Anti-radiation ultra-high molecular weight polyethylene fiber as well as preparation method and application thereof

Abstract

The invention discloses an anti-radiation ultra-high molecular weight polyethylene fiber as well as a preparation method and application thereof, and relates to the technical field of anti-radiation materials. The preparation method comprises the following steps: spinning a spinning solution containing lead tungstate powder and ultra-high molecular weight polyethylene powder to prepare the anti-radiation ultra-high molecular weight polyethylene fiber, wherein the lead tungstate powder is the lead tungstate powder treated by dioctyl succinate sulfonate. The lead tungstate powder is introduced during preparation of the ultra-high molecular weight polyethylene fiber, so that the anti-radiation performance of the ultra-high molecular weight polyethylene fiber is greatly improved, and meanwhile, the ultra-high molecular weight polyethylene fiber also has the characteristics of softness, cutting resistance and the like, so that the ultra-high molecular weight polyethylene fiber greatly improves the wearing comfort of a user; and movement and operation are more convenient.

Description

Technical Field

[0001] The present invention relates to the technical field of radiation protection materials, and in particular to a radiation protection ultra-high molecular weight polyethylene fiber and a preparation method and application thereof. Background Art

[0002] As a clean energy, nuclear energy has the advantages of low pollution and environmental friendliness, and is also an important development direction in the world's energy sector. However, various equipment and workers used in outdoor radiographic inspection operations and other work with radiation sources are exposed to various ionizing radiations, so effective protection is necessary. Nowadays, lead has become the most important X-ray shielding material due to its large atomic number and low price, but lead oxides are toxic and will cause certain pollution to the environment.

[0003] At present, most common radiation protection gloves are also made of lead, but they are relatively thick, uncomfortable for users to wear, and inconvenient to operate. Therefore, it is urgent to solve the disadvantages of traditional radiation protection gloves such as uncomfortable wearing and inconvenient operation.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a radiation-proof ultra-high molecular weight polyethylene fiber and a preparation method and application thereof.

[0006] The present invention is achieved in that:

[0007] In a first aspect, the present invention provides a method for preparing a radiation-proof ultra-high molecular weight polyethylene fiber, comprising:

[0008] The radiation-proof ultra-high molecular weight polyethylene fiber is prepared by spinning a spinning solution containing lead tungstate powder and ultra-high molecular weight polyethylene powder; the lead tungstate powder is lead tungstate powder treated with diisooctyl succinate sulfonate.

[0009] In an optional embodiment, the preparation method of the lead tungstate powder treated with diisooctyl succinate sulfonate comprises: adding a sodium tungstate solution to a triethanolamine solution, dropping a diisooctyl succinate sulfonate solution for dispersion, adjusting the pH to 8 and then dropping a lead acetate solution, stirring the reaction to obtain a lead tungstate solution, and then drying to obtain a lead tungstate powder.

[0010] In an optional embodiment, the mass percentage concentration of triethanolamine in the triethanolamine solution is 4-6%, the concentration of sodium tungstate in the sodium tungstate solution is 0.05-0.15 mol / L, the concentration of diisooctyl succinate sulfonate in the diisooctyl succinate sulfonate solution is 0.05-0.15 mol / L, and the concentration of lead acetate in the lead acetate solution is 0.05-0.15 mol / L; the volume ratio of the triethanolamine solution, the sodium tungstate solution, the diisooctyl succinate sulfonate solution and the lead acetate solution is 1-6:950-1050:475-525:950-1050.

[0011] And / or, the particle size of the lead tungstate powder modified by diisooctyl succinate sulfonate is 0.6-0.7 μm.

[0012] In an optional embodiment, the mass ratio of the ultra-high molecular weight polyethylene powder to the lead tungstate powder is 10-15:1-2;

[0013] And / or, the spinning solution further includes solvent oil and a dispersant, and the mass ratio of the ultra-high molecular weight polyethylene powder, the solvent oil and the dispersant in the spinning solution is 10-15:170-180:0.1-0.3;

[0014] And / or, the mixing temperature of the spinning solution is 40-60° C., and the mixing time is 0.5-1 h.

[0015] In a second aspect, the present invention provides a radiation-proof ultra-high molecular weight polyethylene fiber, which is prepared by the method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber as described in any one of the aforementioned embodiments.

[0016] In a third aspect, the present invention provides the use of the radiation-proof ultra-high molecular weight polyethylene fiber as described in the aforementioned embodiment in the preparation of radiation-proof clothing fabrics or radiation-proof glove fabrics.

[0017] In a fourth aspect, the present invention provides a polyurethane radiation-proof glove, comprising a glove blank made of the radiation-proof ultra-high molecular weight polyethylene fiber as described in the aforementioned embodiment and a rubber layer impregnated on the surface of the glove blank.

[0018] In an optional embodiment, the preparation method of the glove blank comprises: preparing tungsten coated yarn from the ultra-high molecular weight polyethylene fiber, white polyester and tungsten wire, preparing spandex coated yarn from spandex and nylon, and weaving the tungsten coated yarn and the spandex coated yarn together into a glove blank; wherein the preparation method of the glove blank comprises at least one of the following features A to C;

[0019] Feature A: The tungsten coated yarn and the spandex coated yarn are knitted using the U2 weaving method of a 21-needle glove machine, wherein the tungsten coated yarn is introduced into the main yarn mouth, the spandex coated yarn is introduced into the auxiliary yarn mouth, and a 95# elastic thread is introduced into the wrist position to knit together into a glove blank;

[0020] Feature B: The fineness of the ultra-high molecular weight polyethylene fiber in the tungsten wire coated yarn is 80-120D, the fineness of the white polyester is 70-80D, and the diameter of the tungsten wire is 0.02-0.03mm;

[0021] Feature C: The fineness of the spandex in the spandex covered yarn is 15-25D, and the fineness of the nylon is 25-35D.

[0022] In an optional embodiment, the method for preparing the adhesive layer comprises: dipping the glove blank into a polyurethane emulsion containing lead tungstate powder and an aqueous polyurethane resin, and then drying the glove blank; wherein the method for preparing the adhesive layer comprises at least one of the following features D to E;

[0023] Feature D: The preparation method of the polyurethane emulsion comprises: uniformly mixing 50-100 parts of an aqueous polyurethane resin, 30-60 parts of deionized water, 0.5-1.5 parts of the lead tungstate powder, 0.1-0.2 parts of a defoaming agent, 0.05-0.08 parts of a leveling agent and 0.05-0.09 parts of an anti-sticking agent to prepare a polyurethane emulsion;

[0024] Feature E: The drying includes first drying at 75-85°C for 20-40 minutes, then drying at 95-105°C for 20-40 minutes, and then drying at 100-120°C for 60-70 minutes.

[0025] In an optional embodiment, the preparation method of the waterborne polyurethane resin comprises: heating a mixed solution of polyol, diphenylmethane diisocyanate and a catalyst to carry out a prepolymerization reaction, when the isocyanate content in the prepolymer reaches a theoretical value, stopping the reaction, cooling to 30-40° C., adding butanone to dilute, and obtaining a prepolymer terminated with an isocyanate group; subsequently adding triethylamine and dihydroxymethylpropionic acid to carry out a neutralization reaction, then adding deionized water until the solid content of the emulsion reaches 25-35wt%, continuing emulsification for 0.5-1h, adding triethylamine to carry out a chain extension reaction to remove the remaining isocyanate, and obtaining a waterborne polyurethane emulsion; and removing butanone from the waterborne polyurethane emulsion by reduced pressure distillation, maintaining the weight percentage of water in the waterborne polyurethane emulsion at 65-75%, and obtaining the waterborne polyurethane resin; wherein the preparation method of the waterborne polyurethane resin comprises at least one of the following features F to I;

[0026] Feature F: The polyol comprises at least one of polytetrahydrofuran and polyethylene glycol;

[0027] Feature G: Before the polyol reacts with the diphenylmethane diisocyanate, the polyol is subjected to vacuum dehydration treatment; the vacuum dehydration temperature is 80-100°C and the time is 0.5-1.5h.

[0028] Feature H: The mass ratio of the triethylamine to the dimethylolpropionic acid is 0.8-1:1;

[0029] Feature I: The catalyst includes at least one of dibutyltin dilaurate, stannous octoate and bismuth carboxylate.

[0030] The present invention has the following beneficial effects:

[0031] The preparation method of the radiation-proof ultra-high molecular weight polyethylene fiber provided by the present invention introduces lead tungstate powder treated with diisooctyl succinate sulfonate when preparing the ultra-high molecular weight polyethylene fiber. The diisooctyl succinate sulfonate can give the lead tungstate powder better dispersibility and wettability. The introduction of the lead tungstate powder treated with diisooctyl succinate sulfonate greatly improves the radiation-proof performance of the radiation-proof ultra-high molecular weight polyethylene fiber. At the same time, the ultra-high molecular weight polyethylene fiber also has the characteristics of being soft and resistant to cutting, and can be widely used in preparing various radiation-proof fabrics, including but not limited to radiation-proof clothing fabrics and radiation-proof glove fabrics. In particular, with respect to radiation-proof glove fabrics, the present invention also provides a polyurethane radiation-proof glove, which is woven into a glove blank using radiation-proof ultra-high molecular weight polyethylene fibers, and a rubber layer is impregnated on the surface of the glove blank, and the impregnated resin also contains lead tungstate powder. The inner glove blank and the outer impregnation layer of the prepared polyurethane radiation-proof glove both contain lead tungstate powder, so that the polyurethane radiation-proof glove not only has good radiation-proof performance, but also has properties such as softness, high strength, and anti-cutting, which greatly improves the wearing comfort of the user, and because the gloves are overall soft, the user's activities and operations are more convenient. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0033] The present invention provides a method for preparing radiation-proof ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0034] The radiation-proof ultra-high molecular weight polyethylene fiber is prepared by spinning a spinning solution containing lead tungstate powder and ultra-high molecular weight polyethylene powder, wherein the lead tungstate powder is lead tungstate powder treated with diisooctyl succinate sulfonate.

[0035] In the present invention, by introducing the lead tungstate powder treated with diisooctyl succinate sulfonate when preparing the ultra-high molecular weight polyethylene fiber, the diisooctyl succinate sulfonate can give the lead tungstate powder better dispersibility and wettability, and the introduction of the lead tungstate powder treated with diisooctyl succinate sulfonate greatly improves the radiation protection performance of the radiation-proof ultra-high molecular weight polyethylene fiber. At the same time, the ultra-high molecular weight polyethylene fiber also has the characteristics of being soft and resistant to cutting, and can be widely used in the preparation of various radiation-proof fabrics, including but not limited to radiation-proof clothing fabrics and radiation-proof glove fabrics.

[0036] Specifically, the method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber provided by the present invention comprises the following steps:

[0037] S1. A method for preparing lead tungstate powder.

[0038] In the present invention, the lead tungstate powder is lead tungstate powder treated with diisooctyl succinate sulfonate, wherein diisooctyl succinate sulfonate is used as a surfactant to modify the lead tungstate powder. The diisooctyl succinate sulfonate in the present invention is different from conventional surfactants and can give the lead tungstate powder better dispersibility and wettability.

[0039] The preparation method of lead tungstate powder treated with diisooctyl succinate sulfonate includes: adding sodium tungstate solution to triethanolamine solution, dropping diisooctyl succinate sulfonate solution for dispersion, adjusting pH to 8 and then dropping lead acetate solution, stirring for reaction, the reaction time is 1-2h, obtaining lead tungstate solution, and then drying to obtain lead tungstate powder. The mass percentage concentration of triethanolamine in the triethanolamine solution is 4-6%, the concentration of sodium tungstate in the sodium tungstate solution is 0.05-0.15mol / L, the concentration of diisooctyl succinate sulfonate in the diisooctyl succinate sulfonate solution is 0.05-0.15mol / L, and the concentration of lead acetate in the lead acetate solution is 0.05-0.15mol / L; the volume ratio of triethanolamine solution, sodium tungstate solution, diisooctyl succinate sulfonate solution and lead acetate solution is 1-6:950-1050:475-525:950-1050.

[0040] The particle size of the lead tungstate powder modified by diisooctyl succinate sulfonate prepared by the above method is 0.6-0.7 μm. The particle size of lead tungstate directly affects its protection against ionizing radiation. The smaller the particle size, the more uniform the dispersion, and the better the protection ability of the protective device.

[0041] The lead tungstate powder in the present invention is treated with diisooctyl succinate sulfonate, so that the lead tungstate powder has better dispersibility and wettability. At the same time, the lead tungstate has the characteristics of high density, fast response, short radiation length, short light decay time, good resistance to radiation damage and no deliquescence. It is a material with excellent radiation shielding properties and can effectively absorb gamma rays.

[0042] S2. A method for preparing radiation-proof ultra-high molecular weight polyethylene fiber.

[0043] Solvent oil, ultra-high molecular weight polyethylene powder (UHMWPE), lead acid tungsten powder and dispersant are used as spinning raw materials, which are mixed in a mass ratio of 170-180:10-15:1-2:0.1-0.3, fully stirred at a stirring temperature of 40-60°C and a stirring time of 0.5-1h to obtain a spinning solution; the spinning solution is spun in sequence to obtain radiation-proof ultra-high molecular weight polyethylene fibers.

[0044] The ultra-high molecular weight polyethylene powder was purchased from Jiangsu Bosite Chemical Technology Co., Ltd.; CAS number: 9002-88-4.

[0045] The spinning steps include conventional spinning, pre-drawing, extraction, drying and positive drawing, etc., and the specific operation method is not described in detail in the present invention.

[0046] The radiation-proof ultra-high molecular weight polyethylene fiber provided by the present invention has excellent radiation-proof performance, and also has the characteristics of being soft and cut-resistant, and can be widely used in the preparation of various radiation-proof fabrics, including but not limited to radiation-proof clothing fabrics and radiation-proof glove fabrics.

[0047] For example, the present invention further provides a polyurethane radiation-proof glove, which comprises a glove blank made of the above-mentioned radiation-proof ultra-high molecular weight polyethylene fiber and a glue layer impregnated on the surface of the glove blank, specifically, comprising the following steps:

[0048] S1. A method for preparing a glove blank.

[0049] Ultra-high molecular weight polyethylene fiber, white polyester and tungsten wire are made into tungsten wire coated yarn, spandex and nylon are made into spandex coated yarn, and the tungsten wire coated yarn and the spandex coated yarn are woven together into a glove blank.

[0050] The tungsten coated yarn and spandex coated yarn are knitted using the U2 weaving method of a 21-needle glove machine. The tungsten coated yarn is introduced into the main yarn mouth, the spandex coated yarn is introduced into the auxiliary yarn mouth, and the 95# elastic thread is introduced into the wrist position to weave the glove blank together.

[0051] In the present invention, the tungsten wire coated yarn refers to a tungsten wire as a core, and an ultra-high molecular weight polyethylene fiber and a white polyester as an outer layer yarn to cover the elongated tungsten wire in a spiral manner. The fineness of the ultra-high molecular weight polyethylene fiber in the tungsten wire coated yarn is 80-120D, the fineness of the white polyester is 70-80D, and the diameter of the tungsten wire is 0.02-0.03mm.

[0052] Spandex covered yarn refers to a yarn that uses spandex as the core and nylon as the outer yarn to cover the stretched spandex in a spiral shape. The fineness of spandex in the spandex covered yarn is 15-25D, and the fineness of nylon is 25-35D.

[0053] The present invention defines the yarn for knitting the glove blank, wherein the tungsten wire has good density and radiation resistance. The present invention uses the tungsten wire as the core, and coats the surface of the tungsten wire with ultra-high molecular weight polyethylene fiber and white polyester, wherein the ultra-high molecular weight polyethylene fiber contains lead tungstate powder, so the prepared tungsten wire coated yarn has good radiation protection function and can effectively block harmful radiation such as X-rays and gamma rays. At the same time, the ultra-high molecular weight polyethylene fiber has good strength, outstanding impact resistance and cutting resistance, and also has certain resistance to ultraviolet radiation, neutrons and gamma rays, high specific energy absorption, low dielectric constant, high electromagnetic wave transmittance and the like.

[0054] The glove blanks woven by tungsten wire coated yarn and spandex coated yarn are light, thin and dense, which can prevent various rays from passing through the gaps in the gloves to endanger human health. They are also softer, more comfortable and have certain anti-cutting properties.

[0055] S2. A method for preparing a polyurethane emulsion containing lead tungstate powder.

[0056] 50-100 parts of waterborne polyurethane resin, 30-60 parts of deionized water, 0.5-1.5 parts of lead tungstate powder, 0.1-0.2 parts of defoamer, 0.05-0.08 parts of leveling agent and 0.05-0.09 parts of anti-sticking agent are mixed evenly. In the present invention, by adding lead tungstate powder to the waterborne polyurethane resin, the emulsion contains lead tungstate powder. When the glove blank is immersed in the polyurethane emulsion containing lead tungstate powder, the lead tungstate powder can be immersed in the surface of the glove blank together with the waterborne polyurethane resin, thereby also having a certain radiation protection effect on the surface of the glove blank.

[0057] The waterborne polyurethane resin in the present invention may be a conventional commercially available waterborne polyurethane resin, or may be independently prepared by the present invention.

[0058] Specifically, the preparation method of the waterborne polyurethane resin includes: heating a mixed solution of polyol, diphenylmethane diisocyanate and a catalyst to carry out a prepolymerization reaction, wherein the ratio of isocyanate group to hydroxyl group is 1.2, assuming that all hydroxyl groups are completely reacted in the prepolymerization reaction, when the isocyanate content in the prepolymer reaches a theoretical value of 2%, stopping the reaction, cooling to 30-40°C, adding butanone to dilute, and obtaining a prepolymer terminated with an isocyanate group; subsequently, adding triethylamine and dihydroxymethylpropionic acid (mass ratio is 0.8-1:1) to carry out a neutralization reaction, then adding deionized water until the solid content of the emulsion reaches 25-35wt%, continuing emulsification for 0.5-1h, adding triethylamine to carry out a chain extension reaction to remove the remaining isocyanate, and obtaining a waterborne polyurethane emulsion, and removing butanone by vacuum distillation of the waterborne polyurethane emulsion, maintaining the weight percentage of water in the waterborne polyurethane emulsion at 65-75%, and obtaining a waterborne polyurethane resin.

[0059] Preferably, the polyol comprises at least one of polytetrahydrofuran and polyethylene glycol;

[0060] Preferably, before the polyol and diphenylmethane diisocyanate react, the polyol is subjected to vacuum dehydration treatment; the vacuum dehydration temperature is 80-100° C. and the time is 0.5-1.5 h.

[0061] Preferably, the catalyst comprises at least one of dibutyltin dilaurate, stannous octoate and bismuth carboxylate.

[0062] S3, dipping and drying.

[0063] The glove blank is immersed in a polyurethane emulsion containing lead tungstate powder and then dried.

[0064] The dipping time is 8-15 seconds, and the drying includes first drying at 75-85°C for 20-40 minutes, then drying at 95-105°C for 20-40 minutes, and then setting drying at 100-120°C for 60-70 minutes.

[0065] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0066] Example 1

[0067] This embodiment provides a method for preparing polyurethane radiation-proof gloves, which comprises the following steps:

[0068] S1. A method for preparing lead tungstate powder.

[0069] Prepare 0.1mol / L sodium tungstate solution, diisooctyl succinate sulfonate solution and lead acetate solution respectively, and prepare a triethanolamine solution with a mass percentage concentration of 5%. Pour 0.003L of triethanolamine solution into the reactor, then add 1L of sodium tungstate solution, start stirring, drop 0.5L of diisooctyl succinate sulfonate solution for dispersion, adjust the pH to 8, drop 1L of lead acetate solution, stir and react, the reaction time is 1.5h, and obtain lead tungstate solution, which is then dried to obtain lead tungstate powder with a particle size of 0.64μm.

[0070] S2. A method for preparing radiation-proof ultra-high molecular weight polyethylene fiber.

[0071] Solvent oil, ultra-high molecular weight polyethylene powder, lead acid tungsten powder and dispersant are used as spinning raw materials, mixed in a mass ratio of 175:12:1.5:0.2, fully stirred at a stirring temperature of 45°C and a stirring time of 0.7h to obtain a spinning solution; the spinning solution is spun in sequence to obtain radiation-proof ultra-high molecular weight polyethylene fibers.

[0072] S3. A method for preparing a glove blank.

[0073] Tungsten coated yarn was made from one ultra-high molecular weight polyethylene fiber with a fineness of 100D, one white polyester with a fineness of 75D and one tungsten wire with a diameter of 0.025mm, and spandex coated yarn was made from one spandex with a fineness of 20D and one nylon with a fineness of 30D. The tungsten coated yarn and the spandex coated yarn were woven using the U2 weaving method of a 21-needle glove machine, wherein the tungsten coated yarn was introduced into the main yarn mouth, the spandex coated yarn was introduced into the auxiliary yarn mouth, and 95# elastic thread was introduced into the wrist position, and they were woven together into a glove blank.

[0074] S4. A method for preparing a polyurethane emulsion containing lead tungstate powder.

[0075] 100 parts of polyol (polytetrahydrofuran with a molecular weight of 1000) were added to a reactor equipped with a stirrer, a thermometer, a condenser and nitrogen protection, and vacuum dehydration was performed at 90°C for 1 hour. Subsequently, 30 parts of diphenylmethane diisocyanate and 0.0002 parts of a catalyst (dibutyltin dilaurate) were added, and nitrogen was introduced. The mixed solution was stirred at a medium speed (350 rpm) and heated to a constant reaction temperature (100°C) for prepolymerization. After a period of prepolymerization, the content of isocyanate groups in the prepolymer was detected. When the isocyanate content in the prepolymer reached After reaching 2% of the theoretical value, the reaction was stopped, the temperature was lowered to 30°C, butanone was added to dilute, and an isocyanate group-terminated prepolymer was obtained; triethylamine and dihydroxymethylpropionic acid (mass ratio was 0.8:1) were then added for neutralization reaction, and deionized water was then added until the solid content of the emulsion reached 30wt%, and emulsification was continued for 0.5h, and triethylamine was added for chain extension reaction to remove the remaining isocyanate to obtain an aqueous polyurethane emulsion, and the aqueous polyurethane emulsion was distilled under reduced pressure to remove butanone, and the weight percentage of water in the aqueous polyurethane emulsion was kept at 70%, to obtain an aqueous polyurethane resin.

[0076] Mix 70 parts of waterborne polyurethane resin, 40 parts of deionized water, 1 part of lead tungstate powder, 0.15 parts of defoaming agent, 0.06 parts of leveling agent and 0.07 parts of anti-sticking agent evenly.

[0077] S5. Impregnation and drying.

[0078] The glove blank was first preheated to 40°C in an oven, then immersed in a polyurethane emulsion containing lead tungstate powder for 10 seconds, then dried at 80°C for 30 minutes, then dried at 100°C for 30 minutes, and then fixed at 110°C for 65 minutes.

[0079] Example 2

[0080] This embodiment provides a method for preparing polyurethane radiation-proof gloves, which comprises the following steps:

[0081] S1. A method for preparing lead tungstate powder.

[0082] Prepare 0.05mol / L sodium tungstate solution, diisooctyl succinate sulfonate solution and lead acetate solution respectively, and prepare a triethanolamine solution with a mass percentage concentration of 4%. Pour 0.0027L of triethanolamine solution into the reactor, then add 0.5L of sodium tungstate solution, start stirring, drop 0.25L of diisooctyl succinate sulfonate solution for dispersion, adjust pH to 8, drop 0.5L of lead acetate solution, stir and react, the reaction time is 1h, and obtain lead tungstate solution, which is then dried to obtain lead tungstate powder with a particle size of 0.6μm.

[0083] S2. A method for preparing radiation-proof ultra-high molecular weight polyethylene fiber.

[0084] Solvent oil, ultra-high molecular weight polyethylene powder, lead acid tungsten powder and dispersant are used as spinning raw materials, mixed in a mass ratio of 170:10:1:0.1, fully stirred at a stirring temperature of 40°C and a stirring time of 1 hour to obtain a spinning solution; the spinning solution is spun in sequence to obtain radiation-proof ultra-high molecular weight polyethylene fibers.

[0085] S3. A method for preparing a glove blank.

[0086] Tungsten coated yarn was made from one ultra-high molecular weight polyethylene fiber with a fineness of 80D, one white polyester with a fineness of 70D and one tungsten wire with a diameter of 0.02mm, and spandex coated yarn was made from one spandex with a fineness of 15D and one nylon with a fineness of 25D. The tungsten coated yarn and the spandex coated yarn were knitted using the U2 weaving method of a 21-needle glove machine, wherein the tungsten coated yarn was introduced into the main yarn mouth, the spandex coated yarn was introduced into the auxiliary yarn mouth, and 95# elastic thread was introduced into the wrist position, and they were knitted together into a glove blank.

[0087] S4. A method for preparing a polyurethane emulsion containing lead tungstate powder.

[0088] 50 parts of polyol (polytetrahydrofuran with a molecular weight of 1000) were added to a reactor equipped with a stirrer, a thermometer, a condenser and nitrogen protection, and vacuum dehydration was carried out at 80°C for 1.5 hours. Subsequently, 15 parts of diphenylmethane diisocyanate and 0.0001 parts of a catalyst (stannous octoate) were added, and nitrogen was introduced. The mixed solution was stirred at a medium speed (200 rpm) and heated to a constant reaction temperature (85°C) for prepolymerization. After a period of prepolymerization, the content of isocyanate groups in the prepolymer was detected. When the isocyanate content in the prepolymer reached the theoretical value, the prepolymer was heated to a constant temperature of 85°C. After the value reaches 2%, the reaction is stopped, the temperature is lowered to 30-40°C, butanone is added to dilute, and an isocyanate group-terminated prepolymer is obtained; triethylamine and dihydroxymethylpropionic acid (mass ratio is 0.9:1) are subsequently added for neutralization reaction, and deionized water is then added until the solid content of the emulsion reaches 25wt%, and emulsification is continued for 1h, and triethylamine is added for chain extension reaction to remove the remaining isocyanate to obtain an aqueous polyurethane emulsion, and the aqueous polyurethane emulsion is subjected to reduced pressure distillation to remove butanone, and the weight percentage of water in the aqueous polyurethane emulsion is maintained at 75%, to obtain an aqueous polyurethane resin.

[0089] Mix 50 parts of waterborne polyurethane resin, 30 parts of deionized water, 0.5 parts of lead tungstate powder, 0.1 parts of defoaming agent, 0.05 parts of leveling agent and 0.05 parts of anti-sticking agent evenly.

[0090] S5. Impregnation and drying.

[0091] The glove blank was first preheated to 40°C in an oven, then immersed in a polyurethane emulsion containing lead tungstate powder for 8s, then dried at 75°C for 40min, then dried at 95°C for 40min, and then fixed at 100°C for 70min.

[0092] Example 3

[0093] This embodiment provides a method for preparing polyurethane radiation-proof gloves, which comprises the following steps:

[0094] S1. A method for preparing lead tungstate powder.

[0095] Prepare 0.15mol / L sodium tungstate solution, diisooctyl succinate sulfonate solution and lead acetate solution respectively, and prepare a triethanolamine solution with a mass percentage concentration of 6%. Pour 0.004L of triethanolamine solution into the reactor, then add 1.5L of sodium tungstate solution, start stirring, drop 0.75L of diisooctyl succinate sulfonate solution for dispersion, adjust pH to 8, drop 1.5L of lead acetate solution, stir and react for 2h to obtain lead tungstate solution, and then dry to obtain lead tungstate powder with a particle size of 0.7μm.

[0096] S2. A method for preparing radiation-proof ultra-high molecular weight polyethylene fiber.

[0097] Solvent oil, ultra-high molecular weight polyethylene powder, lead acid tungsten powder and dispersant are used as spinning raw materials, mixed in a mass ratio of 180:15:2:0.3, fully stirred at a stirring temperature of 60°C and a stirring time of 0.5h to obtain a spinning solution; the spinning solution is spun in sequence to obtain radiation-proof ultra-high molecular weight polyethylene fibers.

[0098] S3. A method for preparing a glove blank.

[0099] Tungsten coated yarn was made from one ultra-high molecular weight polyethylene fiber with a fineness of 120D, one white polyester with a fineness of 80D and one tungsten wire with a diameter of 0.03mm, and spandex coated yarn was made from one spandex with a fineness of 25D and one nylon with a fineness of 35D. The tungsten coated yarn and the spandex coated yarn were knitted using the U2 weaving method of a 21-needle glove machine, wherein the tungsten coated yarn was introduced into the main yarn mouth, the spandex coated yarn was introduced into the auxiliary yarn mouth, and 95# elastic thread was introduced into the wrist position, and they were knitted together into a glove blank.

[0100] S4. A method for preparing a polyurethane emulsion containing lead tungstate powder.

[0101] 150 parts of polyol (polytetrahydrofuran with a molecular weight of 1000) were added to a reactor equipped with a stirrer, a thermometer, a condenser and nitrogen protection, and vacuum dehydration was carried out at 100°C for 0.5h. Subsequently, 45 parts of diphenylmethane diisocyanate and 0.0003 parts of a catalyst (bismuth carboxylate) were added, and nitrogen was introduced. The mixed solution was stirred at a medium speed (500rpm) and heated to a constant reaction temperature (85°C) for prepolymerization. After a period of prepolymerization, the content of isocyanate groups in the prepolymer was detected. When the isocyanate content in the prepolymer reached the ideal value, the reaction mixture was stirred at a medium speed (500rpm). After the solid content of the emulsion reaches 2%, the reaction is stopped, the temperature is lowered to 30-40°C, butanone is added to dilute, and an isocyanate group-terminated prepolymer is obtained; triethylamine and dihydroxymethylpropionic acid (mass ratio is 1:1) are then added for neutralization reaction, and deionized water is then added until the solid content of the emulsion reaches 35wt%, and emulsification is continued for 0.8h, and triethylamine is added for chain extension reaction to remove the remaining isocyanate to obtain an aqueous polyurethane emulsion, and the aqueous polyurethane emulsion is subjected to reduced pressure distillation to remove butanone, and the weight percentage of water in the aqueous polyurethane emulsion is maintained at 65%, to obtain an aqueous polyurethane resin.

[0102] 100 parts of waterborne polyurethane resin, 60 parts of deionized water, 1.5 parts of lead tungstate powder, 0.2 parts of defoaming agent, 0.08 parts of leveling agent and 0.09 parts of anti-sticking agent were mixed evenly.

[0103] S5. Impregnation and drying.

[0104] The glove blank was first preheated to 40°C in an oven, then immersed in a polyurethane emulsion containing lead tungstate powder for 15 seconds, then dried at 85°C for 20 minutes, then dried at 105°C for 20 minutes, and then fixed at 120°C for 60 minutes.

[0105] Example 4

[0106] This embodiment is substantially the same as embodiment 1, except that the polyol in this embodiment is polyethylene glycol having a molecular weight of 1500.

[0107] Example 5

[0108] This embodiment is substantially the same as Embodiment 1, except that the polyol in this embodiment is a mixture of polytetrahydrofuran and polyethylene glycol in a ratio of 1:2.

[0109] Example 6

[0110] This embodiment is substantially the same as Embodiment 1, except that the mass ratio of triethylamine to dimethylolpropionic acid in this embodiment is 0.8:1.

[0111] Comparative Example 1

[0112] This comparative example provides a common lead radiation protection glove, and the preparation method thereof includes the preparation process of nitrile latex and the preparation process of the impregnated gloves.

[0113] Preparation of nitrile latex: 70 parts of nitrile latex; 0.8 parts of stabilizer; 0.7 parts of TP-95 plasticizer; 0.3 parts of antioxidant; 1.5 parts of titanium dioxide; 0.2 parts of regulator, 20 parts of nano lead powder. Add the above nitrile latex and additives into water and stir at high speed to make them dispersed evenly and make the viscosity at 1000 MPa·s for use.

[0114] The glove blank prepared in step S3 and the above-mentioned latex are used to carry out the following preparation process of the dipped gloves: glove blank → preheat oven to 40°C → glue tank (aqueous polyurethane emulsion) for 10s → oven 80°C (hot baking for 30min) → glue tank (nitrile latex) for 10s → hot baking at 80°C in oven for 30min → oven 100°C → shaping and baking for 65min → finished product.

[0115] Comparative Example 2

[0116] This comparative example is basically the same as Example 1, except that lead tungstate powder is not added in this comparative example. Specifically, step S1 of Example 1 is omitted in this comparative example, and lead tungstate powder is omitted in step S2 and lead tungstate powder is omitted in step S4.

[0117] Comparative Example 3

[0118] This comparative example is substantially the same as Example 1, except that the lead-acid tungsten powder is omitted in step S2 in this comparative example.

[0119] Comparative Example 4

[0120] This comparative example is substantially the same as Example 1, except that the lead-acid tungsten powder is omitted in step S4 in this comparative example.

[0121] Comparative Example 5

[0122] This comparative example is substantially the same as Example 1, except that diisooctyl succinate sulfonate is omitted in this comparative example.

[0123] Comparative Example 6

[0124] This comparative example is basically the same as Example 1, except that in this comparative example, diisooctyl succinate sulfonate is replaced by fatty alcohol polyoxyethylene ether sulfate.

[0125] Comparative Example 7

[0126] This comparative example is substantially the same as Example 1, except that, in this comparative example, the mass ratio of the ultra-high molecular weight polyethylene powder to the lead tungstate powder is 12:3.

[0127] Comparative Example 8

[0128] This comparative example is substantially the same as Example 1, except that, in this comparative example, the mass ratio of the waterborne polyurethane resin to the lead tungstate powder is 50:3.

[0129] Experimental Example 1

[0130] The performance test of the radiation-proof ultra-high molecular weight polyethylene fibers prepared in the above-mentioned embodiments 1-3 and comparative examples 2, 5-8 was carried out. The test method includes detecting whether the color difference is uniformly detected by using a color card comparison detection method; the fineness test method uses a yarn length measuring instrument to detect 20 meters and then convert it into 10,000 meters and 9,000 meters. The comparison with the standard fineness is no more than 7%; the modulus and strength are tested using a strength machine; the shielding rate is tested by relying on 57 Co generates gamma rays for radiation detection. Please refer to Table 1 for the test results.

[0131] Table 1. Statistical table of radiation-proof ultra-high molecular weight polyethylene fiber performance test for different examples

[0132]

[0133] As can be seen from the above table, although the fineness, modulus and strength of the fibers obtained by Examples 1-3 of the present invention and Comparative Examples 2 and 5-8 have certain differences, they all meet the index requirements. As for the shielding rate, the lead acid tungsten powder of step S2 in Comparative Example 2 is omitted, and the fiber has no shielding effect. Diisooctyl succinate sulfonate is omitted in Comparative Example 5. At this time, the dispersibility and wettability of the lead tungstate powder are poor, which will cause the final shielding effect to be significantly reduced, and compared with Example 1, the fineness of Comparative Example 5 is significantly improved, and the modulus and strength are significantly reduced. This is because the dispersibility and wettability of the lead tungstate powder are poor, resulting in poor composite effect with ultra-high molecular weight polyethylene powder, and then the fiber thickens, the fineness becomes larger, and the modulus and strength are reduced. In Comparative Example 6, other surfactants are selected, and it is found that it not only cannot effectively improve the dispersibility and wettability of the lead tungstate powder, but also further reduces the shielding effect. In Comparative Examples 7 and 8, the amount of lead tungstate powder was increased at different steps. It can be seen that when the amount of lead tungstate added increased, the shielding rate value would also increase, but its strength would be slightly reduced.

[0134] Experimental Example 2

[0135] The gloves prepared in the above-mentioned Examples 1-6 and Comparative Examples 1-8 were tested for weight, comfort and radiation protection performance. The test methods included a wearing comfort test and a γ-ray shielding rate test. The wearing comfort test was characterized by the test results of a fabric stiffness tester, and the γ-ray shielding rate test was characterized by the test results of a fabric stiffness tester. 57 Co generates gamma rays for radiation detection. Please refer to Table 1 for the test results.

[0136]

[0137]

[0138] As can be seen from the above table, the weight of Examples 1-5 provided by the present application is significantly lighter than that of the ordinary lead radiation protection gloves in Comparative Example 1, and the comfort and shielding rate are significantly better than those in Comparative Example 1. In Comparative Examples 2-4, the lead acid tungsten powder in different steps is omitted respectively. It can be seen that the amount of lead tungstate powder added has little effect on comfort, but has a greater effect on shielding rate. In this embodiment, lead acid tungsten powder is added to both the glove embryo and the latex, and the two can synergistically increase the shielding effect. Diisooctyl succinate sulfonate is omitted in Comparative Example 5. At this time, the dispersibility and wettability of the lead tungstate powder are poor, which will lead to a certain reduction in the final shielding effect. In Comparative Example 6, other surfactants are selected, and it is found that it not only cannot effectively improve the dispersibility and wettability of the lead tungstate powder, but will further reduce the shielding effect. In Comparative Examples 7 and 8, the amount of lead tungstate powder was increased at different steps. It can be seen that when the amount of lead tungstate added increased, the shielding rate value would also increase, but the comfort level would decrease. When the amount of lead tungstate added decreased, the weight of the gloves would also decrease slightly, and the softness would also increase slightly.

[0139] In summary, the preparation method of the radiation-proof ultra-high molecular weight polyethylene fiber provided by the present invention introduces lead tungstate powder treated with diisooctyl succinate sulfonate when preparing the ultra-high molecular weight polyethylene fiber. Diisooctyl succinate sulfonate can give the lead tungstate powder better dispersibility and wettability. The introduction of the lead tungstate powder treated with diisooctyl succinate sulfonate greatly improves the radiation-proof performance of the radiation-proof ultra-high molecular weight polyethylene fiber. At the same time, the ultra-high molecular weight polyethylene fiber also has the characteristics of being soft and cut-resistant. It can be widely used in the preparation of various radiation-proof fabrics, including but not limited to radiation-proof clothing fabrics and radiation-proof glove fabrics. In particular, with respect to radiation-proof glove fabrics, the present invention also provides a polyurethane radiation-proof glove, which is woven into a glove blank using radiation-proof ultra-high molecular weight polyethylene fibers, and a rubber layer is impregnated on the surface of the glove blank, and the impregnated resin also contains lead tungstate powder. The inner glove blank and the outer impregnation layer of the prepared polyurethane radiation-proof glove both contain lead tungstate powder, so that the polyurethane radiation-proof glove not only has good radiation-proof performance, but also has properties such as softness, high strength, and anti-cutting, which greatly improves the wearing comfort of the user, and because the gloves are overall soft, the user's activities and operations are more convenient.

[0140] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing radiation-proof ultra-high molecular weight polyethylene fiber, characterized in that: include: The radiation-proof ultra-high molecular weight polyethylene fiber is prepared by spinning a spinning solution containing lead tungstate powder and ultra-high molecular weight polyethylene powder; The lead tungstate powder is lead tungstate powder treated with diisooctyl succinate sulfonate.

2. The method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber according to claim 1, characterized in that: The preparation method of the lead tungstate powder treated with diisooctyl succinate sulfonate comprises: adding a sodium tungstate solution to a triethanolamine solution, dropping a diisooctyl succinate sulfonate solution to disperse, adjusting the pH to 8 and then dropping a lead acetate solution, stirring to react, obtaining a lead tungstate solution, and then drying to obtain the lead tungstate powder.

3. The method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber according to claim 2, characterized in that: The mass percentage concentration of triethanolamine in the triethanolamine solution is 4-6%, the concentration of sodium tungstate in the sodium tungstate solution is 0.05-0.15 mol / L, the concentration of diisooctyl succinate sulfonate in the diisooctyl succinate sulfonate solution is 0.05-0.15 mol / L, and the concentration of lead acetate in the lead acetate solution is 0.05-0.15 mol / L; the volume ratio of the triethanolamine solution, the sodium tungstate solution, the diisooctyl succinate sulfonate solution and the lead acetate solution is 1-6:950-1050:475-525:950-1050; And / or, the particle size of the lead tungstate powder modified by diisooctyl succinate sulfonate is 0.6-0.7 μm.

4. The method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber according to any one of claims 1 to 3, characterized in that: The mass ratio of the ultra-high molecular weight polyethylene powder to the lead tungstate powder is 10-15:1-2; And / or, the spinning solution further includes solvent oil and a dispersant, and the mass ratio of the ultra-high molecular weight polyethylene powder, the solvent oil and the dispersant in the spinning solution is 10-15:170-180:0.1-0.3; And / or, the mixing temperature of the spinning solution is 40-60° C., and the mixing time is 0.5-1 h.

5. A radiation-proof ultra-high molecular weight polyethylene fiber, characterized in that: The fiber is prepared by the method for preparing the radiation-proof ultra-high molecular weight polyethylene fiber as described in any one of claims 1 to 4.

6. Use of the radiation-proof ultra-high molecular weight polyethylene fiber according to claim 5 in the preparation of radiation-proof clothing fabrics or radiation-proof glove fabrics.

7. A polyurethane radiation protection glove, characterized in that: The invention comprises a glove blank made of the radiation-proof ultra-high molecular weight polyethylene fiber as claimed in claim 5 and a glue layer impregnated on the surface of the glove blank.

8. The polyurethane radiation protection gloves according to claim 7, characterized in that: The preparation method of the glove blank comprises: preparing tungsten coated yarn from the ultra-high molecular weight polyethylene fiber, white polyester and tungsten wire, preparing spandex coated yarn from spandex and nylon, and weaving the tungsten coated yarn and the spandex coated yarn together into a glove blank; wherein the preparation method of the glove blank comprises at least one of the following features A to C; Feature A: The tungsten coated yarn and the spandex coated yarn are knitted using the U2 weaving method of a 21-needle glove machine, wherein the tungsten coated yarn is introduced into the main yarn mouth, the spandex coated yarn is introduced into the auxiliary yarn mouth, and a 95# elastic thread is introduced into the wrist position to knit together into a glove blank; Feature B: The fineness of the ultra-high molecular weight polyethylene fiber in the tungsten wire coated yarn is 80-120D, the fineness of the white polyester is 70-80D, and the diameter of the tungsten wire is 0.02-0.03mm; Feature C: The fineness of the spandex in the spandex covered yarn is 15-25D, and the fineness of the nylon is 25-35D.

9. The polyurethane radiation protection gloves according to claim 8, characterized in that: The preparation method of the adhesive layer comprises: dipping the glove blank into a polyurethane emulsion containing lead tungstate powder and water-based polyurethane resin, and then drying the glove blank; wherein the preparation method of the adhesive layer comprises at least one of the following features D to E; Feature D: The preparation method of the polyurethane emulsion comprises: uniformly mixing 50-100 parts of an aqueous polyurethane resin, 30-60 parts of deionized water, 0.5-1.5 parts of the lead tungstate powder, 0.1-0.2 parts of a defoaming agent, 0.05-0.08 parts of a leveling agent and 0.05-0.09 parts of an anti-sticking agent to prepare a polyurethane emulsion; Feature E: The drying includes first drying at 75-85°C for 20-40 minutes, then drying at 95-105°C for 20-40 minutes, and then drying at 100-120°C for 60-70 minutes.

10. The polyurethane radiation protection gloves according to claim 9, characterized in that: The preparation method of the waterborne polyurethane resin comprises: heating a mixed solution of polyol, diphenylmethane diisocyanate and a catalyst to carry out a prepolymerization reaction; when the isocyanate content in the prepolymer reaches a theoretical value, stopping the reaction, cooling to 30-40° C., adding butanone to dilute, and obtaining a prepolymer terminated with an isocyanate group; then adding triethylamine and dihydroxymethyl propionic acid to carry out a neutralization reaction, then adding deionized water until the solid content of the emulsion reaches 25-35wt%, continuing emulsification for 0.5-1h, adding triethylamine to carry out a chain extension reaction to remove the remaining isocyanate, and obtaining a waterborne polyurethane emulsion; and removing butanone from the waterborne polyurethane emulsion under reduced pressure distillation, maintaining the weight percentage of water in the waterborne polyurethane emulsion at 65-75%, and obtaining the waterborne polyurethane resin; wherein the preparation method of the waterborne polyurethane resin comprises at least one of the following features F to I; Feature F: The polyol comprises at least one of polytetrahydrofuran and polyethylene glycol; Feature G: Before the polyol reacts with the diphenylmethane diisocyanate, the polyol is subjected to vacuum dehydration treatment; the vacuum dehydration temperature is 80-100° C. and the time is 0.5-1.5 h; Feature H: The mass ratio of the triethylamine to the dimethylolpropionic acid is 0.8-1:1; Feature I: The catalyst includes at least one of dibutyltin dilaurate, stannous octoate and bismuth carboxylate.

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