Low-zinc butyronitrile glove and preparation method thereof

Abstract

The invention discloses a low-zinc butyronitrile glove and a preparation method thereof, and relates to the technical field of butyronitrile gloves. The butyronitrile glove is prepared from a composite adhesive emulsion. The composite adhesive emulsion is prepared from the following raw materials: butyronitrile latex, sodium dodecyl benzene sulfonate, tween-80, zinc oxide, sulfur, an accelerant, an anti-aging agent, titanium dioxide and a modifier dispersion liquid; wherein the modifier dispersion liquid is prepared from deionized water, modified paraffin, tween-80, span-60 and modified cellulose. According to the invention, paraffin is firstly oxidized by air, and then is modified by ethidene diamine amino to prepare modified paraffin; by adding modified cellulose which is prepared by firstly activating carboxylated nanocellulose, then reacting with chitosan and introducing hydroxylated graphene quantum dots, the zinc ion dissolution rate is reduced, and meanwhile, the wear resistance, tensile strength, elongation at break and aging resistance of the butyronitrile gloves are effectively improved. Therefore, the method has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nitrile gloves, in particular to a low-zinc nitrile glove and a preparation method thereof. BACKGROUND

[0002] The nitrile latex prepared by emulsion polymerization of butadiene and acrylonitrile has good oil resistance and chemical resistance, and is widely used in the automotive, aviation, petroleum and medical industries. Nitrile gloves are a kind of synthetic rubber protective gloves made of nitrile rubber as the main raw material through dipping molding process. As a synthetic material product, nitrile gloves do not contain allergenic proteins in natural latex, which can effectively avoid latex allergy problems; at the same time, due to the acrylonitrile segment in the molecular structure of nitrile rubber, it endows it with excellent oil resistance, chemical corrosion resistance, and the butadiene segment provides good elasticity and flexibility, so that it has both tensile strength and fit. Therefore, nitrile gloves are widely used in medical care, food processing, industrial operation, laboratory research and other scenes, mainly for hand protection, to isolate the hands from direct contact with pollutants, chemicals and microorganisms, and to ensure safety and hygiene.

[0003] However, nitrile gloves still have the problems of high zinc content, which can cause allergy in zinc-sensitive groups, and poor wear resistance, tensile strength and elongation at break of low-zinc nitrile gloves, which limits their application. Therefore, the wear resistance, tensile strength and elongation at break of the existing low-zinc nitrile gloves still need to be further improved. SUMMARY

[0004] The present application relates to the technical field of nitrile gloves, in particular to a low-zinc nitrile glove and a preparation method thereof. The existing low-zinc nitrile gloves still have the problems of poor wear resistance, tensile strength and elongation at break.

[0005] The object of the present application can be achieved by the following technical solutions: A low-zinc nitrile glove, the nitrile glove is prepared from a composite latex emulsion; The composite latex emulsion comprises the following raw materials by mass: nitrile latex 100-200 parts, sodium dodecyl benzene sulfonate 0.3-0.5 parts, Tween-80 0.2-0.4 parts, zinc oxide 0.4-0.6 parts, sulfur 0.8-1.2 parts, accelerator BZ 0.5-0.7 parts, accelerator PZ 0.4-0.6 parts, antioxidant 2246 0.4-0.6 parts, titanium white powder 1-2 g parts, and modifier dispersion liquid 38-84 parts; The modifier dispersion liquid is prepared from deionized water, modified paraffin wax, Tween-80, Span-60 and modified cellulose; The modified paraffin wax is prepared by first air-oxidizing paraffin wax and then modifying it with ethylenediamine amino; The modified cellulose is prepared by activating carboxyl groups of carboxylated nanocellulose with 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide ester, then reacting with chitosan, and introducing hydroxylated graphene quantum dots.

[0006] Preferably, the preparation method of the composite latex is as follows: Sodium dodecyl benzene sulfonate and Tween-80 are added into butyronitrile latex and stirred for 10-20 min, then zinc oxide, sulfur, accelerator BZ, accelerator PZ, antioxidant 2246, and titanium white are added in sequence and stirred, then the pH is adjusted to 10-10.5, then the modifier dispersion liquid is added and stirred for 20-30 h to obtain the composite latex.

[0007] Preferably, the preparation method of the modifier dispersion liquid is as follows: Modified paraffin, Tween-80, and Span-60 are added into deionized water and ultrasonically emulsified at 78-80℃ for 20-30 min, then the modified cellulose is added and ultrasonically treated for 30-50 min to obtain the modifier dispersion liquid.

[0008] Preferably, the mass ratio of the deionized water, modified paraffin, Tween-80, Span-60, and modified cellulose is 30-72:2.5-3.5:0.5-0.6:0.2-0.25:5-8.

[0009] Preferably, the preparation method of the modified paraffin is as follows: A1: Paraffin is added into cyclohexane and stirred at 65-70℃ for 20-30 min, then cobalt acetate is added and the temperature is raised to 88-90℃, air is introduced at a rate of 0.5 L / min and reacted at 85-90℃ for 6-7 h, then the temperature is lowered to 50-60℃ to obtain an oxidized paraffin solution; A2: p-Toluenesulfonic acid is added into ethylenediamine and stirred at 38-40℃ for 10-20 min, then the oxidized paraffin solution is added dropwise and reacted at 95-100℃ for 3-4 h, then the temperature is lowered to 50-60℃, petroleum ether is added, and after standing for 30-40 min, the water phase is removed, and the upper solution is distilled under reduced pressure to remove toluene and petroleum ether to obtain the modified paraffin.

[0010] Preferably, the mass ratio of the cyclohexane, paraffin, and cobalt acetate in A1 is 200-250:100-125:0.3-0.4. The mass ratio of the ethylenediamine, p-toluenesulfonic acid, oxidized paraffin solution, and petroleum ether in A2 is 4-5:0.5-0.7:300-375:30-40.

[0011] Preferably, the preparation method of the modified cellulose is as follows: B1: adding carboxylated nanocellulose into deionized water and ultrasonic dispersion for 20-30 min, then adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide ester and stirring for 1-1.5 h to obtain nanocellulose dispersion; B2: dissolving chitosan in acetic acid aqueous solution, then adding into nanocellulose dispersion and stirring at 45-50℃ for 3-4 h, then adding hydroxylated graphene quantum dots and adjusting pH to 4.8-5.2, stirring at 55-60℃ for 2-3 h, centrifugal separation and washing the precipitate, then freeze-drying, grinding and passing through 150-200 mesh sieve to obtain modified cellulose.

[0012] Preferably, the mass ratio of the deionized water, carboxylated nanocellulose, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide ester in B1 is 100-120:5-6:0.5-0.6:0.3-0.36; The mass fraction of the acetic acid aqueous solution in B2 is 1%; The mass ratio of the chitosan, acetic acid aqueous solution, nanocellulose dispersion, hydroxylated graphene quantum dots in B2 is 2-2.4:100-120:105-126:0.5-0.6.

[0013] A preparation method of low-zinc nitrile glove, comprising the following steps: S1: immersing ceramic hand mold into 5% mass fraction sodium hydroxide solution at 55-60℃ for 2-5 min, then washing with deionized water for 3-5 times, drying at 75-80℃ for 10-30 min, then immersing into calcium nitrate aqueous solution containing ethanol for 3-5 s, then drying at 65-70℃ for 2-5 min to obtain pretreated hand mold; S2: immersing pretreated hand mold into 25-30℃ composite latex emulsion for 5-8 s, then taking out at 8-10 cm / min, forming 0.08-0.12 mm thick glue film, then air drying at 45-50℃ for 1-3 min, then performing secondary immersion for 2-3 s on 2-3 cm part of the fingertips, then immersing in 55-60℃ deionized water for 5-10 min, finally air drying at 75-80℃ for 5-7 min to obtain crude glove; S3: rolling up the opening of the crude glove by 2-3 mm by using a rolling machine, then preheating at 80℃ for 5-7 min, then vulcanizing at 110-120℃ for 25-35 min and cooling to 50-60℃, then immersing in active chlorine aqueous solution for 20-30 s, then neutralizing in sodium bisulfate aqueous solution to pH 6-7, finally immersing in antioxidant 1076 aqueous solution for 10 s and washing 5-10 times, then drying and demolding to obtain low-zinc nitrile glove.

[0014] Preferably, the mass fraction of calcium nitrate in the calcium nitrate aqueous solution containing ethanol in S1 is 10%-15%, and the mass fraction of ethanol is 3% The mass fraction of the antioxidant 1076 aqueous solution in S3 is 0.1%.

[0015] The beneficial effects of the present application are as follows: The present application provides a low-zinc nitrile glove and a preparation method thereof.

[0016] (1) The polar groups such as carboxyl and amino introduced into the molecular chain of the modified paraffin can form hydrogen bonds with the nitrile groups in the nitrile latex, uniformly disperse in the rubber film, and reduce the friction coefficient of the material surface as "lubricating phase"; the thin film distribution can absorb stress during the wear process, reducing the direct wear of the surface layer of the rubber film. The modified paraffin can enhance the flowability of the nitrile rubber molecular chain, making the chain segment more easily slide and orient during the stretching process, thereby improving the elongation at break of the material. The amino and carboxyl groups in the modified paraffin can form stable coordination bonds with zinc ions in the system, reducing the dissolution of free zinc ions; at the same time, the dense network formed by the wax phase in the rubber film can physically block the migration of zinc ions to the surface. The amino groups in the modified paraffin can capture free radicals generated during the aging process, inhibiting the oxidative breakdown of the nitrile rubber molecular chain; the continuous thin film formed by the wax phase on the surface of the rubber film can reduce the contact between oxygen, ultraviolet light and the rubber matrix, delaying aging.

[0017] (2) The carboxylated nanocellulose in the modified cellulose can form a continuous network in the latex, dispersing the friction stress through "skeleton support" and reducing local wear; the hydroxylated graphene quantum dots are uniformly embedded in the network, which can directly resist the scratching of sharp objects during the friction process, reducing the surface material shedding; the flexible chain of chitosan is crosslinked with nanocellulose through amide bonds, which can slightly deform during friction, buffer stress impact, and avoid the wear caused by rigid fracture. After activation, the carboxyl groups of nanocellulose form amide bonds with the amino groups of chitosan, constructing a stable crosslinked network. This network is combined with the rubber chains of nitrile latex through van der Waals force, which can efficiently transfer the load during stretching; the hydrogen bonds between the hydroxyl groups of graphene quantum dots and the polar groups of rubber chains can inhibit the sliding of rubber chains at the microscale, improving the tensile strength. The carboxyl and hydroxyl groups in the modified cellulose and the unreacted amino groups in chitosan can form coordination bonds with zinc ions, fixing free zinc ions in the network; the continuous cellulose-chitosan network can wrap the zinc oxide particles, slowing down their dissolution rate during use. The conjugated structure of graphene quantum dots can adsorb oxygen radicals generated during the aging process of rubber, inhibiting the chain oxidation reaction; the amide bond energy between nanocellulose and chitosan is higher than that of the carbon-carbon bond of rubber, which is not easy to break during high-temperature aging, maintaining the structural integrity; the strong absorption capacity of graphene quantum dots to ultraviolet light can reduce the direct damage of ultraviolet light to the rubber chain.

[0018] Therefore, the low-zinc nitrile glove prepared by the application has excellent low-zinc ion dissolution rate, wear resistance, tensile strength, elongation at break and aging resistance, and has a more extensive application prospect. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the application.

[0020] Unless otherwise specified, the following raw material information used in the examples and comparative examples of the application is as follows: The nitrile latex (solid content 43.5%) was purchased from Xingtianwai Chemical (Shanghai) Co., Ltd.

[0021] Example 1: A low-zinc nitrile glove was prepared by the following method: S1: 100 g of paraffin was added to 200 g of cyclohexane and stirred at 65°C for 30 min, then 0.3 g of cobalt acetate was added and the temperature was raised to 88°C, air was introduced at a rate of 0.5 L / min and reacted at 85°C for 6 h, then the temperature was lowered to 50°C, and an oxidized paraffin solution was obtained; S2: 0.5 g of p-toluenesulfonic acid was added to 4 g of ethylenediamine and stirred at 38°C for 20 min, then 300 g of the oxidized paraffin solution was added and reacted at 95°C for 4 h, then cooled to 50°C, 30 g of petroleum ether was added, and after standing for 30 min, the aqueous phase was removed and the upper layer solution was distilled under reduced pressure to remove toluene and petroleum ether, and a modified paraffin was obtained; S3: 5 g of carboxylated nanocellulose was added to 100 mL of deionized water and ultrasonically dispersed for 20 min, then 0.5 g of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.3 g of N-hydroxysuccinimide ester were added and stirred for 1 h to obtain a nanocellulose dispersion; S4: 2 g of chitosan was dissolved in 100 g of 1% acetic acid aqueous solution, then added to 105 g of the nanocellulose dispersion and stirred at 45°C for 4 h, then 0.5 g of hydroxylated graphene quantum dots was added and the pH was adjusted to 4.8, and then stirred at 55°C for 3 h, centrifuged and washed the precipitate with deionized water for 5 times, then freeze-dried at -40°C under a vacuum of 5 Pa, ground and sieved through a 150 mesh sieve to obtain modified cellulose; S5: 2.5 g modified paraffin, 0.5 g Tween-80, 0.2 g Span-60 were added into 30 mL deionized water and ultrasonically emulsified at 78 °C for 30 min, then 5 g modified cellulose was added and ultrasonically treated for 30 min to obtain a modifier dispersion; S6: 0.3 g sodium dodecyl benzene sulfonate, 0.2 g Tween-80 were added into 100 g butyronitrile latex and stirred at 300 r / min for 20 min, then 0.4 g zinc oxide, 0.8 g sulfur, 0.5 g accelerator BZ, 0.4 g accelerator PZ, 0.4 g antioxidant 2246, 1 g titanium white were added in sequence and stirred for 5 min each time, then the pH was adjusted to 10 with 5% sodium hydroxide aqueous solution, then 38 g modifier dispersion was added at 3 g / min and stirred for 20 h to obtain a composite latex; S7: The ceramic hand mold was immersed in a 5% sodium hydroxide solution at 55 °C for 5 min, then rinsed with deionized water for 3 times, dried at 75 °C for 30 min, then immersed in a 10% calcium nitrate aqueous solution containing 3% ethanol for 5 s, then dried at 65 °C for 5 min to obtain a pretreated hand mold; S8: The pretreated hand mold was immersed in the composite latex at 25 °C for 8 s, then taken out at 8 cm / min, then dried at 45 °C for 3 min after forming a 0.08 mm thick glue film, then the 2 cm part at the fingertip was secondarily immersed for 2 s, then immersed in deionized water at 55 °C for 10 min, finally dried at 75 °C for 7 min to obtain a crude glove; S9: The crude glove was rolled up by 2 mm at the opening with a rolling machine, then preheated at 80 °C for 5 min, then vulcanized at 110 °C for 35 min and cooled to 50 °C, then immersed in an active chlorine aqueous solution with a concentration of 100 mg / L for 30 s, then neutralized to pH 6 with a sodium bisulfate aqueous solution, finally immersed in an antioxidant 1076 aqueous solution with a mass fraction of 0.1% for 10 s and washed with water for 5 times, then dried and demolded to obtain a low-zinc butyronitrile glove.

[0022] Example 2: A low-zinc butyronitrile glove was prepared as follows: S1: 112.5 g paraffin was added into 225 g cyclohexane and stirred at 68 °C for 25 min, then 0.35 g cobalt acetate was added and the temperature was raised to 89 °C, air was blown in at a rate of 0.5 L / min and reacted at 88 °C for 6.5 h, then the temperature was lowered to 55 °C to obtain an oxidized paraffin solution; S2: 0.6 g p-toluenesulfonic acid was added into 4.5 g ethylenediamine and stirred at 39 °C for 15 min, then 337.5 g oxidized paraffin solution was added dropwise and reacted at 98 °C for 3.5 h, then 35 g petroleum ether was added after the temperature was cooled to 55 °C, the water phase was removed after standing for 35 min, then the upper solution was distilled under reduced pressure to remove toluene and petroleum ether to obtain modified paraffin. S3: 5.5 g of carboxylated nanocellulose was added to 110 mL of deionized water and ultrasonically dispersed for 25 min, then 0.55 g of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 0.33 g of N-hydroxysuccinimide ester was added and stirred for 1.3 h to obtain a nanocellulose dispersion; S4: 2.2 g of chitosan was dissolved in 110 g of 1% acetic acid aqueous solution, then added to 115.5 g of nanocellulose dispersion and stirred at 48°C for 3.5 h, then 0.55 g of hydroxylated graphene quantum dots was added and the pH was adjusted to 5, then stirred at 58°C for 2.5 h, centrifuged and the precipitate was washed with deionized water for 6 times, then freeze-dried at -40°C under a vacuum of 5 Pa, ground and passed through a 180 mesh sieve to obtain modified cellulose; S5: 3 g of modified paraffin, 0.55 g of Tween-80, 0.23 g of Span-60 was added to 51 mL of deionized water and ultrasonically emulsified at 79°C for 25 min, then 6.5 g of modified cellulose was added and ultrasonically treated for 40 min to obtain a modifier dispersion; S6: 0.4 g of sodium dodecyl benzene sulfonate, 0.3 g of Tween-80 was added to 150 g of butyl nitrile latex and stirred at 350 r / min for 15 min, then 0.5 g of zinc oxide, 1 g of sulfur, 0.6 g of accelerator BZ, 0.5 g of accelerator PZ, 0.5 g of antioxidant 2246, 1.5 g of titanium white was added in turn, each was stirred for 6 min, then the pH was adjusted to 10.3 with 5% sodium hydroxide aqueous solution, 61 g of modifier dispersion was added at 4 g / min and stirred for 25 h to obtain a composite latex; S7: The ceramic hand mold was immersed in a 5% sodium hydroxide solution at 58°C for 4 min, then rinsed with deionized water for 4 times, dried at 78°C for 20 min, then immersed in a 13% calcium nitrate aqueous solution containing 3% ethanol for 4 s, then dried at 68°C for 4 min to obtain a pretreated hand mold; S8: The pretreated hand mold was immersed in the composite latex at 28°C for 7 s, then taken out at 9 cm / min, then the 2.5 cm part of the fingertip was immersed for 2.5 s, then immersed in deionized water at 58°C for 8 min, finally dried at 78°C for 6 min to obtain a glove crude product; S9: The glove crude product is rolled up at the opening by 2.5 mm with a rolling machine, and then preheated at 80℃ for 6 min, vulcanized at 115℃ for 30 min, and cooled to 55℃, and then immersed in an active chlorine aqueous solution with a concentration of 150 mg / L for 25 s, neutralized to pH 6.5 with a sodium bisulfate aqueous solution, and finally immersed in an antioxidant 1076 aqueous solution with a mass fraction of 0.1% for 10 s and washed with water for 8 times, dried and demolded to obtain a low-zinc nitrile glove.

[0023] Example 3: A method for preparing a low-zinc nitrile glove is as follows: S1: 125 g of paraffin is added to 250 g of cyclohexane and stirred at 70℃ for 20 min, and then 0.4 g of cobalt acetate is added and the temperature is raised to 90℃, air is blown at a rate of 0.5 L / min and reacted at 90℃ for 6 h, and then the temperature is lowered to 60℃ to obtain an oxidized paraffin solution; S2: 0.7 g of p-toluenesulfonic acid is added to 5 g of ethylenediamine and stirred at 40℃ for 10 min, and then 375 g of the oxidized paraffin solution is added and reacted at 100℃ for 3 h, and then 40 g of petroleum ether is added after the temperature is cooled to 60℃, and the aqueous phase is removed after standing for 40 min, and the upper solution is distilled under reduced pressure to remove toluene and petroleum ether to obtain a modified paraffin; S3: 6 g of carboxylated nanocellulose is added to 120 g of deionized water and ultrasonicated for 30 min, and then 0.6 g of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.36 g of N-hydroxysuccinimide ester are added and stirred for 1.5 h to obtain a nanocellulose dispersion; S4: 2.4 g of chitosan is dissolved in 120 g of 1% acetic acid aqueous solution, and then added to 126 g of the nanocellulose dispersion and stirred at 50℃ for 3 h, and then 0.6 g of hydroxylated graphene quantum dots is added and the pH is adjusted to 5.2, and then stirred at 60℃ for 2 h, and then centrifuged and the precipitate is washed with deionized water for 7 times, and then freeze-dried at -40℃ under a vacuum degree of 5 Pa, and then ground and passed through a 1200 mesh sieve to obtain a modified cellulose; S5: 3.5 g of modified paraffin, 0.6 g of Tween-80, and 0.25 g of Span-60 are added to 72 mL of deionized water and ultrasonically emulsified at 80℃ for 20 min, and then 8 g of modified cellulose is added and ultrasonically treated for 50 min to obtain a modifier dispersion; S6: 0.5 g of sodium dodecyl benzene sulfonate, 0.4 g of Tween-80 were added into 200 g of nitrile latex, and stirred at 400 r / min for 10 min, then 0.6 g of zinc oxide, 1.2 g of sulfur, 0.7 g of accelerator BZ, 0.6 g of accelerator PZ, 0.6 g of antioxidant 2246, 2 g of titanium white were added in sequence, and stirred for 7 min after adding each one, then the pH was adjusted to 10.5 with 5% sodium hydroxide aqueous solution, then 84 g of modifier dispersion liquid was added at 5 g / min and stirred for 30 h, to obtain a composite latex; S7: the ceramic hand mold was immersed in a 5% sodium hydroxide solution at 60°C for 2 min, then washed with deionized water for 5 times, dried at 80°C for 10 min, then immersed in a 15% calcium nitrate aqueous solution containing 3% ethanol for 3 s, and then dried at 70°C for 2 min, to obtain a pretreated hand mold; S8: the pretreated hand mold was immersed in the composite latex at 30°C for 5 s, then taken out at 10 cm / min, and after forming a 0.12 mm thick glue film, air dried at 50°C for 1 min, then the 3 cm part of the fingertip was secondarily immersed for 3 s, then soaked in deionized water at 60°C for 5 min, and finally air dried at 80°C for 5 min, to obtain a glove crude product; S9: the glove crude product was rolled up by 3 mm at the opening with a rolling machine, then preheated at 80°C for 7 min, vulcanized at 120°C for 25 min, then cooled to 60°C, then immersed in an active chlorine aqueous solution with a concentration of 200 mg / L for 20 s, then neutralized to pH 7 with a sodium bisulfate aqueous solution, finally immersed in an antioxidant 1076 aqueous solution with a mass fraction of 0.1% for 10 s and washed with water for 10 times, dried and demolded to obtain a low-zinc nitrile glove.

[0024] Comparative Example 1: This comparative example is compared with Example 1 only by replacing the "modified paraffin" added in the preparation process of S5 with the "oxidized paraffin" prepared in S1, and the rest of the steps and parameters are the same, this comparative example will not be repeated, finally a low-zinc nitrile glove is obtained.

[0025] Comparative Example 2: This comparative example is compared with Example 1 only by replacing the "modified paraffin" added in the preparation process of S5 with "paraffin", and the rest of the steps and parameters are the same, this comparative example will not be repeated, finally a low-zinc nitrile glove is obtained.

[0026] Comparative Example 3: This comparative example is compared with Example 1 only by not adding "modified paraffin" in the preparation process of S5, and the rest of the steps and parameters are the same, this comparative example will not be repeated, finally a low-zinc nitrile glove is obtained.

[0027] Comparative Example 4: The comparative example is compared with example 1 only without adding “hydroxylated graphene quantum dots” in the preparation process of S4, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, low-zinc nitrile gloves are obtained.

[0028] Comparative example 5: The comparative example is compared with example 1 only by replacing the “modified cellulose” added in the preparation process of S5 with “carboxylated nanocellulose”, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, low-zinc nitrile gloves are obtained.

[0029] Comparative example 6: The comparative example is compared with example 1 only without adding “modified cellulose” in the preparation process of S5, and the rest of the steps and parameters are the same. The comparative example will not be repeated here. Finally, low-zinc nitrile gloves are obtained.

[0030] Performance test: Abrasion resistance test: According to the GB / T 1689-2014 “Determination of Abrasion Resistance of Vulcanized Rubber (Using Akron Abrasion Tester)” standard, the abrasion amount (cm 3 ) of the low-zinc nitrile gloves prepared by the low-zinc nitrile gloves of example 1- example 3 and comparative example 1- comparative example 6 under the constant load of 26.5N after 1.61km of friction was determined. The test results are shown in Table 1; Zinc ion elution amount test: According to the IEST-RP-CC005.3 “Clean Room Glove Finger Test Standard”, the zinc ion elution amount (mg·kg -1 ) of the low-zinc nitrile gloves prepared by the low-zinc nitrile gloves of example 1- example 3 and comparative example 1- comparative example 6 was determined. The test results are shown in Table 1; Tensile strength test: According to the GB / T 528-2009 “Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber” standard, the tensile strength (MPa) of the low-zinc nitrile gloves prepared by the low-zinc nitrile gloves of example 1- example 3 and comparative example 1- comparative example 6 was determined. The test results are shown in Table 1; Elongation at break test: According to the GB / T 528-2009 “Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber” standard, the elongation at break (%) of the low-zinc nitrile gloves prepared by the low-zinc nitrile gloves of example 1- example 3 and comparative example 1- comparative example 6 was determined. The test results are shown in Table 1; Aging resistance test: The tensile strength retention rate (%) of the low-zinc nitrile glove prepared from the application examples 1-3 and the comparative examples 1-6 after aging in a 70℃ oven for 168h was determined according to GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized or thermoplastic rubber", and the test results are shown in Table 1.

[0031] Table 1: Performance test results of the application examples 1-3 and the comparative examples 1-6

[0032] Data analysis: As can be seen from Table 1, the low-zinc nitrile glove prepared from the application examples has excellent wear resistance, tensile strength, elongation at break, aging resistance and low-zinc ion leaching rate.

[0033] The above has described one embodiment of the application in detail, but the content described is only the preferred embodiment of the application, and cannot be considered as limiting the scope of the application. Any equivalent changes and improvements made according to the scope of the application should still belong to the patent coverage of the application.

Claims

1. A low-zinc nitrile glove, characterized in that, The nitrile gloves are made from a composite latex. The composite latex comprises the following raw materials in parts by weight: 100-200 parts of nitrile latex, 0.3-0.5 parts of sodium dodecylbenzenesulfonate, 0.2-0.4 parts of Tween-80, 0.4-0.6 parts of zinc oxide, 0.8-1.2 parts of sulfur, 0.5-0.7 parts of accelerator BZ, 0.4-0.6 parts of accelerator PZ, 0.4-0.6 parts of antioxidant 2246, 1-2 g of titanium dioxide, and 38-84 parts of modifier dispersion; The modifier dispersion was prepared from deionized water, modified paraffin, Tween-80, Span-60, and modified cellulose. The modified paraffin is prepared by first oxidizing paraffin in air and then modifying it with ethylenediamine amino groups. The modified cellulose is prepared by first activating the carboxyl groups of carboxylated nanocellulose with 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide ester, then reacting it with chitosan, and finally introducing hydroxylated graphene quantum dots.

2. The low-zinc nitrile gloves according to claim 1, characterized in that, The preparation method of the composite latex is as follows: Sodium dodecylbenzenesulfonate and Tween-80 were added to nitrile latex and stirred for 10-20 minutes. Then, zinc oxide, sulfur, accelerator BZ, accelerator PZ, antioxidant 2246, and titanium dioxide were added in sequence and stirred. The pH was then adjusted to 10-10.5, and then the modifier dispersion was added and stirred for 20-30 hours to obtain the composite latex.

3. The low-zinc nitrile gloves according to claim 1, characterized in that, The preparation method of the modifier dispersion is as follows: Modified paraffin, Tween-80, and Span-60 were added to deionized water and ultrasonically emulsified at 78-80℃ for 20-30 minutes. Then, modified cellulose was added and ultrasonicated for 30-50 minutes to obtain a modifier dispersion.

4. The low-zinc nitrile gloves according to claim 3, characterized in that, The mass ratio of deionized water, modified paraffin, Tween-80, Span-60, and modified cellulose is 30-72:2.5-3.5:0.5-0.6:0.2-0.25:5-8.

5. The low-zinc nitrile glove according to claim 1, characterized in that, The modified paraffin is prepared as follows: A1: Add paraffin to cyclohexane and stir at 65-70℃ for 20-30 min. Then add cobalt acetate and heat to 88-90℃. Purge air at a rate of 0.5 L / min and react at 85-90℃ for 6-7 h. After cooling to 50-60℃, obtain an oxidized paraffin solution. A2: Add p-toluenesulfonic acid to ethylenediamine and stir at 38-40℃ for 10-20 min. Then add oxidized paraffin solution dropwise and react at 95-100℃ for 3-4 h. After cooling to 50-60℃, add petroleum ether. After standing for 30-40 min, remove the aqueous phase and remove toluene and petroleum ether by vacuum distillation of the upper layer solution to obtain modified paraffin.

6. The low-zinc nitrile glove according to claim 5, characterized in that, The mass ratio of cyclohexane, paraffin, and cobalt acetate in A1 is 200-250:100-125:0.3-0.4; The mass ratio of ethylenediamine, p-toluenesulfonic acid, oxidized paraffin solution, and petroleum ether in A2 is 4-5:0.5-0.7:300-375:30-40.

7. The low-zinc nitrile glove according to claim 1, characterized in that, The modified cellulose is prepared as follows: B1: Add carboxylated nanocellulose to deionized water and ultrasonically disperse for 20-30 min. Then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide ester and stir for 1-1.5 h to obtain nanocellulose dispersion. B2: Chitosan is dissolved in an aqueous acetic acid solution, then added to a nanocellulose dispersion and stirred at 45-50℃ for 3-4 hours. Hydroxygraphene quantum dots are then added and the pH is adjusted to 4.8-5.

2. The mixture is stirred at 55-60℃ for 2-3 hours, centrifuged, and the precipitate is washed and freeze-dried. The precipitate is then ground and passed through a 150-200 mesh sieve to obtain modified cellulose.

8. The low-zinc nitrile glove according to claim 7, characterized in that, The mass ratio of deionized water, carboxylated nanocellulose, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide ester in B1 is 100-120:5-6:0.5-0.6:0.3-0.

36. The mass fraction of the acetic acid aqueous solution in B2 is 1%; The mass ratio of chitosan, aqueous acetic acid solution, nanocellulose dispersion, and hydroxylated graphene quantum dots in B2 is 2-2.4:100-120:105-126:0.5-0.

6.

9. A method for preparing low-zinc nitrile gloves according to any one of claims 1-8, characterized in that, Includes the following steps: S1: After cleaning the ceramic hand mold by immersing it in sodium hydroxide solution, rinse it with deionized water, dry it, immerse it in an aqueous solution of calcium nitrate containing ethanol for 3-5 seconds, and dry it to obtain the pretreated hand mold. S2: Immerse the pre-treated hand mold in the composite latex, remove it and dry it in a forced-air drying at 45-50℃ for 1-3 minutes. Then, immerse the fingertips a second time, and then soak them in deionized water at 55-60℃ for 5-10 minutes. After drying in a forced-air drying, the rough glove is obtained. S3: Roll up the opening of the rough glove by 2-3mm using a rolling machine, then preheat at 80℃ for 5-7 minutes, vulcanize at 110-120℃ for 25-35 minutes, cool to 50-60℃, then chlorine wash, neutralize, immerse in antioxidant 1076 aqueous solution, wash with water, dry, and demold to obtain low zinc nitrile gloves.

10. The method for preparing low-zinc nitrile gloves according to claim 9, characterized in that, The calcium nitrate aqueous solution containing ethanol described in S1 has a calcium nitrate mass fraction of 10%-15% and an ethanol mass fraction of 3%. The mass fraction of the antioxidant 1076 aqueous solution in S3 is 0.1%.

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