Impact-resistant ultra-high molecular weight polyethylene fiber and preparation method thereof

Abstract

The invention relates to the technical field of polymer fibers, and in particular to an impact-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. The invention introduces maleic anhydride for graft modification, and benzoyl peroxide as an initiator can promote the formation of free radicals, so that active sites are generated on the ultra-high molecular weight polyethylene chain. Maleic anhydride as a polar monomer can react with the active sites to form a graft chain, thereby introducing polar groups to enhance the interaction force between molecules, and improving the toughness and processing fluidity of the material to a certain extent. In addition, white oil, decalin and xylene as solvents are conducive to the expansion and dispersion of the ultra-high molecular weight polyethylene, so that the modification process is more uniform and efficient. The toughening polymer component in the invention is synthesized by chemical reaction to obtain a cross-linked network structure with multiple functional groups and a high molecular weight, so that the external impact force can be effectively absorbed and dispersed, and the impact resistance of the material can be significantly improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer fibers, and in particular to an impact-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. Background Art

[0002] Ultra-high molecular weight polyethylene fiber, with its excellent wear resistance, high strength, high modulus and good chemical stability, has shown broad application prospects in many fields such as safety protection, aerospace, deep-sea engineering, sports equipment, etc. However, despite its many advantages, traditional ultra-high molecular weight polyethylene fiber still needs to be improved in impact resistance and flame retardancy, especially in extreme environments such as high-intensity impact, high temperature or flame exposure. The performance of traditional fibers may be significantly affected, and even lead to material failure.

[0003] In the existing technology, in order to improve the impact resistance of ultra-high molecular weight polyethylene fiber, the method of adding toughening agents or chemical modification is usually adopted. However, these methods often lead to a decrease in other properties of the fiber, such as strength and modulus. In addition, the improvement of flame retardant performance usually depends on the addition of flame retardants, but this may also lead to problems such as reduced processing performance, increased costs and uneven overall fiber performance. Therefore, how to improve the impact resistance and flame retardant properties of ultra-high molecular weight polyethylene fiber while maintaining its excellent properties has become a technical problem that needs to be solved in this field. Summary of the invention

[0004] Technical issues solved

[0005] In view of the above-mentioned shortcomings of the prior art, the present invention provides an impact-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof, which can effectively solve the problem that the impact resistance and flame retardancy of the ultra-high molecular weight polyethylene fiber in the prior art need to be improved.

[0006] Technical Solution

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] An impact-resistant ultra-high molecular weight polyethylene fiber, the impact-resistant ultra-high molecular weight polyethylene fiber is composed of the following components: modified ultra-high molecular weight polyethylene, a toughening polymer component, a flame retardant modified component, a modified composite filler component, a silane coupling agent KH-570 and an antioxidant 1010;

[0009] The modified ultra-high molecular weight polyethylene is obtained by grafting and modifying ultra-high molecular weight polyethylene;

[0010] The raw materials for preparing the toughening polymer component include lactide, 4-diaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid, isoprene and benzothiazole;

[0011] The flame retardant modified component is prepared by grafting magnesium hydroxide with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;

[0012] The modified composite filler component is prepared by modifying the composite filler component with a silane coupling agent KH-560.

[0013] Furthermore, the preparation steps of the modified ultra-high molecular weight polyethylene are:

[0014] Step A, weighing 10g of white oil, 10g of decalin, 10g of xylene and 60g of ultra-high molecular weight polyethylene into a flask, heating at an oil bath temperature of 100°C to expand the ultra-high molecular weight polyethylene, then adding 1.5g of benzoyl peroxide and 4g of maleic anhydride and reacting for 5h under nitrogen protection, the obtained product is recorded as a grafted product;

[0015] Step B, placing the grafted product in a Soxhlet extractor and extracting it with acetone for 24 hours, then drying it in an oven at 60° C. for 8 hours, and finally drying it in a vacuum drying oven to constant weight, to obtain the modified ultra-high molecular weight polyethylene.

[0016] Furthermore, the preparation steps of the toughening polymer component are:

[0017] Step 1, pour 5g of lactide and 60mL of toluene into a flask, add 0.2g of benzyl alcohol and 0.04g of stannous octoate under a nitrogen atmosphere, pass nitrogen for 15min, seal and place in an oil bath at 130°C for stirring reaction, add 50mL of dichloromethane after the reaction is completed, mix evenly, drop into anhydrous ethanol to collect the precipitate and place the precipitate at 30°C under vacuum and dry for 20h, the resulting polylactide;

[0018] Step 2, weigh 3g of polylactide, 2g of 4-diaminopyridine, 8g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 15g of 2-(dodecyl trithiocarbonate)-2-methylpropionic acid into a flask, add 100mL of dichloromethane and stir evenly in a water bath at 25°C, place under reduced pressure rotary evaporation at 40°C to remove dichloromethane and pour into methanol for precipitation, and the resulting precipitate is placed under vacuum drying at 80°C for 10h, and the resulting product is recorded as an intermediate product;

[0019] Step 3: weigh 22 g of isoprene, 16 g of the intermediate product, 0.6 g of di-tert-butyl peroxide and 2 g of benzothiazole, pour them into a flask filled with 200 mL of toluene, pass nitrogen for 20 min, seal the flask and place it in an oil bath at 125°C for stirring and reaction. After the reaction is completed, add it dropwise into methanol to collect the precipitate and place the precipitate at 30°C for vacuum drying for 20 hours to obtain the toughened polymer component.

[0020] Furthermore, the specific operation of stirring the reaction in step 1 is stirring at a stirring speed of 200 r / min for 24 hours, the specific operation of mixing evenly in step 1 is stirring at a stirring speed of 300 r / min for 10 minutes, and the dripping rate in step 1 is 1 drop / s.

[0021] Furthermore, the specific operation of stirring uniformly in step 2 is stirring at a stirring speed of 300 r / min for 30 minutes, and the specific operation of stirring the reaction in step 3 is stirring at a stirring speed of 200 r / min for 24 hours.

[0022] Furthermore, the preparation method of the flame retardant modified component is:

[0023] Weigh 5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 9 g of silane coupling agent KH-560, mix them, stir them at a temperature of 160°C and a stirring speed of 300 r / min for 2 hours, pour them into 100 mL of anhydrous ethanol, add 12 g of magnesium hydroxide, stir them at a temperature of 120°C and a stirring speed of 200 r / min for 2 hours, filter to remove the filtrate, place it in an oven at 120°C and dry it for 2 hours, and grind it through a 200-mesh sieve to obtain a flame retardant modified component.

[0024] Furthermore, the composite filler components are prepared by mixing nano silicon dioxide, mica powder, nano alumina, carbon nano tubes and nano glass beads in equal weight ratios and pouring the mixture into a ball mill for 1 hour.

[0025] Furthermore, the preparation method of the modified composite filler component is:

[0026] Weigh 5g of silane coupling agent KH-560 and 200mL of anhydrous ethanol, mix them, stir at a stirring speed of 500r / min for 30min, then add 15-20g of composite filler component, ultrasonically disperse at a frequency of 30kHz for 30min, stir at a stirring speed of 200r / min in a water bath at 58°C until the anhydrous ethanol is completely volatilized, then place in an oven at 60°C to dry for 6h and grind through a 200-mesh sieve to obtain the modified composite filler component.

[0027] A method for preparing impact-resistant ultra-high molecular weight polyethylene fiber, the preparation method comprising:

[0028] S1, weighing 100 parts by weight of modified ultra-high molecular weight polyethylene, 15-20 parts by weight of toughening polymer component, 3-5 parts by weight of flame retardant modified component, 5-8 parts by weight of modified composite filler component, 1-2 parts by weight of silane coupling agent KH-570 and 1-2 parts by weight of antioxidant 1010 into an internal mixer, mixing at a temperature of 140-150° C. and a speed of 60 r / min for 10 min, and extruding and granulating the obtained product through a twin-screw extruder as impact-resistant ultra-high molecular weight polyethylene masterbatch;

[0029] S2. Tetralin and decalin are mixed in an equal weight ratio to prepare a solvent component, and the impact-resistant ultra-high molecular weight polyethylene masterbatch is mixed with the solvent component in a weight ratio of 10-15% to prepare a spinning solution, which is then extruded into filaments through a twin-screw spinning machine, and then cooled, extracted, dried and subjected to multi-stage heat drawing treatment to obtain impact-resistant ultra-high molecular weight polyethylene fibers.

[0030] Furthermore, in S2, the extractant is any one of toluene, methyl chloride, dichloromethane, chloroform and carbon tetrachloride, or a combination of two or more thereof, the extraction time is 30-60 min, the extraction temperature is 50-60°C, the multi-stage stretching treatment adopts a stretching temperature of 120-150°C, a stretching time of 5-10 min, and a stretching multiple of 30-60 times.

[0031] Beneficial Effects

[0032] The present invention provides an impact-resistant ultra-high molecular weight polyethylene fiber and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The present invention introduces maleic anhydride for graft modification. Benzoyl peroxide as an initiator can promote the formation of free radicals, so that active sites are generated on the ultra-high molecular weight polyethylene chain. Maleic anhydride as a polar monomer can react with the active sites to form a graft chain, thereby introducing polar groups to enhance the interaction between molecules, and to a certain extent, improving the toughness and processing fluidity of the material. In addition, white oil, decalin and xylene as solvents are conducive to the expansion and dispersion of ultra-high molecular weight polyethylene, making the modification process more uniform and efficient; the toughening polymer component in the present invention is synthesized by chemical reaction to obtain a cross-linked network structure with multiple functional groups and high molecular weight, so that it can effectively absorb and disperse external impact forces, and can significantly improve the impact resistance of the material. At the same time, the interaction between the cross-linked network structures can also enhance the heat resistance and chemical stability of the material, further improving the durability of the fiber.

[0034] 2. The flame retardant modified component in the present invention is based on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is modified by grafting magnesium hydroxide to obtain a composite material with both physical and chemical flame retardant effects. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a highly efficient phosphorus-based flame retardant that can produce non-combustible substances such as phosphates during combustion, which cover the surface of the material to form a protective layer, isolate oxygen, and inhibit the combustion chain reaction. The addition of magnesium hydroxide can not only enhance the thermal stability of the material, but also decompose and absorb heat at high temperatures, reduce the surface temperature of the material, and further delay the combustion process; secondly, the introduction of silane coupling agent KH-560 can improve the compatibility between the flame retardant and the base material, ensuring the uniform distribution of flame retardant properties.

[0035] 3. The composite filler component in the present invention is prepared by mixed ball milling of nano-silicon dioxide, mica powder, nano-alumina, carbon nanotubes and nano-glass beads. These nano-scale fillers have extremely high specific surface area and surface energy, and can significantly improve the mechanical properties and heat resistance of the material. The modification treatment of silane coupling agent KH-560 can not only enhance the interfacial bonding force between the filler and the matrix material, but also promote the uniform dispersion of the filler, thereby avoiding agglomeration and achieving a dual improvement in material strength and toughness.

[0036] 4. In the preparation process of the present invention, a series of finely controlled steps such as mixing, extrusion granulation, spinning, cooling, extraction, drying and multi-stage hot stretching can ensure the uniformity and orientation of the fiber structure, further improve the mechanical properties and stability of the fiber, and the multi-stage hot stretching treatment can optimize the internal structure of the fiber to make it have higher strength and better impact resistance. At the same time, the selection of appropriate extractants and extraction conditions can effectively remove solvent residues in the fiber to ensure the purity and quality of the fiber. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The present invention will be further described below in conjunction with the embodiments.

[0039] Example 1

[0040] The impact-resistant ultra-high molecular weight polyethylene fiber of this embodiment is composed of the following components: modified ultra-high molecular weight polyethylene, a toughening polymer component, a flame retardant modified component, a modified composite filler component, a silane coupling agent KH-570 and an antioxidant 1010;

[0041] The modified ultra-high molecular weight polyethylene is obtained by grafting and modifying ultra-high molecular weight polyethylene, and the specific preparation steps are as follows:

[0042] Step A, weighing 10g of white oil, 10g of decalin, 10g of xylene and 60g of ultra-high molecular weight polyethylene into a flask, heating at an oil bath temperature of 100°C to expand the ultra-high molecular weight polyethylene, then adding 1.5g of benzoyl peroxide and 4g of maleic anhydride and reacting for 5h under nitrogen protection, the obtained product is recorded as a grafted product;

[0043] Step B, placing the grafted product in a Soxhlet extractor and extracting it with acetone for 24 hours, then drying it in an oven at 60° C. for 8 hours, and finally drying it in a vacuum drying oven to constant weight, to obtain the modified ultra-high molecular weight polyethylene.

[0044] The raw materials for preparing the toughening polymer component include lactide, 4-diaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid, isoprene and benzothiazole. The specific preparation steps are as follows:

[0045] Step 1, 5g of lactide and 60mL of toluene are poured into a flask, 0.2g of benzyl alcohol and 0.04g of stannous octoate are added under a nitrogen atmosphere, nitrogen is introduced for 15min, the mixture is sealed and placed in an oil bath at 130°C and stirred at a stirring speed of 200r / min for 24h, 50mL of dichloromethane is added after the reaction is completed and stirred at a stirring speed of 300r / min for 10min, anhydrous ethanol is dripped at a dripping rate of 1 drop / s, a precipitate is collected and the precipitate is placed at a temperature of 30°C and vacuum dried for 20h to obtain polylactide;

[0046] Step 2, weigh 3g of polylactide, 2g of 4-diaminopyridine, 8g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 15g of 2-(dodecyl trithiocarbonate)-2-methylpropionic acid into a flask, add 100mL of dichloromethane, stir at a stirring speed of 300r / min for 30min in a water bath at 25°C, place under reduced pressure rotary evaporation at 40°C to remove dichloromethane, and then pour into methanol for precipitation. The resulting precipitate is placed at 80°C and vacuum dried for 10h, and the resulting product is recorded as an intermediate product;

[0047] Step 3, weigh 22g of isoprene, 16g of the intermediate product, 0.6g of di-tert-butyl peroxide and 2g of benzothiazole, pour into a flask filled with 200mL of toluene, pass nitrogen for 20min, seal the flask and place it in an oil bath at 125°C and stir at a speed of 200r / min for 24h. After the reaction is completed, add it dropwise into methanol to collect the precipitate and place the precipitate at 30°C and vacuum dry it for 20h to obtain the toughened polymer component.

[0048] The flame retardant modified component is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide onto magnesium hydroxide. The specific preparation method is as follows:

[0049] Weigh 5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 9 g of silane coupling agent KH-560, mix them, stir them at a temperature of 160°C and a stirring speed of 300 r / min for 2 hours, pour them into 100 mL of anhydrous ethanol, add 12 g of magnesium hydroxide, stir them at a temperature of 120°C and a stirring speed of 200 r / min for 2 hours, filter to remove the filtrate, place it in an oven at 120°C and dry it for 2 hours, and grind it through a 200-mesh sieve to obtain a flame retardant modified component.

[0050] The modified composite filler component is prepared by modifying the composite filler component with a silane coupling agent KH-560, wherein the composite filler component is prepared by mixing nano-silicon dioxide, mica powder, nano-alumina, carbon nanotubes and nano-glass microbeads in equal weight ratios and pouring them into a ball mill for ball milling for 1 hour;

[0051] The preparation method of the modified composite filler component is:

[0052] Weigh 5g of silane coupling agent KH-560 and 200mL of anhydrous ethanol, mix them, stir at a stirring speed of 500r / min for 30min, then add 15g of composite filler component, ultrasonically disperse at a frequency of 30kHz for 30min, stir at a stirring speed of 200r / min in a water bath at 58°C until the anhydrous ethanol is completely volatilized, then place in an oven at 60°C to dry for 6h and grind through a 200-mesh sieve to obtain the modified composite filler component.

[0053] A method for preparing impact-resistant ultra-high molecular weight polyethylene fiber, the preparation method comprising:

[0054] S1, weighing 100 parts by weight of modified ultra-high molecular weight polyethylene, 15 parts by weight of toughening polymer component, 3 parts by weight of flame retardant modified component, 5 parts by weight of modified composite filler component, 1 part by weight of silane coupling agent KH-570 and 1 part by weight of antioxidant 1010 into an internal mixer, mixing at a temperature of 140° C. and a speed of 60 r / min for 10 min, and extruding and granulating the obtained product through a twin-screw extruder as impact-resistant ultra-high molecular weight polyethylene masterbatch;

[0055] S2. Tetralin and decalin are mixed in an equal weight ratio to prepare a solvent component, and the impact-resistant ultra-high molecular weight polyethylene masterbatch is mixed with the solvent component in a weight ratio of 10% to prepare a spinning solution, which is then extruded into filaments through a twin-screw spinning machine, and then cooled, extracted, dried and subjected to multi-stage heat drawing treatment to obtain impact-resistant ultra-high molecular weight polyethylene fibers.

[0056] In S2, the extractant is toluene, the extraction time is 30 minutes, the extraction temperature is 50°C, the multi-stage stretching treatment adopts a stretching temperature of 120°C, a stretching time of 5 minutes, and a stretching multiple of 30 times.

[0057] Example 2

[0058] The impact-resistant ultra-high molecular weight polyethylene fiber of this embodiment is composed of the following components: modified ultra-high molecular weight polyethylene, a toughening polymer component, a flame retardant modified component, a modified composite filler component, a silane coupling agent KH-570 and an antioxidant 1010;

[0059] The modified ultra-high molecular weight polyethylene is obtained by grafting and modifying ultra-high molecular weight polyethylene, and the specific preparation steps are as follows:

[0060] Step A, weighing 10g of white oil, 10g of decalin, 10g of xylene and 60g of ultra-high molecular weight polyethylene into a flask, heating at an oil bath temperature of 100°C to expand the ultra-high molecular weight polyethylene, then adding 1.5g of benzoyl peroxide and 4g of maleic anhydride and reacting for 5h under nitrogen protection, the obtained product is recorded as a grafted product;

[0061] Step B, placing the grafted product in a Soxhlet extractor and extracting it with acetone for 24 hours, then drying it in an oven at 60° C. for 8 hours, and finally drying it in a vacuum drying oven to constant weight, to obtain the modified ultra-high molecular weight polyethylene.

[0062] The raw materials for preparing the toughening polymer component include lactide, 4-diaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid, isoprene and benzothiazole. The specific preparation steps are as follows:

[0063] Step 1, 5g of lactide and 60mL of toluene are poured into a flask, 0.2g of benzyl alcohol and 0.04g of stannous octoate are added under a nitrogen atmosphere, nitrogen is introduced for 15min, the mixture is sealed and placed in an oil bath at 130°C and stirred at a stirring speed of 200r / min for 24h, 50mL of dichloromethane is added after the reaction is completed and stirred at a stirring speed of 300r / min for 10min, anhydrous ethanol is dripped at a dripping rate of 1 drop / s, a precipitate is collected and the precipitate is placed at a temperature of 30°C and vacuum dried for 20h to obtain polylactide;

[0064] Step 2, weigh 3g of polylactide, 2g of 4-diaminopyridine, 8g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 15g of 2-(dodecyl trithiocarbonate)-2-methylpropionic acid into a flask, add 100mL of dichloromethane, stir at a stirring speed of 300r / min for 30min in a water bath at 25°C, place under reduced pressure rotary evaporation at 40°C to remove dichloromethane, and then pour into methanol for precipitation. The resulting precipitate is placed at 80°C and vacuum dried for 10h, and the resulting product is recorded as an intermediate product;

[0065] Step 3, weigh 22g of isoprene, 16g of the intermediate product, 0.6g of di-tert-butyl peroxide and 2g of benzothiazole, pour into a flask filled with 200mL of toluene, pass nitrogen for 20min, seal the flask and place it in an oil bath at 125°C and stir at a speed of 200r / min for 24h. After the reaction is completed, add it dropwise into methanol to collect the precipitate and place the precipitate at 30°C and vacuum dry it for 20h to obtain the toughened polymer component.

[0066] The flame retardant modified component is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide onto magnesium hydroxide. The specific preparation method is as follows:

[0067] Weigh 5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 9 g of silane coupling agent KH-560, mix them, stir them at a temperature of 160°C and a stirring speed of 300 r / min for 2 hours, pour them into 100 mL of anhydrous ethanol, add 12 g of magnesium hydroxide, stir them at a temperature of 120°C and a stirring speed of 200 r / min for 2 hours, filter to remove the filtrate, place it in an oven at 120°C and dry it for 2 hours, and grind it through a 200-mesh sieve to obtain a flame retardant modified component.

[0068] The modified composite filler component is prepared by modifying the composite filler component with a silane coupling agent KH-560, wherein the composite filler component is prepared by mixing nano-silicon dioxide, mica powder, nano-alumina, carbon nanotubes and nano-glass microbeads in equal weight ratios and pouring them into a ball mill for ball milling for 1 hour;

[0069] The preparation method of the modified composite filler component is:

[0070] Weigh 5g of silane coupling agent KH-560 and 200mL of anhydrous ethanol, mix them, stir at a stirring speed of 500r / min for 30min, then add 20g of composite filler component, ultrasonically disperse at a frequency of 30kHz for 30min, stir at a stirring speed of 200r / min in a water bath at 58°C until the anhydrous ethanol is completely volatilized, then place in an oven at 60°C to dry for 6h and grind through a 200-mesh sieve to obtain the modified composite filler component.

[0071] A method for preparing impact-resistant ultra-high molecular weight polyethylene fiber, the preparation method comprising:

[0072] S1, weighing 100 parts by weight of modified ultra-high molecular weight polyethylene, 20 parts by weight of toughening polymer component, 5 parts by weight of flame retardant modified component, 8 parts by weight of modified composite filler component, 2 parts by weight of silane coupling agent KH-570 and 2 parts by weight of antioxidant 1010 into an internal mixer, mixing at a temperature of 150° C. and a speed of 60 r / min for 10 min, and extruding and granulating the obtained product through a twin-screw extruder as impact-resistant ultra-high molecular weight polyethylene masterbatch;

[0073] S2. Tetralin and decalin are mixed in an equal weight ratio to prepare a solvent component, and the impact-resistant ultra-high molecular weight polyethylene masterbatch is mixed with the solvent component in a weight ratio of 15% to prepare a spinning solution, which is then extruded into filaments through a twin-screw spinning machine, and then cooled, extracted, dried and subjected to multi-stage heat drawing treatment to obtain impact-resistant ultra-high molecular weight polyethylene fibers.

[0074] In S2, the extractant is methyl chloride, the extraction time is 60 minutes, the extraction temperature is 60°C, the multi-stage drawing treatment adopts a drawing temperature of 150°C, a drawing time of 10 minutes, and a drawing multiple of 60 times.

[0075] Example 3

[0076] The impact-resistant ultra-high molecular weight polyethylene fiber of this embodiment is composed of the following components: modified ultra-high molecular weight polyethylene, a toughening polymer component, a flame retardant modified component, a modified composite filler component, a silane coupling agent KH-570 and an antioxidant 1010;

[0077] The modified ultra-high molecular weight polyethylene is obtained by grafting and modifying ultra-high molecular weight polyethylene, and the specific preparation steps are as follows:

[0078] Step A, weighing 10g of white oil, 10g of decalin, 10g of xylene and 60g of ultra-high molecular weight polyethylene into a flask, heating at an oil bath temperature of 100°C to expand the ultra-high molecular weight polyethylene, then adding 1.5g of benzoyl peroxide and 4g of maleic anhydride and reacting for 5h under nitrogen protection, the obtained product is recorded as a grafted product;

[0079] Step B, placing the grafted product in a Soxhlet extractor and extracting it with acetone for 24 hours, then drying it in an oven at 60° C. for 8 hours, and finally drying it in a vacuum drying oven to constant weight, to obtain the modified ultra-high molecular weight polyethylene.

[0080] The raw materials for preparing the toughening polymer component include lactide, 4-diaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid, isoprene and benzothiazole. The specific preparation steps are as follows:

[0081] Step 1, 5g of lactide and 60mL of toluene are poured into a flask, 0.2g of benzyl alcohol and 0.04g of stannous octoate are added under a nitrogen atmosphere, nitrogen is introduced for 15min, the mixture is sealed and placed in an oil bath at 130°C and stirred at a stirring speed of 200r / min for 24h, 50mL of dichloromethane is added after the reaction is completed and stirred at a stirring speed of 300r / min for 10min, anhydrous ethanol is dripped at a dripping rate of 1 drop / s, a precipitate is collected and the precipitate is placed at a temperature of 30°C and vacuum dried for 20h to obtain polylactide;

[0082] Step 2, weigh 3g of polylactide, 2g of 4-diaminopyridine, 8g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 15g of 2-(dodecyl trithiocarbonate)-2-methylpropionic acid into a flask, add 100mL of dichloromethane, stir at a stirring speed of 300r / min for 30min in a water bath at 25°C, place under reduced pressure rotary evaporation at 40°C to remove dichloromethane, and then pour into methanol for precipitation. The resulting precipitate is placed at 80°C and vacuum dried for 10h, and the resulting product is recorded as an intermediate product;

[0083] Step 3, weigh 22g of isoprene, 16g of the intermediate product, 0.6g of di-tert-butyl peroxide and 2g of benzothiazole, pour into a flask filled with 200mL of toluene, pass nitrogen for 20min, seal the flask and place it in an oil bath at 125°C and stir at a speed of 200r / min for 24h. After the reaction is completed, add it dropwise into methanol to collect the precipitate and place the precipitate at 30°C and vacuum dry it for 20h to obtain the toughened polymer component.

[0084] The flame retardant modified component is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide onto magnesium hydroxide. The specific preparation method is as follows:

[0085] Weigh 5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 9 g of silane coupling agent KH-560, mix them, stir them at a temperature of 160°C and a stirring speed of 300 r / min for 2 hours, pour them into 100 mL of anhydrous ethanol, add 12 g of magnesium hydroxide, stir them at a temperature of 120°C and a stirring speed of 200 r / min for 2 hours, filter to remove the filtrate, place it in an oven at 120°C and dry it for 2 hours, and grind it through a 200-mesh sieve to obtain a flame retardant modified component.

[0086] The modified composite filler component is prepared by modifying the composite filler component with a silane coupling agent KH-560, wherein the composite filler component is prepared by mixing nano-silicon dioxide, mica powder, nano-alumina, carbon nanotubes and nano-glass microbeads in equal weight ratios and pouring them into a ball mill for ball milling for 1 hour;

[0087] The preparation method of the modified composite filler component is:

[0088] Weigh 5g of silane coupling agent KH-560 and 200mL of anhydrous ethanol, mix them, stir at a stirring speed of 500r / min for 30min, then add 18g of composite filler component, ultrasonically disperse at a frequency of 30kHz for 30min, stir at a stirring speed of 200r / min in a water bath at 58°C until the anhydrous ethanol is completely volatilized, then place in an oven at 60°C to dry for 6h and grind through a 200-mesh sieve to obtain the modified composite filler component.

[0089] A method for preparing impact-resistant ultra-high molecular weight polyethylene fiber, the preparation method comprising:

[0090] S1, weighing 100 parts by weight of modified ultra-high molecular weight polyethylene, 18 parts by weight of toughening polymer component, 4 parts by weight of flame retardant modified component, 6 parts by weight of modified composite filler component, 2 parts by weight of silane coupling agent KH-570 and 2 parts by weight of antioxidant 1010 into an internal mixer, mixing at a temperature of 145° C. and a speed of 60 r / min for 10 min, and extruding and granulating the obtained product through a twin-screw extruder as impact-resistant ultra-high molecular weight polyethylene masterbatch;

[0091] S2. Tetralin and decalin are mixed in an equal weight ratio to prepare a solvent component, and the impact-resistant ultra-high molecular weight polyethylene masterbatch is mixed with the solvent component in a weight ratio of 12% to prepare a spinning solution, which is then extruded into filaments through a twin-screw spinning machine, and then cooled, extracted, dried and subjected to multi-stage heat drawing treatment to obtain impact-resistant ultra-high molecular weight polyethylene fibers.

[0092] In S2, the extractant is chloroform, the extraction time is 45 minutes, the extraction temperature is 55°C, the multi-stage drawing treatment adopts a drawing temperature of 15°C, a drawing time of 8 minutes, and a drawing multiple of 45 times.

[0093] Comparative Example 1

[0094] The impact-resistant ultra-high molecular weight polyethylene fiber and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 1, the modified ultra-high molecular weight polyethylene in Example 1 is replaced with ultra-high molecular weight polyethylene.

[0095] Comparative Example 2

[0096] The impact-resistant ultra-high molecular weight polyethylene fiber and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 2, the toughening polymer component in Example 1 is replaced by the modified ultra-high molecular weight polyethylene in Example 1.

[0097] Comparative Example 3

[0098] The impact-resistant ultra-high molecular weight polyethylene fiber and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 3, the modified composite filler component in Example 1 is replaced by the composite filler component in Example 1.

[0099] Comparative Example 4

[0100] The impact-resistant ultra-high molecular weight polyethylene fiber and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 4, the flame-retardant modified component in Example 1 is replaced with magnesium hydroxide.

[0101] Performance Testing

[0102] 1. The impact strength of the impact-resistant ultra-high molecular weight polyethylene masterbatch prepared in Examples 1-3 and Comparative Examples 1-4 was tested using an XJJD-50 electronic simply supported beam impact tester according to GB / T21461-2008 "Plastic Ultra-High Molecular Weight Polyethylene (PE-UHMW) Molding and Extrusion Materials" standard, and the obtained data are recorded in Table 1;

[0103] 2. The tensile strength and elongation at break of the impact-resistant ultra-high molecular weight polyethylene masterbatch prepared in Examples 1-3 and Comparative Examples 1-4 were tested using a CMT6104 electronic universal testing machine according to GB / T1040-2018 "Determination of Tensile Properties of Plastics" standard, and the obtained data are recorded in Table 1;

[0104] 3. The limiting oxygen index of the impact-resistant ultra-high molecular weight polyethylene masterbatch prepared in Examples 1-3 and Comparative Examples 1-4 was tested with reference to the standard of GB / T2406.2-2009, and the obtained data are recorded in Table 1;

[0105] 4. The fiber strength, modulus and elongation at break of the impact-resistant ultra-high molecular weight polyethylene fibers prepared in Examples 1-3 and Comparative Examples 1-4 were tested with reference to GB / T19975-2005 standard, and the obtained data are recorded in Table 2;

[0106] Table 1

[0107]

[0108]

[0109] Table 2

[0110]

[0111] It can be seen from the data in the above table that the mechanical properties of the impact-resistant ultrahigh molecular weight polyethylene masterbatch in Examples 1-3 are significantly better than those in Comparative Examples 1-3, indicating that the modified ultrahigh molecular weight polyethylene, toughening polymer component and modified composite filler component added in the preparation process can play a role in improving the mechanical properties, and the flame retardant properties of the impact-resistant ultrahigh molecular weight polyethylene masterbatch in Examples 1-3 are significantly better than those in Comparative Example 4, indicating that the flame retardant effect of the flame retardant modified component in the present invention is better than that of a single magnesium hydroxide; secondly, the comprehensive performance of the impact-resistant ultrahigh molecular weight polyethylene fiber prepared in Examples 1-3 of the present invention is also better than that in Comparative Examples 1-4, indicating that the method for preparing the impact-resistant ultrahigh molecular weight polyethylene fiber provided by the present invention has better application prospects.

[0112] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0113] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An impact-resistant ultra-high molecular weight polyethylene fiber, characterized in that: The impact-resistant ultra-high molecular weight polyethylene fiber is composed of the following components: modified ultra-high molecular weight polyethylene, a toughening polymer component, a flame retardant modified component, a modified composite filler component, a silane coupling agent KH-570 and an antioxidant 1010; The modified ultra-high molecular weight polyethylene is obtained by grafting and modifying ultra-high molecular weight polyethylene; The raw materials for preparing the toughening polymer component include lactide, 4-diaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 2-(dodecyl trithiocarbonate)-2-methylpropionic acid, isoprene and benzothiazole; The flame retardant modified component is prepared by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide onto magnesium hydroxide; The modified composite filler component is prepared by modifying the composite filler component with a silane coupling agent KH-560.

2. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The preparation steps of the modified ultra-high molecular weight polyethylene are: Step A, weighing 10g of white oil, 10g of decalin, 10g of xylene and 60g of ultra-high molecular weight polyethylene into a flask, heating at an oil bath temperature of 100°C to expand the ultra-high molecular weight polyethylene, then adding 1.5g of benzoyl peroxide and 4g of maleic anhydride and reacting for 5h under nitrogen protection, the obtained product is recorded as a grafted product; Step B, placing the grafted product in a Soxhlet extractor and extracting it with acetone for 24 hours, then drying it in an oven at 60° C. for 8 hours, and finally drying it in a vacuum drying oven to constant weight, to obtain the modified ultra-high molecular weight polyethylene.

3. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The preparation steps of the toughening polymer component are: Step 1, pour 5g of lactide and 60mL of toluene into a flask, add 0.2g of benzyl alcohol and 0.04g of stannous octoate under a nitrogen atmosphere, pass nitrogen for 15min, seal and place in an oil bath at 130°C for stirring reaction, add 50mL of dichloromethane after the reaction is completed, mix evenly, drop into anhydrous ethanol to collect the precipitate and place the precipitate at 30°C under vacuum and dry for 20h, the resulting polylactide; Step 2, weigh 3g of polylactide, 2g of 4-diaminopyridine, 8g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 15g of 2-(dodecyl trithiocarbonate)-2-methylpropionic acid into a flask, add 100mL of dichloromethane and stir evenly in a water bath at 25°C, place under reduced pressure rotary evaporation at 40°C to remove dichloromethane and pour into methanol for precipitation, and the resulting precipitate is placed under vacuum drying at 80°C for 10h, and the resulting product is recorded as an intermediate product; Step 3: weigh 22 g of isoprene, 16 g of the intermediate product, 0.6 g of di-tert-butyl peroxide and 2 g of benzothiazole, pour them into a flask filled with 200 mL of toluene, pass nitrogen for 20 min, seal the flask and place it in an oil bath at 125°C for stirring and reaction. After the reaction is completed, add it dropwise into methanol to collect the precipitate and place the precipitate at 30°C for vacuum drying for 20 hours to obtain the toughened polymer component.

4. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 3, characterized in that: The specific operation of stirring the reaction in step 1 is stirring at a stirring speed of 200 r / min for 24 hours, the specific operation of mixing evenly in step 1 is stirring at a stirring speed of 300 r / min for 10 minutes, and the dripping rate in step 1 is 1 drop / s.

5. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 3, characterized in that: The specific operation of stirring uniformly in step 2 is stirring at a stirring speed of 300 r / min for 30 min, and the specific operation of stirring the reaction in step 3 is stirring at a stirring speed of 200 r / min for 24 h.

6. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The preparation method of the flame retardant modified component is: Weigh 5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 9 g of silane coupling agent KH-560, mix them, stir them at a temperature of 160°C and a stirring speed of 300 r / min for 2 hours, pour them into 100 mL of anhydrous ethanol, add 12 g of magnesium hydroxide, stir them at a temperature of 120°C and a stirring speed of 200 r / min for 2 hours, filter to remove the filtrate, place it in an oven at 120°C and dry it for 2 hours, and grind it through a 200-mesh sieve to obtain a flame retardant modified component.

7. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The composite filler components are prepared by mixing nano silicon dioxide, mica powder, nano aluminum oxide, carbon nanotubes and nano glass microbeads in equal weight ratios and pouring the mixture into a ball mill for ball milling for 1 hour.

8. The impact-resistant ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The preparation method of the modified composite filler component is: Weigh 5g of silane coupling agent KH-560 and 200mL of anhydrous ethanol, mix them, stir at a stirring speed of 500r / min for 30min, then add 15-20g of composite filler component, ultrasonically disperse at a frequency of 30kHz for 30min, stir at a stirring speed of 200r / min in a water bath at 58°C until the anhydrous ethanol is completely volatilized, then place in an oven at 60°C to dry for 6h and grind through a 200-mesh sieve to obtain the modified composite filler component.

9. The method for preparing an impact-resistant ultra-high molecular weight polyethylene fiber according to any one of claims 1 to 8, characterized in that: The preparation method is: S1, weighing 100 parts by weight of modified ultra-high molecular weight polyethylene, 15-20 parts by weight of toughening polymer component, 3-5 parts by weight of flame retardant modified component, 5-8 parts by weight of modified composite filler component, 1-2 parts by weight of silane coupling agent KH-570 and 1-2 parts by weight of antioxidant 1010 into an internal mixer, mixing at a temperature of 140-150° C. and a speed of 60 r / min for 10 min, and extruding and granulating the mixture through a twin-screw extruder to obtain an impact-resistant ultra-high molecular weight polyethylene masterbatch; S2. Tetralin and decalin are mixed in an equal weight ratio to prepare a solvent component, and the impact-resistant ultra-high molecular weight polyethylene masterbatch is mixed with the solvent component in a weight ratio of 10-15% to prepare a spinning solution, which is then extruded into filaments through a twin-screw spinning machine, and then cooled, extracted, dried and subjected to multi-stage heat drawing treatment to obtain impact-resistant ultra-high molecular weight polyethylene fibers.

10. The method for preparing an impact-resistant ultra-high molecular weight polyethylene fiber according to claim 9, characterized in that: In S2, the extractant is any one of toluene, methyl chloride, dichloromethane, chloroform and carbon tetrachloride or a combination of two or more thereof, the extraction time is 30-60 min, the extraction temperature is 50-60°C, the multi-stage stretching treatment adopts a stretching temperature of 120-150°C, a stretching time of 5-10 min, and a stretching multiple of 30-60 times.

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