parameters are: pressure 80 MPa, time 15 s.

[0066] Example 3: A method for preparing a high and low temperature resistant polyamide cable tie:

[0067] S1: Preparation of modifier: (1) Under nitrogen protection, 1 part of maleic anhydride, 4 parts of alkali lignin, and 20 parts of acetic acid were added to a reaction vessel, stirred at 35°C for 6 hours, the reaction was terminated, and maleic anhydride-modified lignin was obtained through separation and purification; (2) Under nitrogen protection, 4 parts of maleic anhydride-modified lignin, 4 parts of p-aminobenzenesulfonic acid, 5 parts of N,N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine, and 40 parts of deionized water were added to a reaction vessel, stirred at 55°C for 6 hours, the reaction was terminated, and sulfonated modified lignin was obtained through separation and purification; (3) 10 parts of polyetheretherketone, 2 parts of sodium borohydride, and 100 parts of dimethyl sulfoxide were added to a reaction vessel, stirred at 120°C for 9 hours, the reaction was terminated, and the sulfonated modified lignin was obtained through separation and purification. (4) under nitrogen protection, 3 parts of sulfonated modified lignin, 14 parts of hydroxylated polyether ether ketone, 17 parts of N, N-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine and 100 parts of N-methylpyrrolidone were added to a reaction vessel, stirred and reacted at 55 ° C for 9 hours, and the reaction was terminated. After separation and purification, lignin-modified polyether ether ketone was obtained; (5) under nitrogen protection, 15 parts of lignin-modified polyether ether ketone, 2.25 parts of vinyl-terminated polydimethylsiloxane and 0.75 parts of maleic anhydride were added to a reaction vessel, stirred and mixed uniformly, and 0.3 parts of benzoyl peroxide was added dropwise to the reaction solution at 60 ° C while stirring. After the addition was completed, the stirring reaction was continued for 3 hours to obtain a modifier;

[0068] S2: Preparation of modified glass fiber: (1) Add 2 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of anhydrous ethanol, and 0.5 parts of acetic acid into a reaction vessel, and stir and mix for 30 minutes to obtain a silane hydrolyzate; (2) Add 20 parts of chopped glass fibers into the silane hydrolyzate, stir and mix at 55°C for 12 hours, filter, wash, and dry to obtain a modified glass fiber;

[0069] S3: Preparing a high and low temperature resistant polyamide cable tie: S31: Adding polyamide-6, a modifier, polyetheretherketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and a lubricant into a twin-screw extruder, performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, performing heating and melting, and injection molding to obtain a high and low temperature resistant polyamide cable tie;

[0070] The high and low temperature resistant polyamide cable tie composite material comprises the following components and raw materials: by weight: 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant;

[0071] The twin-screw extruder is divided into seven heating zones, the temperatures of which are: the first heating zone temperature is 230°C, the second heating zone temperature is 240°C, the third heating zone temperature range is 245°C, the fourth heating zone temperature range is 255°C, the fifth heating zone temperature range is 270°C, the sixth heating zone temperature range is 265°C, and the seventh heating zone temperature range is 265; the extrusion temperature is 265°C and the screw speed is 400r / min;

[0072] The heating and melting temperature is 270° C.; the injection molding parameters are: pressure 80 MPa, time 15 s.

[0073] The following comparative experiments are conducted based on Example 1, and comparative examples 1 to 5 are set as follows:

[0074] Comparative Example 1: Comparative Example 1 is based on Example 1, with the following adjustments: only maleic anhydride is used to modify lignin, and other processes remain unchanged, specifically:

[0075] A preparation method of a high and low temperature resistant polyamide cable tie:

[0076] S1: Preparation of maleic anhydride-modified lignin: (1) Under nitrogen protection, 3.2 parts of maleic anhydride, 16.8 parts of alkali lignin, and 80 parts of acetic acid were added to a reaction vessel, stirred at 35°C for 3 hours, and the reaction was terminated. Maleic anhydride-modified lignin was obtained through separation and purification;

[0077] S2: Preparation of modified glass fiber: (1) Add 1.5 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of anhydrous ethanol, and 0.5 parts of acetic acid into a reaction vessel, and stir and mix for 20 minutes to obtain a silane hydrolyzate; (2) Add 20 parts of chopped glass fibers into the silane hydrolyzate, stir and mix at 55°C for 6 hours, filter, wash, and dry to obtain a modified glass fiber;

[0078] S3: Preparing a high and low temperature resistant polyamide cable tie: S31: Adding polyamide-6, maleic anhydride modified lignin, polyetheretherketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and lubricant into a twin-screw extruder, performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, performing heating and melting, and injection molding to obtain a high and low temperature resistant polyamide cable tie;

[0079] The high and low temperature resistant polyamide cable tie composite material comprises the following components and raw materials: by weight: 50 parts of polyamide-6, 14 parts of maleic anhydride modified lignin, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant;

[0080] The twin-screw extruder is divided into seven heating zones, the temperatures of which are: the first heating zone temperature is 230°C, the second heating zone temperature is 240°C, the third heating zone temperature range is 245°C, the fourth heating zone temperature range is 255°C, the fifth heating zone temperature range is 270°C, the sixth heating zone temperature range is 265°C, and the seventh heating zone temperature range is 265; the extrusion temperature is 265°C and the screw speed is 400r / min;

[0081] The heating and melting temperature is 270° C.; the injection molding parameters are: pressure 80 MPa, time 15 s.

[0082] Comparative Example 2: Comparative Example 2 is based on Example 1, with the following adjustments: no modifier is added, and other processes remain unchanged, specifically:

[0083] The high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: by weight, 50 parts of polyamide-6, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant.

[0084] Comparative Example 3: Comparative Example 3 is based on Example 1, with the following adjustments: no polyetheretherketone is added, and other processes remain unchanged, specifically:

[0085] The high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant.

[0086] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustments: no maleic anhydride grafted ethylene-octene copolymer is added, and other processes remain unchanged;

[0087] The high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyetheretherketone, 18 parts of modified glass fiber, 7030.8 parts of antioxidant, and 0.5 parts of lubricant.

[0088] Comparative Example 5: Comparative Example 5 is based on Example 1, with the following adjustments: no modified glass fiber is added, and other processes remain unchanged, specifically:

[0089] The high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyetheretherketone, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 7030.8 parts of antioxidant, and 0.5 parts of lubricant.

[0090] Performance test: The high and low temperature resistant polyamide cable ties prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were subjected to high and low temperature resistance performance tests and compared with polyamide cable ties prepared using only polyamide-6. The specific test method is as follows:

[0091] (1) Place the high and low temperature resistant polyamide cable tie in a high temperature box, and heat the box to 150°C at a heating rate of 10K / min. After 12 hours, take out the high and low temperature resistant polyamide cable tie and immediately perform a high temperature tensile test on it at a tensile rate of 5cm / min. Combined with the tensile strength measured at room temperature, calculate its tensile strength retention rate (%);

[0092] (2) Place the high and low temperature resistant polyamide cable tie in a low temperature box, cool it to -50°C at a cooling rate of 10K / min, take it out after 12 hours, and immediately perform a low temperature tensile test on it at a tensile rate of 5cm / min. Combined with the tensile strength measured at room temperature, calculate its tensile strength retention rate (%);

[0093] The tensile strength retention rate (%) = tensile strength measured at high (low) temperature / tensile strength measured at room temperature × 100%; the test data results are shown in the following Table 1:

[0094] Table 1

[0095]

[0096]

[0097] Result analysis: From the data in Table 1 above, it can be seen that the present invention achieves comprehensive modification of polyamide-6 through the synergistic effect of modifier, polyetheretherketone, toughening agent and modified glass fiber. The high and low temperature resistant polyamide cable tie finally prepared shows excellent temperature resistance both at a high temperature of 150°C and at a low temperature of -50°C. Among them, the tensile strength retention rate is as high as 92% after being placed at -50°C for 12 hours, and the tensile strength retention rate is as high as 85% after being placed at 150°C for 12 hours.

[0098] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high and low temperature resistant polyamide cable tie, characterized in that: The following steps are involved: S1: Preparation of modifier: S11: maleic anhydride and lignin undergo esterification reaction to obtain maleic anhydride-modified lignin; S12: Maleic anhydride-modified lignin undergoes amidation reaction with p-aminobenzenesulfonic acid to obtain sulfonated modified lignin; S13: reducing the polyetheretherketone with sodium borohydride to obtain a hydroxylated polyetheretherketone; S14: Sulfonated modified lignin reacts with hydroxylated polyetheretherketone to produce lignin-modified polyetheretherketone; S15: Lignin-modified polyetheretherketone is polymerized with vinyl-terminated polydimethylsiloxane and maleic anhydride to obtain a modifier; S2: Preparation of modified glass fiber: S21: Modifying glass fiber with γ-aminopropyltriethoxysilane to obtain modified glass fiber; S3: Preparation of high and low temperature resistant polyamide cable ties: S31: adding polyamide-6, a modifier, polyetheretherketone, modified glass fiber, a toughening agent, an antioxidant, and a lubricant into a twin-screw extruder, and performing melt mixing, extrusion, and pelletizing to obtain a high and low temperature resistant polyamide cable tie composite material; S32: adding the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, heating and melting it, and injection molding it to obtain the high and low temperature resistant polyamide cable tie; Wherein, in S11, the lignin is alkaline lignin; In S31, the high and low temperature resistant polyamide cable tie composite material includes the following component raw materials: in parts by weight, 40 to 60 parts of polyamide-6, 12 to 15 parts of modifier, 5 to 15 parts of polyetheretherketone, 15 to 20 parts of modified glass fiber, 5 to 10 parts of toughening agent, 0.5 to 1 part of antioxidant, and 0.3 to 0.6 part of lubricant.

2. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 1, characterized in that: The preparation method of the modifier is: (1) Under nitrogen protection, maleic anhydride, lignin, and acetic acid are added to a reaction vessel, stirred and reacted at 30-40°C for 1-6 hours, and the reaction is terminated. Maleic anhydride-modified lignin is obtained by separation and purification; (2) Under nitrogen protection, maleic anhydride-modified lignin, p-aminobenzenesulfonic acid, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and deionized water are added to a reaction vessel, stirred at 50-60°C for 1-6 hours, and the reaction is terminated. After separation and purification, sulfonated modified lignin is obtained; (3) Add polyetheretherketone, sodium borohydride, and dimethyl sulfoxide into a reaction vessel, stir and react at 115-125°C for 3-9 hours, terminate the reaction, and separate and purify to obtain hydroxylated polyetheretherketone; (4) Under nitrogen protection, sulfonated modified lignin, hydroxylated polyetheretherketone, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and N-methylpyrrolidone are added to a reaction vessel, stirred at 50-60°C for 3-9 hours, and the reaction is terminated. After separation and purification, lignin-modified polyetheretherketone is obtained; (5) Under nitrogen protection, lignin-modified polyetheretherketone, vinyl-terminated polydimethylsiloxane, and maleic anhydride are added to a reaction vessel and stirred to mix evenly. Benzoyl peroxide is added dropwise to the reaction solution at 50-70°C while stirring. After the addition is complete, the reaction is continued with stirring for 1-3 hours to obtain a modifier.

3. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 2, characterized in that: The mass ratio of maleic anhydride, lignin and acetic acid is (0.5-1):(4-4.5):20; the mass ratio of maleic anhydride-modified lignin, p-aminobenzenesulfonic acid, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and deionized water is 2:(1-2):(2-3):1:20; the mass ratio of polyetheretherketone, sodium borohydride and dimethyl sulfoxide is 1:(0.1-0.2):10; the sulfonated modified lignin is 0.5-1: ... is 0.5-1:(4-4.5):20; the mass ratio of maleic anhydride-modified lignin is 0.5-1:(4-4.5):20; the mass ratio of maleic anhydride-modified lignin is 0.5-1:(4-4.5):20; the mass ratio of maleic anhydride-modified lignin is 0.5-1:(4-4.5):20; the mass ratio of maleic anhydride-modified lignin is 0.5-1:(4-4.5):20 The mass ratio of lignin, hydroxylated polyetheretherketone, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and N-methylpyrrolidone is (1-3):(14-16):(16-18):2:100; the mass ratio of lignin-modified polyetheretherketone, vinyl-terminated polydimethylsiloxane, maleic anhydride, and benzoyl peroxide is 2:(0.1-0.3):(0.05-0.1):(0.03-0.05).

4. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 1, characterized in that: The preparation method of the modified glass fiber is: (1) Add γ-aminopropyltriethoxysilane, deionized water, anhydrous ethanol, and acetic acid into a reaction vessel and stir for 10 to 30 minutes to obtain a silane hydrolyzate; (2) Add glass fiber to silane hydrolyzate, stir and mix at 50-60°C for 2-12 hours, filter, wash and dry to obtain modified glass fiber.

5. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 4, characterized in that: The raw materials required for preparing the modified glass fiber, The invention comprises the following components: 20 parts of glass fiber, 1-2 parts of gamma-aminopropyltriethoxysilane, 0.3-0.6 parts of acetic acid, 10-15 parts of deionized water and 30-40 parts of anhydrous ethanol, calculated by weight.

6. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 1, characterized in that: The toughening agent is one or a combination of maleic anhydride grafted EPDM rubber, maleic anhydride grafted ethylene-octene copolymer, and maleic anhydride grafted ethylene-acrylate copolymer.

7. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 1, characterized in that: The twin-screw extruder is divided into seven heating zones, and the temperature of the heating zones is 210-280°C; the temperature of the first heating zone is 210-240°C, the temperature of the second heating zone is 230-250°C, the temperature of the third heating zone is 240-250°C, the temperature of the fourth heating zone is 250-260°C, the temperature of the fifth heating zone is 260-280°C, the temperature of the sixth heating zone is 260-270°C, and the temperature of the seventh heating zone is 260-270; the extrusion temperature is 260-270°C, and the screw speed is 300-500r / min.

8. The method for preparing a high and low temperature resistant polyamide cable tie according to claim 1, characterized in that: The heating and melting temperature is 250-280° C.; the injection molding parameters are: pressure 50-100 MPa, and time 10-20 s.

9. A high and low temperature resistant polyamide cable tie prepared according to the method for preparing a high and low temperature resistant polyamide cable tie according to any one of claims 1 to 8.

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