High and low temperature resistant polyamide cable tie and preparation method thereof

Abstract

The 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 in parts by weight: 40 to 60 parts of polyamide-6, 12 to 15 parts of a modifier, 5 to 15 parts of polyether-ether-ketone, 15 to 20 parts of modified glass fiber, 5 to 10 parts of a flexibilizer, 0.5 to 1 part of an antioxidant and 0.3 to 0.6 part of a lubricant. By controlling reaction conditions, lignin is prevented from being dissolved, modification grafting is carried out on the surface of the lignin, a sulfonate group, a polyether-ether-ketone chain segment, a polydimethylsiloxane chain segment and an anhydride structure are introduced, meanwhile, the rigid structure of the lignin is kept, and then the modifier is prepared. The modifier can further cooperate with polyether-ether-ketone, modified glass fibers and a flexibilizer to effectively improve 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, and specifically to a polyamide cable tie resistant to high and low temperatures and a preparation method thereof. Background Art

[0002] Due to its excellent mechanical properties, chemical corrosion resistance, and processing convenience, polyamide materials are widely used in cable ties, electronic connectors, automotive parts, and other fields. However, traditional polyamide cable ties (such as polyamide-6, polyamide-66) have significant performance defects in extreme temperature environments (such as high temperature > 120°C or low temperature < -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, leading to 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 polyamide cable tie resistant to high and low temperatures, which can well solve the defects of traditional polyamide cable ties and has practical significance. Summary of the Invention

[0004] The purpose of the present invention is to provide a polyamide cable tie resistant to high and low temperatures and a preparation method thereof to solve the problems raised in the above background art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] A preparation method of a polyamide cable tie resistant to high and low temperatures, comprising the following steps:

[0007] S1: Prepare a modifier:

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

[0009] S12: Maleic anhydride-modified lignin and sulfanilic acid undergo an amidation reaction to obtain sulfonated modified lignin;

[0010] S13: Polyether ether ketone is reduced with sodium borohydride to obtain hydroxylated polyether ether ketone;

[0011] S14: Sulfonated modified lignin and hydroxylated polyether ether ketone undergo a sulfonic acid esterification reaction to obtain lignin-modified polyether ether ketone;

[0012] S15: Lignin-modified polyether ether ketone, vinyl-terminated polydimethylsiloxane, and maleic anhydride initiate polymerization to obtain a modifier;

[0013] S2: Prepare modified glass fiber:

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

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

[0016] S31: Add polyamide - 6, modifier, polyether ether ketone, modified glass fiber, toughening agent, antioxidant, and lubricant into a twin - screw extruder, melt - mix, extrude, and pelletize to obtain a high and low temperature resistant polyamide cable tie composite material;

[0017] S32: Add the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, heat and melt it, and injection - mold to obtain high and low temperature resistant polyamide cable ties.

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

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

[0020] Preferably, the lignin is alkali lignin.

[0021] Preferably, 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.

[0022] Preferably, the mass ratio of polyether ether ketone, sodium borohydride, and dimethyl sulfoxide is 1:(0.1 - 0.2):10.

[0023] Preferably, 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] Preferably, 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. Introducing it into the resin can improve the high-temperature resistance of the resin. In addition, lignin also has a rigid structure. If its compatibility is improved, it can also enhance the mechanical properties of the resin. Based on this, in the present invention, by controlling the reaction conditions, lignin dissolution is avoided, and graft modification treatment is always carried out on the surface of lignin. While introducing other beneficial chain segments or groups, its rigid structure is maintained, and finally a modifier is prepared. The specific preparation process is as follows: In the present invention, acetic acid is first used as a solvent and a catalyst to carry out an esterification reaction between the anhydride of maleic anhydride and the phenolic hydroxyl group on lignin to obtain maleic anhydride-modified lignin with unsaturated double bonds and carboxyl groups; then the double bond on the maleic anhydride-modified lignin reacts with the amino group on sodium p-aminobenzenesulfonate to carry out an amidation reaction to obtain sulfonated modified lignin still having unsaturated bonds; then after hydroxylation treatment of polyetheretherketone, the hydroxyl group on the hydroxylated polyetheretherketone reacts with the sulfonic acid group on the sulfonated modified lignin to carry out a sulfonic acid esterification reaction to obtain lignin-modified polyetheretherketone with unsaturated bonds; finally, the unsaturated bond on the lignin-modified polyetheretherketone initiates polymerization with the unsaturated bonds on vinyl-terminated polydimethylsiloxane and maleic anhydride to obtain a modifier. Among them, in the preparation process of maleic anhydride-modified lignin, the reason for using acetic acid as a solvent is that maleic anhydride has higher reactivity than acetic acid, so maleic anhydride will react first; and because there is no water in acetic acid, maleic anhydride will not undergo hydrolysis, so that no side reactions will occur during the reaction, and a fast esterification rate can be continuously maintained; in addition, the reaction is carried out at 30-40 °C, and the lignin dissolution rate is extremely low at this temperature. Finally, maleic anhydride can quickly carry out an esterification reaction with the phenolic hydroxyl groups on the surface or in the shallow pores of lignin; in the subsequent preparation of sulfonated modified lignin, lignin-modified polyetheretherketone, and the modifier, the reaction process is promoted by a catalyst, effectively reducing the reaction temperature, avoiding an increase in the solubility of lignin, and ensuring the rigid structure of lignin.

[0026] The obtained modifier is added to polyamide-6. Since the modifier contains a lignin rigid structure, a sulfonate group, a polyether ether ketone chain segment, a polydimethylsiloxane chain segment, and an anhydride structure; first, the presence of the anhydride structure can form a stable chemical bond with the amide group in polyamide-6, that is, the modifier has a good compatibility with polyamide-6; second, under the action of the lignin rigid structure, the modifier plays a role in improving the mechanical properties and high-temperature resistance of polyamide-6; furthermore, the polyether ether ketone chain segment can improve the compatibility between polyamide-6 and polyether ether ketone. Therefore, a part of polyether ether ketone can be further introduced into polyamide-6. Under the action of the modifier, polyether ether ketone and polyamide-6 also have good compatibility, which can further enhance the mechanical properties and high-temperature resistance of polyamide-6; and the sulfonate group and the amide group can form a hydrogen bond, which can also enhance the compatibility between the modifier and polyamide-6 to a certain extent. At the same time, due to the hydrogen bond, the mechanical properties and high-temperature resistance of polyamide-6 will also be enhanced; finally, the end of the polydimethylsiloxane chain is a flexible chain end, and the flexible chain end 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. And because the modifier has good compatibility with polyether ether ketone, it can also be used as a compatibilizer for polyether ether ketone and polyamide-6. Finally, under the synergistic action of the modifier and polyether ether ketone, the effective improvement of the mechanical properties and high and low temperature resistance of polyamide-6 is realized.

[0027] Preferably, the preparation method of the modified glass fiber is as follows: (1) Add γ-aminopropyltriethoxysilane, deionized water, absolute ethanol, and acetic acid into a reaction vessel, stir and mix for 10 - 30 min to obtain a silane hydrolysis solution; (2) Add the glass fiber into the silane hydrolysis solution, stir and mix at 50 - 60 °C for 2 - 12 h, and after filtration, washing, and drying, obtain the modified glass fiber.

[0028] Preferably, the raw materials required for the preparation of the modified glass fiber include the following components: by weight, 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 absolute ethanol.

[0029] Preferably, the glass fiber is a chopped glass fiber with a single filament diameter of 10 μm.

[0030] In the present invention, in order to further enhance the heat resistance of polyamide-6, γ-aminopropyltriethoxysilane is used to modify glass fibers to obtain modified glass fibers; the modified glass fibers contain amino groups, which can form hydrogen bonds with the amide groups on polyamide-6, and can play a role in enhancing the dispersibility and compatibility of glass fibers in polyamide-6. By introducing glass fibers, a reinforcing network can be formed in polyamide-6, thereby enhancing the mechanical properties of polyamide-6 at high and low temperatures.

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

[0032] In the present invention, a toughening agent is further added to further modify polyamide-6 in cooperation with the modifier, polyetheretherketone, and modified glass fibers, so as to balance the heat resistance and mechanical properties of polyamide-6.

[0033] Preferably, the high and low temperature resistant polyamide tie material composite includes the following component raw materials: by weight, 40-60 parts of polyamide-6, 12-15 parts of modifier, 5-15 parts of polyetheretherketone, 15-20 parts of modified glass fibers, 5-10 parts of toughening agent, 0.5-1 part of antioxidant, and 0.3-0.6 part of lubricant.

[0034] Preferably, 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 °C; the extrusion temperature is 260-270 °C, and the screw speed is 300-500 r / min.

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

[0036] Compared with the prior art, the beneficial effects achieved by the present invention are:

[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 both polyamide-6 and polyetheretherketone, and can also be used as a compatibilizer to promote the compatibility of polyetheretherketone and polyamide-6;

[0038] (2) In the present invention, a toughening agent and modified glass fiber are further introduced to improve polyamide-6 in cooperation with polyetheretherketone and a modifier. Moreover, each component is evenly dispersed and has good compatibility, effectively improving the mechanical properties and high and low temperature resistance of polyamide-6. Detailed implementation manners

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part rather than all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0040] It should be noted that the following parts are by weight. There are no special restrictions on the purchase manufacturers of all the raw materials involved in the present invention. Exemplarily, they include:

[0041] In the following embodiments,

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

[0043] Polyetheretherketone, 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, and a product number of N216, was purchased from Ningbo Yikun Import and Export Co., Ltd.;

[0045] Short cut glass fiber, with a purity of 99%, a single filament diameter of 10 μm, and a length of 3-6 mm, was purchased from Shanghai Yuanye Biotechnology Co., Ltd.;

[0046] Antioxidant 703, with a purity of 99%, was purchased from Shandong Tianhong Biomedicine Co., Ltd.;

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

[0048] Maleic anhydride, with a purity of 99%, was purchased from Shanghai Bangcheng Chemical Industry Co., Ltd.;

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

[0050] Terminal vinyl polydimethylsiloxane, with a purity of 99% and a molecular weight of 1000, was purchased from Hubei Shixing Chemical Industry Co., Ltd.;

[0051] Each of the following parts by weight is 100 g.

[0052] Example 1: A preparation method of a high and low temperature resistant polyamide tie:

[0053] S1: Preparation of modifier: (1) Under nitrogen protection, 0.8 part of maleic anhydride, 4.2 parts of alkali lignin, and 20 parts of acetic acid were added into a reaction vessel, and stirred at 35 °C for 3 h to end the reaction. 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 into a reaction vessel, and stirred at 55 °C for 3 h to end the reaction. After separation and purification, sulfonated modified lignin was obtained; (3) 10 parts of polyether ether ketone, 1.5 parts of sodium borohydride, and 100 parts of dimethyl sulfoxide were added into a reaction vessel, and stirred at 120 °C for 6 h to end the reaction. After separation and purification, hydroxylated polyether ether ketone was obtained; (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, and stirred at 55 °C for 6 h to end the reaction. 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 terminal vinyl polydimethylsiloxane, and 0.6 part of maleic anhydride were added into a reaction vessel, stirred and mixed evenly. At 60 °C, 0.3 part of benzoyl peroxide was added dropwise to the reaction solution while stirring. After the addition was completed, stirring was continued for 2 h to obtain the modifier;

[0054] S2: Preparation of modified glass fiber: (1) 1.5 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of absolute ethanol, and 0.5 part of acetic acid were added into a reaction vessel, and stirred and mixed for 20 min to obtain a silane hydrolysis solution; (2) 20 parts of chopped glass fiber were added into the silane hydrolysis solution, and stirred and mixed at 55 °C for 6 h. After filtration, washing, and drying, modified glass fiber was obtained;

[0055] S3: Prepare high and low temperature resistant polyamide cable ties: S31: Add polyamide-6, modifier, polyether ether ketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and lubricant into a twin-screw extruder. After melting and mixing, extrude and pelletize to obtain high and low temperature resistant polyamide cable tie composite materials; S32: Add the high and low temperature resistant polyamide cable tie composite materials into an injection molding machine. After heating and melting, injection mold to obtain high and low temperature resistant polyamide cable ties;

[0056] Among them, the high and low temperature resistant polyamide cable tie composite materials include the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyether ether ketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 parts of antioxidant 703, and 0.5 parts of lubricant;

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

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

[0059] Example 2: A preparation method of high and low temperature resistant polyamide cable ties:

[0060] S1: Preparation of modifier: (1) Under nitrogen protection, 0.5 part of maleic anhydride, 4.5 parts of alkali lignin, and 20 parts of acetic acid are added into a reaction vessel, and stirred at 35 °C for 1 h to end the reaction. After separation and purification, maleic anhydride-modified lignin is 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 are added into a reaction vessel, and stirred at 55 °C for 1 h to end the reaction. After separation and purification, sulfonated modified lignin is obtained; (3) 10 parts of polyether ether ketone, 1 part of sodium borohydride, and 100 parts of dimethyl sulfoxide are added into a reaction vessel, and stirred at 120 °C for 3 h to end the reaction. After separation and purification, hydroxylated polyether ether ketone is 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 are added into a reaction vessel, and stirred at 55 °C for 3 h to end the reaction. After separation and purification, lignin-modified polyether ether ketone is obtained; (5) Under nitrogen protection, 15 parts of lignin-modified polyether ether ketone, 0.75 part of vinyl-terminated polydimethylsiloxane, and 0.375 part of maleic anhydride are added into a reaction vessel, stirred and mixed evenly. At 60 °C, 0.3 part of benzoyl peroxide is added dropwise to the reaction solution while stirring. After the addition, stirring reaction is continued for 2 h to obtain the modifier;

[0061] S2: Preparation of modified glass fiber: (1) 1 part of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of absolute ethanol, and 0.5 part of acetic acid are added into a reaction vessel and stirred and mixed for 10 min to obtain a silane hydrolysis solution; (2) 20 parts of chopped glass fiber are added into the silane hydrolysis solution, stirred and mixed at 55 °C for 2 h, and after filtration, washing, and drying, modified glass fiber is obtained;

[0062] S3: Preparation of high and low temperature resistant polyamide tie straps: S31: Polyamide-6, modifier, polyether ether ketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and lubricant are added into a twin-screw extruder, melt-mixed, extruded, and pelletized to obtain a high and low temperature resistant polyamide tie strap composite material; S32: The high and low temperature resistant polyamide tie strap composite material is added into an injection molding machine, heated and melted, and injection molded to obtain a high and low temperature resistant polyamide tie strap;

[0063] Among them, the high and low temperature resistant polyamide tie strap composite material includes the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyether ether ketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 part of antioxidant 703, and 0.5 part of lubricant;

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

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

[0066] Example 3: A preparation method of 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 are added to the reaction vessel, and stirred at 35 °C for 6 h to end the reaction. After separation and purification, maleic anhydride modified lignin is obtained; (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 are added to the reaction vessel, and stirred at 55 °C for 6 h to end the reaction. After separation and purification, sulfonated modified lignin is obtained; (3) 10 parts of polyetheretherketone, 2 parts of sodium borohydride, and 100 parts of dimethyl sulfoxide are added to the reaction vessel, and stirred at 120 °C for 9 h to end the reaction. After separation and purification, hydroxylated polyetheretherketone is obtained; (4) Under nitrogen protection, 3 parts of sulfonated modified lignin, 14 parts of hydroxylated polyetheretherketone, 17 parts of N,N'-dicyclohexylcarbodiimide, 2 parts of 4-dimethylaminopyridine, and 100 parts of N-methylpyrrolidone are added to the reaction vessel, and stirred at 55 °C for 9 h to end the reaction. After separation and purification, lignin modified polyetheretherketone is obtained; (5) Under nitrogen protection, 15 parts of lignin modified polyetheretherketone, 2.25 parts of vinyl-terminated polydimethylsiloxane, and 0.75 part of maleic anhydride are added to the reaction vessel, stirred and mixed evenly. At 60 °C, 0.3 part of benzoyl peroxide is added dropwise to the reaction solution, stirring while adding. After the addition is complete, continue to stir and react for 3 h to obtain the modifier;

[0068] S2: Preparation of modified glass fiber: (1) 2 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of absolute ethanol, and 0.5 part of acetic acid are added to the reaction vessel, stirred and mixed for 30 min to obtain a silane hydrolysis solution; (2) 20 parts of chopped glass fiber are added to the silane hydrolysis solution, stirred and mixed at 55 °C for 12 h, and after filtration, washing, and drying, modified glass fiber is obtained;

[0069] S3: Prepare high and low temperature resistant polyamide cable ties: S31: Add polyamide-6, modifier, polyether ether ketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and lubricant into a twin-screw extruder, melt and mix, extrude, and pelletize to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Add the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, heat and melt, and injection mold to obtain high and low temperature resistant polyamide cable ties;

[0070] Among them, 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 polyether ether ketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 part of antioxidant 703, and 0.5 part of lubricant;

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

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

[0073] The following is based on Example 1 for a control experiment, setting Comparative Examples 1-5, specifically as follows:

[0074] Comparative Example 1: Comparative Example 1 is based on Example 1 and adjusted: only maleic anhydride is used to modify lignin, and other processes remain unchanged. Specifically:

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

[0076] S1: Prepare maleic anhydride modified lignin: (1) Under nitrogen protection, add 3.2 parts of maleic anhydride, 16.8 parts of alkali lignin, and 80 parts of acetic acid into a reaction vessel, stir and react at 35 °C for 3 h, end the reaction, and obtain maleic anhydride modified lignin through separation and purification;

[0077] S2: Prepare modified glass fiber: (1) Add 1.5 parts of γ-aminopropyltriethoxysilane, 13 parts of deionized water, 37 parts of absolute ethanol, and 0.5 part of acetic acid into a reaction vessel, stir and mix for 20 min to obtain a silane hydrolysis solution; (2) Add 20 parts of chopped glass fiber into the silane hydrolysis solution, stir and mix at 55 °C for 6 h, and obtain modified glass fiber through filtration, washing, and drying;

[0078] S3: Prepare high and low temperature resistant polyamide cable ties: S31: Add polyamide-6, maleic anhydride modified lignin, polyether ether ketone, maleic anhydride grafted ethylene-octene copolymer, modified glass fiber, antioxidant 703, and lubricant into a twin-screw extruder, melt and mix, extrude, and pelletize to obtain a high and low temperature resistant polyamide cable tie composite material; S32: Add the high and low temperature resistant polyamide cable tie composite material into an injection molding machine, heat and melt, and injection mold to obtain high and low temperature resistant polyamide cable ties;

[0079] Among them, 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 maleic anhydride modified lignin, 10 parts of polyether ether ketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 part of antioxidant 703, and 0.5 part of lubricant;

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

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

[0082] Comparative Example 2: Comparative Example 2 is based on Example 1 and is adjusted as follows: 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 polyether ether ketone, 18 parts of modified glass fiber, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 part of antioxidant 703, and 0.5 part of lubricant.

[0084] Comparative Example 3: Comparative Example 3 is based on Example 1 and is adjusted as follows: no polyether ether ketone 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, 0.8 part of antioxidant 703, and 0.5 part of lubricant.

[0086] Comparative Example 4: Comparative Example 4 is based on Example 1, with the following adjustments: maleic anhydride grafted ethylene-octene copolymer is not added, and other processes remain unchanged;

[0087] The high and low temperature resistant polyamide cable tie composite material comprises the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyether ether ketone, 18 parts of modified glass fiber, 0.8 part of antioxidant 7030, and 0.5 part of lubricant.

[0088] Comparative Example 5: Comparative Example 5 is based on Example 1, with the following adjustments: modified glass fiber is not added, and other processes remain unchanged. Specifically:

[0089] The high and low temperature resistant polyamide cable tie composite material comprises the following component raw materials: by weight, 50 parts of polyamide-6, 14 parts of modifier, 10 parts of polyether ether ketone, 8 parts of maleic anhydride grafted ethylene-octene copolymer, 0.8 part of antioxidant 7030, and 0.5 part 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 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 oven. The high temperature oven is heated at a heating rate of 10 K / min to 150 °C. After 12 h, take out the high and low temperature resistant polyamide cable tie and immediately conduct a high temperature tensile test on it at a tensile rate of 5 cm / min. Combine with the tensile strength measured at room temperature to calculate its tensile strength retention rate (%).

[0092] (2) Place the high and low temperature resistant polyamide cable tie in a low temperature oven. The low temperature oven is cooled at a cooling rate of 10 K / min to -50 °C. After 12 h, take out the high and low temperature resistant polyamide cable tie and immediately conduct a low temperature tensile test on it at a tensile rate of 5 cm / min. Combine with the tensile strength measured at room temperature to 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 Table 1 below:

[0094] Table 1

[0095]

[0096]

[0097] Result analysis: It can be known from the data in Table 1 above that through the synergistic effect of the modifier, polyether ether ketone, toughening agent, and modified glass fiber, the comprehensive modification of polyamide-6 is realized in the present invention. The finally prepared polyamide cable tie with high and low temperature resistance exhibits excellent heat resistance whether at a high temperature of 150 °C or at a low temperature of -50 °C. Among them, when placed at -50 °C for 12 hours, the highest tensile strength retention rate is 92%, and when placed at 150 °C for 12 hours, the highest tensile strength retention rate is 85%.

[0098] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope 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 hydroxylated polyetheretherketone; S14: Sulfonated modified lignin reacts with hydroxylated polyetheretherketone to obtain lignin modified polyetheretherketone; S15: Polyetheretherketone modified with lignin is polymerized with vinyl-terminated polydimethylsiloxane and maleic anhydride to obtain a modifier; S2: Preparation of modified glass fiber: S21: modifying the 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, and injection molding to obtain the high and low temperature resistant polyamide cable tie.

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 into a reaction vessel, stirred and reacted at 30-40° C. for 1-6 hours, the reaction is terminated, and 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 into a reaction vessel, stirred at 50-60° C. for 1-6 hours, the reaction is terminated, and the sulfonated modified lignin is obtained by separation and purification; (3) adding polyetheretherketone, sodium borohydride and dimethyl sulfoxide into a reaction container, stirring and reacting at 115-125° C. for 3-9 hours, terminating the reaction, and separating and purifying to obtain hydroxylated polyetheretherketone; (4) under nitrogen protection, adding sulfonated modified lignin, hydroxylated polyetheretherketone, N,N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, and N-methylpyrrolidone into a reaction container, stirring and reacting at 50-60° C. for 3-9 hours, terminating the reaction, and separating and purifying to obtain lignin-modified polyetheretherketone; (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 to 70° C. while stirring. After the addition is completed, the reaction is continued with stirring for 1 to 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 1:(0.1-0.2):

10. 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) adding γ-aminopropyltriethoxysilane, deionized water, anhydrous ethanol, and acetic acid into a reaction container, stirring and mixing for 10 to 30 minutes to obtain a silane hydrolyzate; (2) Adding glass fiber to silane hydrolyzate, stirring and mixing at 50-60° C. for 2-12 hours, filtering, washing and drying 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: by weight, 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.

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, 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 high and low temperature resistant polyamide cable tie composite material comprises 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.

8. 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.

9. 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 of 50-100 MPa, and time of 10-20 s.

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

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