An ultra-high molecular weight polyethylene fiber and a method for preparing and using the same

Abstract

The application provides an ultra-high molecular weight polyethylene fiber and a preparation method and application thereof, and the preparation method comprises the following steps: (1) mixing an ultra-high molecular weight polyethylene resin with a first solvent to obtain a spinning solution; (2) the spinning solution is subjected to swelling and dissolution in sequence to obtain a uniform solution; (3) the uniform solution is subjected to spinning and cooling in sequence to obtain a gel primary filament; (4) the gel primary filament is placed in a dispersion liquid to be extracted to obtain a modified gel primary filament; the dispersion liquid comprises a combination of a photo-initiator modified inorganic nano-particle, a cross-linking agent and a second solvent; (5) the modified gel primary filament is subjected to drawing and cross-linking reaction in sequence to obtain the ultra-high molecular weight polyethylene fiber. By using the preparation method provided by the application, the inorganic nano-particle and the polyethylene chain can be linked through a covalent bond, and a cross-linking network structure is formed between the polyethylene chains to some extent, so that the anti-creep performance of the ultra-high molecular weight polyethylene fiber can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials, and particularly relates to an ultrahigh molecular weight polyethylene fiber and a preparation method and application thereof. BACKGROUND

[0002] The ultrahigh molecular weight polyethylene (UHMWPE) fiber has a molecular weight generally greater than 1 million, is a high-strength and high-modulus fiber, and is invented by the DSM Company in the Netherlands in the 1970s, and is called as one of the three high-performance fibers together with aramid fiber and carbon fiber.

[0003] The UHMWPE fiber has excellent properties of low density, high specific strength and high modulus, and has good weather resistance, ultraviolet resistance, hydrophobicity and corrosion resistance, and excellent low-temperature resistance compared with aramid fiber and carbon fiber. At present, the UHMWPE fiber is widely applied in the military field and the industrial field. In the military field, the UHMWPE fiber is mainly used for personal armed protection (such as bulletproof clothes, bulletproof helmets and the like), tank, ship and helicopter armor protection. In the industrial field, the UHMWPE fiber is mainly used for marine fabrics, fishing nets, marine ropes, cables, impact-resistant materials, containers, sports equipment, radar radomes and the like.

[0004] The UHMWPE fiber has very excellent properties, but also has many defects. This is mainly because the UHMWPE fiber is a flexible high polymer material composed of -CH2-, and the molecular chain has no polar group and no branched chain, and the interaction force between the molecular chains is small. Therefore, the UHMWPE fiber is prone to creep under long-term external force, has poor size stability, and has serious morphological deformation, which limits its application in long-term load application.

[0005] In order to improve the creep property of the UHMWPE fiber, domestic and foreign researchers have carried out modification research on the UHMWPE fiber through various methods, such as spinning with UHMWPE raw material containing branched chains, spinning with UHMWPE powder with ultrahigh molecular weight, ultraviolet light crosslinking, electron beam irradiation crosslinking, inorganic nanoparticle reinforcement, and the like, and improving the creep property of the UHMWPE fiber by increasing the interaction force between the molecular chains and reducing the chain end group defects.

[0006] CN101821436A, CN103608501A and CN108431309A adopt UHMWPE raw material containing branched chains for spinning, which improves the creep property of the material. However, the UHMWPE raw material containing branched chains is not easy to obtain, the branched chain content is not easy to control and cannot be accurately measured. In addition, the UHMWPE raw material containing branched chains also has the problem of increased viscosity in the spinning process, especially in the commonly used gel spinning process. The increased viscosity of the spinning system and the poor drawability of the gel fiber bring great difficulties to the production process, resulting in reduced production efficiency.

[0007] CN109749208A, CN109824961A, CN103572396A and the like use silicon carbide whiskers, inorganic nanoparticles, graphene, carbon nanotubes and other nanomaterials to modify UHMWPE fibers. Inorganic nanoparticles, graphene and carbon nanotubes can increase the crystallization nucleation point, improve the crystallinity, and also play the role of physical crosslinking point. However, inorganic nanoparticles, graphene and carbon nanotubes have no chemical bond with the polyethylene molecular chain, the interaction force is not strong, and the improvement effect of creep resistance is not outstanding. The prior art generally has the problem of unsatisfactory improvement effect of the creep resistance of UHMWPE fibers, and therefore it is urgent to find a new method for preparing UHMWPE fibers to effectively improve the creep resistance of UHMWPE fibers. SUMMARY

[0008] In view of the deficiencies of the prior art, the purpose of the present application is to provide a kind of ultra-high molecular weight polyethylene fiber and its preparation method and application. Through the design of raw materials and process steps, the obtained ultra-high molecular weight polyethylene fiber has excellent creep resistance.

[0009] To achieve this purpose, the present application adopts the following technical solutions:

[0010] In the first aspect, the present application provides a preparation method of an ultra-high molecular weight polyethylene fiber, which comprises the following steps:

[0011] (1) mixing an ultra-high molecular weight polyethylene resin with a first solvent to obtain a spinning solution;

[0012] (2) the spinning solution is sequentially subjected to swelling and dissolution to obtain a uniform solution;

[0013] (3) the uniform solution is sequentially subjected to spinning and cooling to obtain a gel original fiber;

[0014] (4) the gel original fiber is placed in a dispersion liquid for extraction to obtain a modified gel original fiber; the dispersion liquid comprises a combination of photo-initiator modified inorganic nanoparticles, a crosslinking agent and a second solvent;

[0015] (5) the modified gel original fiber is sequentially subjected to drawing and crosslinking reaction to obtain the ultra-high molecular weight polyethylene fiber.

[0016] In the present application, the inorganic nanoparticles are modified by a photoinitiator, a photosensitive group is introduced on the surface of the inorganic nanoparticles, the surface of the gel original filament is modified by the modified inorganic nanoparticles, and then the obtained modified gel original filament is subjected to a crosslinking reaction, so that the covalent bond linkage between the inorganic nanoparticles and the polyethylene molecular chain can be realized, and a crosslinking network structure between the polyethylene chains is formed to a certain extent. The covalent bond linkage between the polyethylene chains and the inorganic nanoparticles and the crosslinking network structure formed between the polyethylene chains can effectively prevent the mutual sliding between the polyethylene molecular chains, thereby improving the anti-creep performance of the polyethylene fiber.

[0017] The following is a preferred technical solution of the present application, but is not a limitation on the technical solutions provided by the present application. Through the following preferred technical solution, the purpose and beneficial effects of the present application can be better achieved and realized.

[0018] As a preferred technical solution, the first solvent includes any one or a combination of at least two of white oil, paraffin oil, paraffin, kerosene or soybean oil.

[0019] Preferably, the mass percentage of the ultra-high molecular weight polyethylene resin in the spinning solution is 5-15%, for example, it can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, and specific point values between the above point values. Due to the limited space and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0020] Preferably, the swelling and dissolution are carried out in a twin-screw extruder.

[0021] Preferably, the temperature of each zone of the twin-screw extruder is independently 65-310°C, for example, it can be 65°C, 70°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C or 310°C, and specific point values between the above point values. Due to the limited space and the consideration of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0022] Preferably, the length-diameter ratio of the screw of the twin-screw extruder is (40-88):1, for example, it can be 40:1, 42:1, 45:1, 48:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1 or 88:1, etc.

[0023] Preferably, the rotation speed of the twin-screw extruder is 100-300 rpm, for example, it can be 100 rpm, 120 rpm, 150 rpm, 180 rpm, 200 rpm, 220 rpm, 250 rpm, 280 rpm or 300 rpm, and specific point values between the above-mentioned point values, the present application does not list the specific point values included in the range for the sake of brevity and conciseness.

[0024] Preferably, the total length of swelling and dissolution is 3-20 min, for example, it can be 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 19 min or 20 min, and specific point values between the above-mentioned point values, the present application does not list the specific point values included in the range for the sake of brevity and conciseness.

[0025] Preferably, the diameter of the gel filament is 0.2-2 mm, for example, it can be 0.2 mm, 0.4 mm, 0.6 mm, 0.8 mm, 1 mm, 1.2 mm, 1.4 mm, 1.6 mm, 1.8 mm or 2 mm, and specific point values between the above-mentioned point values, the present application does not list the specific point values included in the range for the sake of brevity and conciseness.

[0026] Preferably, the method of cooling comprises cooling using a cold water bath.

[0027] Preferably, the temperature of the cold water bath is <20℃, for example, it can be 0.5℃, 1℃, 2℃, 3℃, 4℃, 5℃, 6℃, 7℃, 8℃, 9℃, 10℃, 11℃, 12℃, 13℃, 14℃, 15℃, 16℃, 17℃, 18℃ or 19℃, etc.

[0028] Preferably, the photo-initiator modified inorganic nanoparticles are prepared by a method comprising the following steps:

[0029] (S1) mixing the hydroxyl-containing inorganic nanoparticles, chlorinating agent and first organic solvent to perform a first reaction, to obtain chlorinated inorganic nanoparticles;

[0030] (S2) mixing the chlorinated inorganic nanoparticles, photo-initiator, catalyst and second organic solvent to perform a second reaction, to obtain the photo-initiator modified inorganic nanoparticles.

[0031] Preferably, the hydroxyl-containing inorganic nanoparticles include any one of hydroxyl-containing nano-SiO2 particles, hydroxyl-containing nano-TiO2 particles, hydroxyl-containing nano-Al2O3 particles, or hydroxyl-containing nano-ZnO particles, or a combination of at least two of them.

[0032] Preferably, the hydroxyl-containing inorganic nanoparticles have a particle size of 5-100 nm, such as 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, or 100 nm, and specific point values between the aforementioned point values. Due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range any more.

[0033] Preferably, the chlorinating agent includes any one of thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, methanesulfonyl chloride, or p-toluenesulfonyl chloride, or a combination of at least two of them.

[0034] Preferably, the first organic solvent includes any one of benzene, toluene, xylene, or n-hexane, or a combination of at least two of them.

[0035] Preferably, the mass ratio of the hydroxyl-containing inorganic nanoparticles to the chlorinating agent is 1:(5-20), such as 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20, etc.

[0036] Preferably, the volume of the first organic solvent is 5-50 mL, such as 5 mL, 10 mL, 15 mL, 20 mL, 25 mL, 30 mL, 35 mL, 40 mL, 45 mL, or 50 mL, and specific point values between the aforementioned point values, based on 1 g of the mass of the hydroxyl-containing inorganic nanoparticles. Due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range any more.

[0037] Preferably, the time of the first reaction is 10-50 h, such as 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, or 50 h, and specific point values between the aforementioned point values. Due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range any more.

[0038] Preferably, the temperature of the first reaction is 50-150°C, for example, it can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, and specific point values between the above-mentioned point values, the present application does not enumerate specific point values included in the range for the sake of brevity and consideration of the length of the article.

[0039] The first reaction is refluxed by controlling the temperature of the first reaction.

[0040] Preferably, the photoinitiator includes any one or a combination of at least two of a hydroxyl-containing photoinitiator, a carboxyl-containing photoinitiator, or an amino-containing photoinitiator.

[0041] Preferably, the hydroxyl-containing photoinitiator includes any one or a combination of at least two of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, or 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone.

[0042] Preferably, the carboxyl-containing photoinitiator includes benzophenone-4,4-dicarboxylic acid.

[0043] Preferably, the amino-containing photoinitiator includes any one or a combination of at least two of 1-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, 1,4-diaminoanthraquinone, or 1,5-diaminoanthraquinone.

[0044] Preferably, the catalyst includes any one or a combination of at least two of NaHCO3, KHCO3, or NH4HCO3.

[0045] Preferably, the second organic solvent includes any one or a combination of at least two of N,N-dimethylformamide, dimethyl sulfoxide, benzene, toluene, xylene, tetrahydrofuran, or n-hexane.

[0046] Preferably, the mass ratio of the chlorinated inorganic nanoparticles to the photoinitiator is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, etc.

[0047] Preferably, the mass ratio of the chlorinated inorganic nanoparticles to the catalyst is 1:(0.04-0.1), for example, it can be 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, or 1:0.1, etc.

[0048] Preferably, the volume of the second organic solvent is 100-200 mL, for example, can be 100 mL, 110 mL, 120 mL, 130 mL, 140 mL, 150 mL, 160 mL, 170 mL, 180 mL, 190 mL or 200 mL, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range.

[0049] Preferably, the temperature of the second reaction is 10-40℃, for example, can be 10℃, 12℃, 14℃, 15℃, 18℃, 20℃, 22℃, 25℃, 28℃, 30℃, 32℃, 35℃, 38℃ or 40℃, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range.

[0050] Preferably, the time of the second reaction is 12-24h, for example, can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range.

[0051] Preferably, the mass percentage content of the photoinitiator in the photoinitiator modified inorganic nanoparticles is 3-20%, for example, can be 3%, 4%, 5%, 6%, 7%, 8%, 10%, 12%, 15%, 16%, 18% or 20%, and specific point values between the above-mentioned point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range.

[0052] Preferably, the crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, trimethylolpropane triacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, dicumyl peroxide or benzoyl peroxide.

[0053] Preferably, the second solvent includes any one or a combination of at least two of dichloromethane, toluene, xylene, gasoline, n-hexane, petroleum ether, carbon tetrachloride or 1,2-dichloroethane.

[0054] Preferably, the mass ratio of the photoinitiator modified inorganic nanoparticles to the crosslinking agent is (1-10):1, for example, can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0055] Preferably, the mass of the photo-initiator modified inorganic nanoparticles is 1-20% based on 100% of the mass of the dispersion, for example, can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, and the specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0056] Preferably, the mass of the crosslinking agent is 0.5-20% based on 100% of the mass of the dispersion, for example, can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, and the specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0057] Preferably, the extraction time is 1-20 min, for example, can be 1 min, 2 min, 4 min, 6 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, or 20 min, and the specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0058] Preferably, the mass ratio of the dispersion to the gel original wire is (10-500): 1, for example, can be 10:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, or 500:1, etc.

[0059] Preferably, the extraction further comprises the step of placing the gel original wire in a third solvent for a first extraction before the extraction is performed.

[0060] Preferably, the third solvent comprises any one or a combination of at least two of dichloromethane, toluene, xylene, gasoline, n-hexane, petroleum ether, carbon tetrachloride, or 1,2-dichloroethane.

[0061] Preferably, the first extraction time is 1-5 min, for example, can be 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, or 5 min, and the specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed the specific point values included in the range.

[0062] Preferably, the mass ratio of the third solvent to the gel filaments is (50-500):1, for example, it can be 50:1, 80:1, 100:1, 120:1, 150:1, 180:1, 200:1, 220:1, 250:1, 280:1, 300:1, 350:1, 400:1, 450:1 or 500:1, etc.

[0063] Preferably, the mass percentage of the first solvent in the first gel filaments is 10-60%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%, and specific point values between the above point values, due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range.

[0064] Preferably, the draw ratio is 5-15 times, for example, it can be 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times or 15 times, and specific point values between the above point values, due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range.

[0065] Preferably, the temperature of the drawing is 135-155℃, for example, it can be 135℃, 138℃, 140℃, 146℃, 147℃, 148℃, 149℃, 150℃ or 155℃, and specific point values between the above point values, due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range.

[0066] Preferably, the cross-linking reaction is carried out under ultraviolet light irradiation.

[0067] Preferably, the irradiation time is 1-30min, for example, it can be 1min, 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, and specific point values between the above point values, due to the limitation of the length and for the sake of simplicity, the present application will not list the specific point values included in the range.

[0068] Preferably, the preparation method specifically comprises the following steps:

[0069] (1) mixing the ultra-high molecular weight polyethylene resin with the first solvent to obtain a spinning solution;

[0070] The mass percentage of the ultra-high molecular weight polyethylene resin in the spinning solution is 5-15%;

[0071] (2) the spinning solution is sequentially subjected to swelling and dissolution in a twin-screw extruder to obtain a uniform solution;

[0072] The temperature of each zone of the twin-screw extruder is independently 65-310°C;

[0073] The length-diameter ratio of the screw of the twin-screw extruder is (40-88):1;

[0074] The rotation speed of the twin-screw extruder is 100-300 rpm;

[0075] The total time length of the swelling and dissolution is 3-20 min;

[0076] (3) the uniform solution is subjected to spinning and then cooled in a cold water bath to obtain a frozen gel original fiber;

[0077] The diameter of the frozen gel original fiber is 0.2-2 mm;

[0078] The temperature of the cold water bath is <20°C;

[0079] (4) the frozen gel original fiber is placed in a third solvent to perform a first extraction to obtain a first frozen gel original fiber, and the first frozen gel original fiber is placed in a dispersion liquid to perform an extraction to obtain a modified frozen gel original fiber; the dispersion liquid comprises a combination of a photo-initiator modified inorganic nano-particle, a cross-linking agent and a second solvent;

[0080] The time of the first extraction is 1-5 min;

[0081] The mass ratio of the third solvent to the frozen gel original fiber is (50-500):1;

[0082] The mass percentage content of the first solvent in the first frozen gel original fiber is 10-60%;

[0083] The time of the extraction is 1-20 min;

[0084] The mass ratio of the dispersion liquid to the frozen gel original fiber is (10-500):1;

[0085] In the photo-initiator modified inorganic nano-particle, the mass percentage content of the photo-initiator is 3-20%;

[0086] The mass ratio of the photo-initiator modified inorganic nano-particle to the cross-linking agent is (1-10):1;

[0087] Taking the mass of the dispersion liquid as 100%, the mass of the photo-initiator modified inorganic nano-particle is 1-20%, and the mass of the cross-linking agent is 0.5-20%;

[0088] (5) drawing the modified gel filaments, and then performing a cross-linking reaction under irradiation of ultraviolet light to obtain the ultra-high molecular weight polyethylene fiber;

[0089] The temperature of the drawing is 135-155 DEG C.

[0090] The draw ratio is 5-15 times.

[0091] The irradiation time is 1-30 min.

[0092] In the second aspect, the present application provides an ultra-high molecular weight polyethylene fiber prepared by the preparation method of the first aspect. The viscosity average molecular weight of the ultra-high molecular weight polyethylene fiber is 1.5-12 million.

[0093] The ultra-high molecular weight polyethylene fiber prepared by the preparation method of the present application is composed of inorganic nano-particles and polyethylene, and the polyethylene and the inorganic nano-particles are linked by chemical bonds. A part of the polyethylene is cross-linked, and a part of the polyethylene has a crystalline structure. The content of the cross-linked polyethylene is represented by the gel content.

[0094] In the third aspect, the present application provides an application of the ultra-high molecular weight polyethylene fiber of the second aspect. The ultra-high molecular weight polyethylene fiber is applied in military materials or industrial materials.

[0095] Compared with the prior art, the present application has the following beneficial effects:

[0096] The preparation method of the ultra-high molecular weight polyethylene fiber of the present application can realize covalent bond linking between the inorganic nano-particles and the polyethylene molecular chain, and meanwhile, a cross-linking network structure is formed between the polyethylene chains to effectively improve the creep resistance of the ultra-high molecular weight polyethylene fiber. Under the condition that the load is 20% of the fiber breaking force, and the test temperature is 25 DEG C, the creep rate is 2.69-10.82% / year, and the creep rate is 0.265-1.067%. The preparation method of the ultra-high molecular weight polyethylene fiber of the present application has the following advantages: the breaking strength of the ultra-high molecular weight polyethylene fiber prepared by the preparation method is 30.67-32.13 cN / dtex, the modulus is 1100-1225 cN / dtex, the elongation at break is 2.79-3.17%, and the gel content is 12.1-23.6%. BRIEF DESCRIPTION OF DRAWINGS

[0097] Figure 1 is a comparison chart of infrared absorption spectra of the nano-SiO2 particles and SiO2-2959 in Preparation Example 1;

[0098] Figure 2is an infrared absorption spectrum of the residue and eluate of the ultra-high molecular weight polyethylene fiber provided in Example 1 after xylene treatment. DETAILED DESCRIPTION

[0099] The technical solutions of the present application are further illustrated below in conjunction with the drawings and through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations on the present application.

[0100] Some components in the examples and comparative examples are derived as follows:

[0101] Preparation Example 1

[0102] A 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone modified nano-SiO2 particle and a preparation method thereof, the preparation method comprising the following steps:

[0103] (S1) 1 g of a hydroxyl-containing nano-SiO2 particle (particle size of 10 nm) and 10 g of sulfurous chloride were poured into a reaction bottle, 10 mL of benzene was added, and the reaction was carried out at 80°C for 24 h to obtain chlorinated nano-SiO2 particles;

[0104] (S2) 1 g of the chlorinated nano-SiO2 particles, 1.5 g of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 0.05 g of NaHCO3, and 150 mL of N,N-dimethylformamide were mixed, stirred at 30°C, and reacted in the dark for 16 h, then filtered and washed, and dried to obtain the 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone modified nano-SiO2 particle, named SiO2-2959, which was stored in the dark for later use; the mass percentage content of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone in the SiO2-2959 was 19.5%.

[0105] Infrared absorption spectrum characterization: an infrared spectrometer (manufacturer: ThermoFisher Company, model: iZ10) was used to characterize and analyze the infrared absorption spectra of the nano-SiO2 particles and the SiO2-2959, respectively, and the spectra are as follows Figure 1 The infrared absorption spectra of the nano-SiO2 particles and the SiO2-2959 are shown in the following figure, wherein Figure 1 It can be seen that the SiO2-2959 has benzene ring vibration peaks at 1600 cm -1 , 1456 cm -1 , and 1418 cm -1 , a C=O vibration peak at 1662 cm -1 , and a C-O vibration peak at 1375 cm -1The methyl vibration peak appeared, which indicated that the photoinitiator 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone reacted with the surface of the nano-SiO2 particles, and the photoinitiator group was introduced onto the surface of the nano-SiO2 particles.

[0106] Preparation Example 2

[0107] A kind of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone modified nano-TiO2 particles and its preparation method, only difference from preparation example 1 is that replace hydroxyl-containing nano-SiO2 particles with equivalent hydroxyl-containing nano-TiO2 particles, other raw materials, process parameters and steps are same with preparation example 1, obtain the 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone modified nano-TiO2 particles, named TiO2-2959, keep in dark for standby use;2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone in the TiO2-2959, mass percentage content is 18.7%.

[0108] Preparation Example 3

[0109] A kind of benzophenone-4,4-dicarboxylic acid modified nano-SiO2 particles and its preparation method, only difference from preparation example 1 is that replace 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone with equivalent benzophenone-4,4-dicarboxylic acid, other raw materials, process parameters and steps are same with preparation example 1, obtain the benzophenone-4,4-dicarboxylic acid modified nano-SiO2 particles, named SiO2-BPDA, keep in dark for standby use;Benzophenone-4,4-dicarboxylic acid in the SiO2-BPDA, mass percentage content is 15.4%.

[0110] Preparation Example 4

[0111] A kind of 1-aminoanthraquinone modified nano-SiO2 particles and its preparation method, only difference from preparation example 1 is that replace 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) phenyl]-1-propanone with equivalent 1-aminoanthraquinone, other raw materials, process parameters and steps are same with preparation example 1, obtain the 1-aminoanthraquinone modified nano-SiO2 particles, named SiO2-AA, keep in dark for standby use;1-aminoanthraquinone in the SiO2-AA, mass percentage content is 12.7%.

[0112] Example 1

[0113] An ultrahigh molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0114] (1) 5 kg of ultra-high molecular weight polyethylene resin is mixed with 45 kg of white oil to obtain a spinning solution;

[0115] (2) A twin-screw extruder (screw length-diameter ratio of 64:1) is divided into 16 temperature zones, with the temperature set at 65°C, 180°C, 200°C, 220°C, 220°C, 240°C, 240°C, 260°C, 260°C, 280°C, 280°C, 300°C, 300°C, 280°C, 260°C, and 250°C, respectively. After the temperature reaches the preset value and stabilizes, the twin-screw extruder is started, and the rotation speed of the twin-screw extruder is adjusted to 150 rpm. The spinning solution is added to the twin-screw extruder through a feeding system, and swelling and dissolution are performed in sequence. After 10 minutes, a uniform solution is obtained;

[0116] (3) The uniform solution is spun through a spinning pack and then rapidly cooled in a 10°C cold water bath to obtain a gel original yarn. The diameter of the gel original yarn is 0.8 mm;

[0117] (4) 50 g of SiO2-2959, 25 g of triallyl isocyanurate, and 925 g of dichloromethane are mixed to obtain a dispersion liquid. 500 g of the gel original yarn is placed in 100 kg of dichloromethane and extracted for 2 minutes to obtain a first gel original yarn, and the mass percentage of white oil in the first gel original yarn is 10%. The first gel original yarn is placed in the dispersion liquid and extracted for 5 minutes and then dried to obtain a modified gel original yarn;

[0118] (5) The modified gel original yarn is placed in a hot oven and subjected to three-stage drawing at 150°C with a draw ratio of 6, and then subjected to a crosslinking reaction under ultraviolet light irradiation for 10 minutes to obtain the ultra-high molecular weight polyethylene fiber.

[0119] Example 2

[0120] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0121] (1) 5 kg of ultra-high molecular weight polyethylene resin is mixed with 45 kg of white oil to obtain a spinning solution;

[0122] (2) A twin-screw extruder (screw length-diameter ratio of 64:1) is divided into 16 temperature zones, with the temperature set at 65°C, 180°C, 200°C, 220°C, 220°C, 240°C, 240°C, 260°C, 260°C, 280°C, 280°C, 300°C, 300°C, 280°C, 260°C, and 250°C, respectively. After the temperature reaches the preset value and stabilizes, the twin-screw extruder is started, and the rotation speed of the twin-screw extruder is adjusted to 150 rpm. The spinning solution is added to the twin-screw extruder through a feeding system, and swelling and dissolution are performed in sequence. After 10 minutes, a uniform solution is obtained;

[0123] (3) the uniform solution is jetted through a spinning pack and then quenched in a 10°C cold water bath to obtain a frozen gelatinous fiber; the diameter of the frozen gelatinous fiber is 0.8 mm;

[0124] (4) 50 g of SiO2-2959, 50 g of triallyl isocyanurate and 900 g of dichloromethane are mixed to obtain a dispersion liquid; 500 g of the frozen gelatinous fiber is placed in 75 kg of dichloromethane and extracted for 3 min to obtain a first frozen gelatinous fiber, the mass percentage of white oil in the first frozen gelatinous fiber is 10%; the first frozen gelatinous fiber is placed in the dispersion liquid, extracted for 2 min and then dried to obtain a modified frozen gelatinous fiber;

[0125] (5) the modified frozen gelatinous fiber is placed in a hot oven, drawn by 6 times at 150°C, and then subjected to a crosslinking reaction under ultraviolet light irradiation for 15 min to obtain the ultra-high molecular weight polyethylene fiber.

[0126] Example 3

[0127] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0128] (1) 5 kg of ultra-high molecular weight polyethylene resin is mixed with 45 kg of white oil to obtain a spinning solution;

[0129] (2) a twin-screw extruder (screw length-diameter ratio is 64:1) has 16 temperature zones, the temperatures are set as 65°C, 180°C, 200°C, 220°C, 220°C, 240°C, 240°C, 260°C, 260°C, 280°C, 280°C, 300°C, 300°C, 280°C, 260°C and 250°C respectively, after the temperature reaches the preset value and is stable, the twin-screw extruder is started, the rotation speed of the twin-screw extruder is adjusted to 150 rpm, the spinning solution is added into the twin-screw extruder through a feeding system, and swelling and dissolution are sequentially performed, and 10 min later a uniform solution is obtained;

[0130] (3) the uniform solution is jetted through a spinning pack and then quenched in a 10°C cold water bath to obtain a frozen gelatinous fiber; the diameter of the frozen gelatinous fiber is 0.8 mm;

[0131] (4) 50 g of TiO2-2959, 25 g of triallyl isocyanurate and 925 g of dichloromethane are mixed to obtain a dispersion liquid; 500 g of the frozen gelatinous fiber is placed in 150 kg of dichloromethane and extracted for 1 min to obtain a first frozen gelatinous fiber, the mass percentage of white oil in the first frozen gelatinous fiber is 10%; the first frozen gelatinous fiber is placed in the dispersion liquid, extracted for 2 min and then dried to obtain a modified frozen gelatinous fiber;

[0132] (5) the modified gel original wire is placed into a hot oven, three-stage drawing is carried out at 150 DEG C, the drawing multiple is 6 times, then crosslinking reaction is carried out under ultraviolet light irradiation for 10 min, the ultrahigh molecular weight polyethylene fiber is obtained.

[0133] Example 4

[0134] An ultrahigh molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0135] (1) 5 kg of ultrahigh molecular weight polyethylene resin is mixed with 45 kg of white oil to obtain a spinning solution;

[0136] (2) the temperature of a double-screw extruder (screw length-diameter ratio is 64:1) is divided into 16 sections, and the temperature is set to 65 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 220 DEG C, 240 DEG C, 240 DEG C, 260 DEG C, 260 DEG C, 280 DEG C, 280 DEG C, 300 DEG C, 300 DEG C, 280 DEG C, 260 DEG C, and 250 DEG C respectively, the double-screw extruder is started after the temperature reaches the preset value and is stable, the rotating speed of the double-screw extruder is adjusted to 150 rpm, the spinning solution is added into the double-screw extruder through a feeding system, and swelling and dissolution are sequentially carried out, and a uniform solution is obtained after 10 min;

[0137] (3) the uniform solution is jetted through a spinning pack and is rapidly cooled in a 10 DEG C cold water bath to obtain a gel original wire; the diameter of the gel original wire is 0.8 mm;

[0138] (4) 50 g of TiO2-2959, 50 g of triallyl isocyanurate and 900 g of dichloromethane are mixed to obtain a dispersion liquid; 500 g of the gel original wire is placed in 50 kg of dichloromethane, and extraction is carried out for 1 min to obtain a first gel original wire, the mass percentage content of white oil in the first gel original wire is 18%; the first gel original wire is placed into the dispersion liquid, and extraction is carried out for 2 min and then dried to obtain a modified gel original wire;

[0139] (5) the modified gel original wire is placed into a hot oven, three-stage drawing is carried out at 150 DEG C, the drawing multiple is 6 times, then crosslinking reaction is carried out under ultraviolet light irradiation for 10 min, the ultrahigh molecular weight polyethylene fiber is obtained.

[0140] Example 5

[0141] An ultrahigh molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0142] (1) 4 kg of ultrahigh molecular weight polyethylene resin is mixed with 46 kg of white oil to obtain a spinning solution;

[0143] (2) a twin-screw extruder (screw length-diameter ratio of 64:1) is divided into 16 temperature zones, and the temperatures are set to 65°C, 180°C, 200°C, 220°C, 220°C, 240°C, 240°C, 260°C, 260°C, 280°C, 280°C, 300°C, 300°C, 280°C, 260°C, and 250°C, respectively; after the temperature reaches the preset value and is stable, the twin-screw extruder is started, the rotating speed of the twin-screw extruder is adjusted to 150 rpm, the spinning solution is added into the twin-screw extruder through a feeding system, and swelling and dissolution are sequentially performed, and an even solution is obtained after 10 minutes;

[0144] (3) the even solution is jetted through a jetting assembly and then rapidly cooled in a 10°C cold water bath to obtain a gel original fiber; the diameter of the gel original fiber is 0.8 mm;

[0145] (4) 50g of SiO2-BPDA, 25g of trimethylolpropane triacrylate, and 925g of dichloromethane are mixed to obtain a dispersion liquid; 500g of the gel original fiber is placed in 100kg of dichloromethane, and extraction is performed for 2 minutes to obtain a first gel original fiber, and the mass percentage content of white oil in the first gel original fiber is 10%; the first gel original fiber is placed in the dispersion liquid, and extraction is performed for 5 minutes and then dried to obtain a modified gel original fiber;

[0146] (5) the modified gel original fiber is placed in a hot oven, and tertiary drawing is performed at 150°C with a draw ratio of 8 times, and then crosslinking is performed under ultraviolet light irradiation for 10 minutes to obtain the ultra-high molecular weight polyethylene fiber.

[0147] Example 6

[0148] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, the preparation method comprising the following steps:

[0149] (1) 3kg of ultra-high molecular weight polyethylene resin is mixed with 47kg of white oil to obtain a spinning solution;

[0150] (2) a twin-screw extruder (screw length-diameter ratio of 64:1) is divided into 16 temperature zones, and the temperatures are set to 65°C, 180°C, 200°C, 220°C, 220°C, 240°C, 240°C, 260°C, 260°C, 280°C, 290°C, 300°C, 310°C, 290°C, 260°C, and 250°C, respectively; after the temperature reaches the preset value and is stable, the twin-screw extruder is started, the rotating speed of the twin-screw extruder is adjusted to 200 rpm, the spinning solution is added into the twin-screw extruder through a feeding system, and swelling and dissolution are sequentially performed, and an even solution is obtained after 8 minutes;

[0151] (3) the uniform solution is extruded through a spinneret and then quenched in a 10°C cold water bath to obtain the frozen collagen filaments; the diameter of the frozen collagen filaments is 0.8 mm;

[0152] (4) 50 g of SiO2-AA, 25 g of triallyl cyanurate and 925 g of dichloromethane are mixed to obtain a dispersion liquid; 500 g of the frozen collagen filaments are placed in 100 kg of dichloromethane and extracted for 1 min to obtain first frozen collagen filaments, the mass percentage of white oil in the first frozen collagen filaments is 20%; the first frozen collagen filaments are placed in the dispersion liquid, extracted for 5 min and then dried to obtain modified frozen collagen filaments;

[0153] (5) the modified frozen collagen filaments are placed in a hot oven, drawn by 10 times at 150°C, and then subjected to a crosslinking reaction under ultraviolet light irradiation for 10 min to obtain the ultra-high molecular weight polyethylene fiber.

[0154] Comparative Example 1

[0155] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, which are different from Example 1 only in that 500 g of the frozen collagen filaments are placed in 150 kg of dichloromethane and extracted for 10 min to obtain frozen collagen filaments in step (4); no crosslinking reaction is performed in step (5); and other raw materials, process parameters and steps are the same as those in Example 1, to obtain the ultra-high molecular weight polyethylene fiber.

[0156] Comparative Example 2

[0157] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, which are different from Example 1 in that 52 g of nano-SiO2 particles and 948 g of dichloromethane are mixed to obtain a dispersion liquid in step (4); no crosslinking reaction is performed in step (5); and other raw materials, process parameters and steps are the same as those in Example 1, to obtain the ultra-high molecular weight polyethylene fiber.

[0158] Comparative Example 3

[0159] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, which are different from Example 1 in that 10 g of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 25 g of triallyl isocyanurate and 965 g of dichloromethane are mixed to obtain a dispersion liquid in step (4); and other raw materials, process parameters and steps are the same as those in Example 1, to obtain the ultra-high molecular weight polyethylene fiber.

[0160] Comparative Example 4

[0161] An ultra-high molecular weight polyethylene fiber and a preparation method thereof, which is different from example 1 in that 10 g of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 52 g of nano-SiO2 particles, 25 g of triallyl isocyanurate and 913 g of dichloromethane are mixed to obtain a dispersion liquid in step (4); the other raw materials, process parameters and steps are the same as those in example 1, and the ultra-high molecular weight polyethylene fiber is obtained.

[0162] Performance test:

[0163] (1) Nanoparticle content test: take a fiber sample with a mass of m1, calcine at 500 DEG C for 1 h in an air atmosphere, then weigh the remaining ash, record the mass as m2, and calculate the nanoparticle content according to the following formula: nanoparticle content (%) = 100% x m2 / m1;

[0164] (2) Mechanical test: according to GB / T19975-2005 "High-strength fiber filament tensile property test method", an electronic tensile testing machine (manufacturer: INSTRON company, model: 34SC-2 type) is used for testing;

[0165] (3) Fiber gel content test: cut a 300-mesh metal mesh into a 60 mm x 60 mm square mesh, clean it with an ultrasonic cleaner, dry it and weigh it, record the mass as W1; weigh about 0.2 g of the fiber to be tested, wrap it with the metal mesh, and weigh it, record the mass as W2; place it in a 500 mL three-necked flask, add 1% by mass of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, and add an appropriate amount of dimethylbenzene, and place it in an oil bath at a temperature of 155 DEG C for boiling extraction for 24 h, during which new extraction agent dimethylbenzene is replaced twice. Then take out the metal mesh bag and dry it in a fume hood, weigh it, record the mass as W3, then calculate the gel content of the fiber according to the following formula: gel content (%) = 100% x (W3-W1) / (W2-W1);

[0166] (4) In the above gel content test, the dissolved substance of the ultra-high molecular weight polyethylene fiber gel provided in example 1 in dimethylbenzene is subjected to methanol sedimentation treatment, the specific operation is as follows: the solution (dissolved substance) in the three-necked flask is poured into the methanol solution for sedimentation, and then the sediment is washed and dried to obtain the dissolved substance part in the ultra-high molecular weight polyethylene fiber; then the residue (gel part) in the metal mesh belt and the treated dissolved substance are respectively subjected to infrared absorption spectrum test, and the spectrum is as follows: Figure 2The infrared absorption spectrum of the residue and the eluate of the UHMWPE fiber provided by Example 1 after xylene treatment is shown in the spectrum. It can be seen from the spectrum that the eluate spectrum is a typical polyethylene characteristic absorption spectrum, and in addition to the characteristic peaks of polyethylene, C=O absorption peaks and Si-O absorption peaks appear in the residue (gel part), which indicates that the nano-SiO2 particles in the gel form a chemical bond with a high bonding force between the cross-linked structure of the polyethylene chain;

[0167] (5) Creep rate and creep rate test: at 25℃, take 1.5m of the fiber to be tested, clamp the upper and lower ends with clamps, load the size of the fiber breaking force by 20%, record the fiber length between the clamps as L0 after preloading for 15min, then keep the loading unchanged at 20% of the fiber breaking force, and start recording the time at the same time. The test time is 36 days. The fiber length between the clamps corresponding to the test time t (day) is Lt, the creep rate (%) = 100% × (Lt-L0) / L0; the creep rate (%) = 365 × [100% × (Lt-L0) / L0] / t.

[0168] The UHMWPE fibers provided by Examples 1-6 and Comparative Examples 1-4 are tested according to the above performance test method, and the test results are shown in Table 1:

[0169] Table 1

[0170]

[0171]

[0172] As can be seen from the test data in Table 1, in the UHMWPE fibers provided by Examples 1-6, part of the polyethylene chains are cross-linked, the gel content is 12.1-23.6%, and the creep rate and the creep rate are significantly reduced, and the anti-creep property is improved.

[0173] The comparison of Example 1 and Comparative Example 1 shows that Comparative Example 1 does not modify the gel fiber, and the polyethylene molecular chains are not cross-linked, resulting in a low gel content of the UHMWPE fiber, a significantly increased creep rate, and a poor anti-creep property.

[0174] As can be seen from the comparison of Example 1 and Comparative Example 2, only adding unmodified inorganic nanoparticles to the UHMWPE fiber does not chemically react with the polyethylene chain, but only a physical modification, and the improvement effect on the anti-creep property of the UHMWPE fiber is not obvious.

[0175] As can be seen from the comparison of Example 1, Comparative Example 1 and Comparative Example 3, although the anti-creep performance of the ultra-high molecular weight polyethylene fiber can be improved by adding only the photoinitiator and the crosslinking agent, the creep rate of the ultra-high molecular weight polyethylene fiber is lower when the inorganic nanoparticles are added after being modified by the photoinitiator, which indicates that the ultra-high molecular weight polyethylene fiber containing the inorganic nanoparticles, having the crosslinking structure and having the chemical bond linkage between the nanoparticles and the crosslinking structure has the more excellent anti-creep performance.

[0176] As can be seen from the comparison of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, although the anti-creep performance of the ultra-high molecular weight polyethylene fiber can be improved by adding the photoinitiator, the crosslinking agent and the nano-SiO2 particles, the creep rate of the ultra-high molecular weight polyethylene fiber is lower when the inorganic nanoparticles are added after being modified by the photoinitiator, which indicates that the ultra-high molecular weight polyethylene fiber containing the inorganic nanoparticles, having the crosslinking structure and having the chemical bond linkage between the inorganic nanoparticles and the crosslinking structure has the more excellent anti-creep performance.

[0177] The applicant declares that the detailed process equipment and process flow of the present application are illustrated by the above examples, but the present application is not limited to the above detailed process equipment and process flow, that is, it does not mean that the present application must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for producing an ultrahigh molecular weight polyethylene fiber, characterized by, The preparation method comprises the following steps: (1) mixing an ultra-high molecular weight polyethylene resin with a first solvent to obtain a spinning solution; (2) the spinning solution is subjected to swelling and dissolution in sequence to obtain a uniform solution; (3) the uniform solution is subjected to spinning and cooling in sequence to obtain a gel original yarn; (4) the gel original yarn is subjected to extraction in a dispersion liquid to obtain a modified gel original yarn; the dispersion liquid comprises a combination of a photo-initiator modified inorganic nano-particle, a cross-linking agent and a second solvent; (5) the modified gel original yarn is subjected to drawing and cross-linking reaction in sequence to obtain the ultra-high molecular weight polyethylene fiber; The preparation method of the photo-initiator modified inorganic nano-particle comprises the following steps: (S1) mixing a hydroxyl-containing inorganic nano-particle, a chlorinating agent and a first organic solvent to perform a first reaction to obtain a chlorinated inorganic nano-particle; (S2) mixing the chlorinated inorganic nano-particle, a photo-initiator, a catalyst and a second organic solvent to perform a second reaction to obtain the photo-initiator modified inorganic nano-particle; The hydroxyl-containing inorganic nano-particle comprises any one or a combination of at least two of a hydroxyl-containing nano-SiO2 particle, a hydroxyl-containing nano-TiO2 particle, a hydroxyl-containing nano-Al2O3 particle or a hydroxyl-containing nano-ZnO particle; The chlorinating agent comprises any one or a combination of at least two of thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, methanesulfonyl chloride or p-toluenesulfonyl chloride; The photo-initiator comprises any one or a combination of at least two of a hydroxyl-containing photo-initiator, a carboxyl-containing photo-initiator or an amino-containing photo-initiator.

2. The production method according to claim 1, characterized by, The first solvent comprises any one or a combination of at least two of white oil, paraffin oil, paraffin, kerosene or soybean oil.

3. The preparation method according to claim 1, characterized in that, The mass percentage content of the ultra-high molecular weight polyethylene resin in the spinning solution is 5-15%.

4. The method of claim 1, wherein, The swelling and dissolution are performed in a twin-screw extruder.

5. The production method according to claim 4, characterized by, The temperature of each zone of the twin-screw extruder is independently 65-310 ℃.

6. The preparation method according to claim 4, characterized in that, The length-diameter ratio of the screw of the twin-screw extruder is (40-88):

1.

7. The preparation method according to claim 4, characterized in that, The rotation speed of the twin-screw extruder is 100-300 rpm.

8. The method of claim 1, wherein, The total time length of the swelling and dissolution is 3-20 min.

9. The method of claim 1, wherein, The diameter of the gel original yarn is 0.2-2 mm.

10. The method of claim 1, wherein, The cooling method comprises cooling using a cold water bath.

11. The method of claim 10, wherein, The temperature of the cold water bath is <20 ℃.

12. The method of claim 1, wherein, The particle size of the hydroxyl-containing inorganic nano-particle is 5-100 nm.

13. The method of claim 1, wherein, The first organic solvent comprises any one or a combination of at least two of benzene, toluene, xylene or n-hexane.

14. The method of claim 1, wherein, The mass ratio of the hydroxyl-containing inorganic nano-particle to the chlorinating agent is 1:(5-20).

15. The method of claim 1, wherein, The volume of the first organic solvent is 5-50 mL based on 1 g of the mass of the hydroxyl-containing inorganic nano-particle.

16. The method of claim 1, wherein, The time of the first reaction is 10-50 h.

17. The method of claim 1, wherein, The temperature of the first reaction is 50-150 ℃.

18. The method of claim 1, wherein, The hydroxyl-containing photoinitiator includes any one of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone or a combination of at least two.

19. The method of claim 1, wherein, The carboxyl-containing photoinitiator includes benzophenone-4,4-dicarboxylic acid.

20. The method of claim 1, wherein, The amino-containing photoinitiator includes any one of 1-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, 1,4-diaminoanthraquinone or 1,5-diaminoanthraquinone or a combination of at least two.

21. The method of claim 1, wherein, The catalyst includes any one of NaHCO3, KHCO3 or NH4HCO3 or a combination of at least two.

22. The method of claim 1, wherein, The second organic solvent includes any one of N,N-dimethylformamide, dimethyl sulfoxide, benzene, toluene, xylene, tetrahydrofuran or n-hexane or a combination of at least two.

23. The method of claim 1, wherein, The mass ratio of the chlorinated inorganic nanoparticles to the photoinitiator is 1:(1-2).

24. The method of claim 1, wherein, The mass ratio of the chlorinated inorganic nanoparticles to the catalyst is 1:(0.04-0.1).

25. The method of claim 1, wherein, The volume of the second organic solvent is 100-200 mL, based on 1 g of the chlorinated inorganic nanoparticles.

26. The method of claim 1, wherein, The temperature of the second reaction is 10-40 ℃.

27. The method of claim 1, wherein, The time of the second reaction is 12-24 h.

28. The method of claim 1, wherein, The mass percentage of the photoinitiator in the photoinitiator-modified inorganic nanoparticles is 3-20%.

29. The method of claim 1, wherein, The crosslinking agent includes any one of triallyl isocyanurate, trimethylolpropane triacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, dicumyl peroxide or benzoyl peroxide or a combination of at least two.

30. The method of claim 1, wherein, The second solvent includes any one of dichloromethane, toluene, xylene, gasoline, n-hexane, petroleum ether, carbon tetrachloride or 1,2-dichloroethane or a combination of at least two.

31. The method of claim 1, wherein, The mass ratio of the photoinitiator-modified inorganic nanoparticles to the crosslinking agent is (1-10):

1.

32. The method of claim 1, wherein, The mass of the photoinitiator-modified inorganic nanoparticles is 1-20% and the mass of the crosslinking agent is 0.5-20%, based on 100% of the mass of the dispersion.

33. The method of claim 1, wherein, The time of the extraction is 1-20 min.

34. The method of claim 1, wherein, The mass ratio of the dispersion to the gel original filament is (10-500):

1.

35. The method of claim 1, wherein, The extraction further includes a step of placing the gel original filament in a third solvent to perform a first extraction, to obtain a first gel original filament.

36. The preparation method according to claim 35, characterized in that, The third solvent includes any one of dichloromethane, toluene, xylene, gasoline, n-hexane, petroleum ether, carbon tetrachloride or 1,2-dichloroethane or a combination of at least two.

37. The preparation method according to claim 35, characterized in that, The time of the first extraction is 1-5 min.

38. The preparation method according to claim 35, characterized in that, The mass ratio of the third solvent to the gel original filament is (50-500):

1.

39. The method of claim 35, wherein the method is performed in a single step. The mass percentage of the first solvent in the first gel original filament is 10-60%.

40. The method of claim 1, wherein, The draw ratio is 5-15 times.

41. The method of claim 1, wherein, The temperature of the draw is 135-155 ℃.

42. The method of claim 1, wherein, The crosslinking reaction is performed under ultraviolet light irradiation.

43. The method of claim 42, wherein the method is performed in a single step. The irradiation time is 1-30 min.

44. The method of any one of claims 1-43, wherein, The preparation method specifically comprises the following steps: (1) mixing the ultra-high molecular weight polyethylene resin with a first solvent to obtain a spinning solution; The mass percentage content of the ultra-high molecular weight polyethylene resin in the spinning solution is 5-15%; (2) the spinning solution is subjected to swelling and dissolution in a double-screw extruder in sequence to obtain a uniform solution; The temperature of each zone of the double-screw extruder is independently 65-310 ℃; The length-diameter ratio of the screw of the double-screw extruder is (40-88):1; The rotation speed of the double-screw extruder is 100-300 rpm; The total time length of the swelling and dissolution is 3-20 min; (3) the uniform solution is subjected to spinning and then cooled in a cold water bath to obtain a gel original fiber; The diameter of the gel original fiber is 0.2-2 mm; The temperature of the cold water bath is <20 ℃; (4) the gel original fiber is placed in a third solvent to perform first extraction to obtain a first gel original fiber, and the first gel original fiber is placed in a dispersion liquid to perform extraction to obtain a modified gel original fiber; the dispersion liquid comprises a combination of a photo-initiator modified inorganic nano-particle, a cross-linking agent and a second solvent; The first extraction time is 1-5 min; The mass ratio of the third solvent to the gel original fiber is (50-500):1; The mass percentage content of the first solvent in the first gel original fiber is 10-60%; The extraction time is 1-20 min; The mass ratio of the dispersion liquid to the gel original fiber is (10-500):1; In the photo-initiator modified inorganic nano-particle, the mass percentage content of the photo-initiator is 3-20%; The mass ratio of the photo-initiator modified inorganic nano-particle to the cross-linking agent is (1-10):1; Taking the mass of the dispersion liquid as 100%, the mass of the photo-initiator modified inorganic nano-particle is 1-20%, and the mass of the cross-linking agent is 0.5-20%; (5) the modified gel original fiber is subjected to drawing, and then subjected to cross-linking reaction under ultraviolet irradiation to obtain the ultra-high molecular weight polyethylene fiber; The drawing temperature is 135-155 ℃; The drawing multiple is 5-15 times; The irradiation time is 1-30 min.

45. An ultra-high molecular weight polyethylene fiber, characterized in that, The ultra-high molecular weight polyethylene fiber is prepared by the preparation method in any one of claims 1-44.

46. Use of the ultra-high molecular weight polyethylene fiber according to claim 45, characterized in that, The ultra-high molecular weight polyethylene fiber is applied to military materials or industrial materials.

Images