Antistatic protective glove and preparation method thereof

Abstract

The invention discloses an antistatic protective glove and a preparation method thereof, and relates to the technical field of protective gloves. The antistatic protective glove is prepared from the following raw materials in parts by weight: 50 to 60 parts of natural latex, 40 to 50 parts of neoprene latex, 0.4 to 2 parts of potassium hydroxide, 1.2 to 1.8 parts of peregal O, 1.5 to 3 parts of sulfur, 1 to 2 parts of accelerant BZ, 3.5 to 5 parts of antistatic agent, 0.5 to 1 part of sodium carboxymethyl cellulose and 1.2 to 1.8 parts of anti-aging agent. The preparation method of the antistatic agent comprises the following steps: firstly, reacting 1, 3, 5-tri (2, 3-epoxypropoxy) benzene with N1, N7 dimethyl heptane-1, 7-diamine to obtain a hyperbranched polymer, and then carrying out quaternization on the hyperbranched polymer and chlorinated octadecane to obtain the antistatic agent. The antistatic protective glove provided by the invention has excellent antistatic performance and anti-aging performance.

Description

Technical Field

[0001] The invention relates to the technical field of protective gloves, and in particular to an antistatic protective glove and a preparation method thereof. Background Art

[0002] During the use of latex gloves, static electricity will be generated under the action of dynamic stress and friction, which will affect the performance of natural latex gloves. Especially in highly sensitive environments, such as the electronics manufacturing industry, even a tiny static discharge can break through the internal circuits of electronic components and cause component damage; in the chemical industry, the generation and accumulation of static electricity may cause static sparks, and the consequences will be disastrous when encountering flammable and explosive chemicals; in the medical field, static electricity may interfere with the normal operation of medical equipment and affect the accuracy of diagnosis and treatment. Antistatic latex gloves can allow workers to avoid static interference during operation and ensure the smooth progress of work.

[0003] In order to eliminate static electricity in gloves, technicians generally add antistatic agents to the raw materials to improve the antistatic performance of latex gloves. However, due to the poor compatibility of antistatic agents with latex, or easy precipitation and shedding, the stability of the antistatic performance of latex gloves is poor. Therefore, it is necessary to develop an antistatic latex glove.

[0004] A Chinese invention patent application with publication number CN117534883A discloses an antistatic latex glove and a preparation method thereof. The antistatic latex gloves prepared by the invention use a MOFs-carbon quantum dot composite as an antistatic agent and have good antistatic properties, but have poor compatibility with latex and are prone to precipitation, resulting in poor stability of the antistatic properties of the latex gloves. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention aims to provide an antistatic protective glove.

[0006] To achieve the above object, the present invention is implemented through the following technical solutions: An antistatic protective glove comprising the following raw materials in parts by weight: Natural latex: 50-60 parts; Chloroprene latex: 40-50 parts; Potassium hydroxide: 0.4-2 parts; Pingpingjia O: 1.2-1.8 parts; Sulfur: 1.5-3 parts; Accelerator BZ: 1-2 parts; Antistatic agent: 3.5-5 parts; Sodium carboxymethyl cellulose: 0.5-1 part; Anti-aging agent: 1.2-1.8 parts; The antistatic agent is firstly prepared by reacting 1,3,5-tri(2,3-epoxypropoxy)benzene with N1,N7 dimethylheptane-1,7-diamine to obtain a hyperbranched polymer, which is then quaternized with chlorooctadecane.

[0007] The antistatic agent is prepared by the following method: S1: Under nitrogen protection, 1,3,5-tri(2,3-epoxypropoxy)benzene, N1,N7 dimethylheptane-1,7-diamine and salicylic acid were stirred and mixed, heated to 140-160°C, reacted for 40-50h, and post-treated to obtain a hyperbranched polymer. The reaction equation is as follows: ; It should be noted that the structural formula of the above hyperbranched polymer is only used to represent the reaction between the functional groups in this step.

[0008] S2: Mix dichloromethane and hyperbranched polymer, add octadecane chloride dropwise, raise the temperature to reflux, react for 6-10 hours, and post-treat to obtain an antistatic agent. The reaction equation is as follows: ; In step S1, the molar ratio of 1,3,5-tris(2,3-epoxypropoxy)benzene, N1,N7 dimethylheptane-1,7-diamine and salicylic acid is 1:(2-2.5):(0.1-0.5).

[0009] In step S1, the mass ratio of the hyperbranched polymer to octadecane is 1:(7-10).

[0010] The antioxidant is prepared by the following method: S1: Under nitrogen protection, 2-[(3-aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid were mixed, heated to 140-160°C, reacted for 15-20h, and post-treated to obtain intermediate 1, the reaction equation of which is shown as follows: ; S2: Mix the intermediate 1, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol, p-toluenesulfonic acid and toluene, raise the temperature to 100-120°C, remove the generated water through a water separator, react for 6-10 hours, and post-treat to obtain an antioxidant. The reaction equation is as follows: ; In step S1, the molar ratio of 2-[(3-aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid is (2-2.5):1:(0.1-0.2).

[0011] In step S2, the molar ratio of the intermediate 1, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and p-toluenesulfonic acid is 1:(2-2.5):(0.1-0.2).

[0012] The potassium hydroxide is a 5-15wt% aqueous solution.

[0013] The solid content of the natural latex and the chloroprene latex is 50wt%; the peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant are all in an aqueous dispersion with a total solid content of 50wt%; the aqueous dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 0.4-1.0wt% of disodium methylene dinaphthalene sulfonate is added to the ground aqueous dispersion as a surfactant.

[0014] The preparation method of antistatic protective gloves comprises the following steps: S1: natural rubber latex, chloroprene latex, potassium hydroxide, peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant are mixed, stirred at 40°C, pre-vulcanized for 2 hours, and then kept at room temperature for 48 hours to obtain matured latex; S2: Clean the mold and dry it at 80°C for 5 minutes; S3: immersing the mold in a 20wt% calcium nitrate aqueous solution and drying at 90°C for 5 minutes; S4: immersing the mold in the matured latex for 30 seconds, and drying the latex at 80°C for 5 minutes; S5: passing the mold through a curling machine to curl the opening of the latex; S6: leaching at 60±5℃; S7: Drying and vulcanization at 110°C for 25 minutes; S8: demoulding, washing with hot water at 60°C to obtain protective gloves.

[0015] Due to the adoption of the above technical solution, the beneficial effects of the present invention include: (1) The present invention prepares an antistatic agent by reacting 1,3,5-tri(2,3-epoxypropoxy)benzene with N1,N7 dimethylheptane-1,7-diamine to obtain a hyperbranched polymer, which is then quaternized with octadecyl chloride.

[0016] (2) The present invention obtains intermediate 1 by reacting 2-[(3-aminophenyl)amino]benzoic acid with tetraethylene glycol diglycidyl ether, and then reacts with 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol to obtain an antioxidant.

[0017] (3) The antistatic agent prepared by the present invention preferentially adsorbs negative charges on the surface of the material through the positively charged quaternary ammonium salt to form an electrostatic shielding layer; the hydroxyl group (-OH) absorbs environmental moisture hygroscopically and can provide an ion migration channel to accelerate charge dissipation; the long alkyl chain structure is combined with the polymer matrix through van der Waals force, which promotes the polar end to be oriented to the surface to form a conductive monolayer, and continuously repairs the loss layer through dynamic migration, thereby improving the antistatic performance of the protective gloves.

[0018] (4) The antioxidant prepared by the present invention has excellent anti-aging performance through the synergistic effect of hindered phenol and aromatic amine; the flexible chain segment gives the molecular chain dynamic adaptability, which can improve the compatibility of the material, and the higher molecular weight improves the migration resistance of the antioxidant. DETAILED DESCRIPTION

[0019] The invention will be further described below in conjunction with the embodiments, but the invention is not limited to these embodiments.

[0020] Example 1 Preparation of antistatic agent: S1: Under nitrogen protection, 1 mol 1,3,5-tri(2,3-epoxypropoxy)benzene, 2 mol N1,N7 dimethylheptane-1,7-diamine, and 0.1 mol salicylic acid were added to a reaction bottle in sequence, the temperature was raised to 140°C, the reaction was carried out for 50 hours, the mixture was cooled to room temperature, 500 g of dichloromethane was added and stirred to mix, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times), deionized water (200 g × 3 times), and the mixture was distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, add 700 g of chlorooctadecane dropwise for 30 minutes, raise the temperature to reflux, react for 6 hours, distill at 40°C under reduced pressure for 2 hours, wash with 500 ml of toluene, filter, and vacuum dry at 80°C for 10 hours to obtain an antistatic agent.

[0021] Example 2 Preparation of antistatic agent: S1: Under nitrogen protection, 1 mol 1,3,5-tri(2,3-epoxypropoxy)benzene, 2.2 mol N1,N7 dimethylheptane-1,7-diamine, and 0.3 mol salicylic acid were added to a reaction bottle, heated to 150°C, reacted for 48 hours, cooled to room temperature, added 500 g of dichloromethane and stirred to mix well, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, add 900 g of chlorooctadecane dropwise for 30 minutes, raise the temperature to reflux, react for 8 hours, distill at 40°C under reduced pressure for 2 hours, wash with 500 ml of toluene, filter, and vacuum dry at 80°C for 10 hours to obtain an antistatic agent.

[0022] Example 3 Preparation of antistatic agent: S1: Under nitrogen protection, 1 mol 1,3,5-tri(2,3-epoxypropoxy)benzene, 2.5 mol N1,N7 dimethylheptane-1,7-diamine, and 0.5 mol salicylic acid were added to a reaction bottle, heated to 160°C, reacted for 40 hours, cooled to room temperature, added 500 g of dichloromethane and stirred to mix, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, add 1000 g of chlorooctadecane dropwise for 30 minutes, raise the temperature to reflux, react for 6-10 hours, distill at 40°C under reduced pressure for 2 hours, wash with 500 ml of toluene, filter, and vacuum dry at 80°C for 10 hours to obtain an antistatic agent.

[0023] Example 4 Preparation of antioxidant: S1: Under nitrogen protection, 2 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of tetraethylene glycol diglycidyl ether and 0.1 mol of salicylic acid were mixed, heated to 140°C, reacted for 20 hours, cooled to room temperature, 500 g of dichloromethane was added and stirred, the organic phase was extracted and washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain intermediate 1, whose H NMR spectrum data are as follows: 1H NMR (500MHz, Chloroform-d) δ 13.31 (s, 2H), 8.23 ​​(s, 2H), 7.87 (dd, J=8.0, 1.6 Hz, 2H), 7.43 (td, J=7.8, 1.5 Hz, 2H), 7.25 (d, J=7.7 Hz, 2H), 7.19 (dd, J=7.9,1.4 Hz, 2H), 7.11 (ddd, J=7.6, 2.2, 1.3 Hz, 2H), 7.05 (td, J=7.9, 1.4 Hz,2H), 6.61 (ddd, J=7.8, 2.0, 1.1 Hz, 2H), 6.36 (t, J=2.2 Hz, 2H), 5.86 (t, J=6.3 Hz, 2H), 4.02 (d, J=5.7 Hz, 2H), 3.96 (dp, J=6.1, 5.0 Hz, 2H), 3.95-3.85(m, 4H), 3.74 (dd, J=12.4, 4.9 Hz, 2H), 3.70 (s, 8H), 3.71-3.60 (m, 4H), 3.52-3.42 (m, 4H), 3.21 (ddd, J=13.5, 6.2, 5.0 Hz, 2H). S2: 3000ml toluene, 1mol intermediate 1, 2mol 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.1mol p-toluenesulfonic acid were added to the reaction bottle in sequence, the temperature was raised to 100°C, the generated water was removed by a water separator, the reaction was carried out for 10h, the mixture was cooled to room temperature, the toluene was removed by vacuum distillation at 70°C for 3h, the residue was dissolved in 800ml ethyl acetate, the mixture was washed with 200ml 5wt% sodium bicarbonate aqueous solution and 200ml saturated brine in sequence, the mixture was rotary evaporated at 60°C for 2h, and vacuum dried at 80°C for 10h to obtain an antioxidant, the hydrogen nuclear magnetic resonance spectrum data of which are as follows: 1H NMR (500 MHz, Chloroform-d) δ 8.08 (s, 2H), 7.95-7.87(m, 2H), 7.47-7.38 (m, 4H), 7.31-7.21 (m, 4H), 7.11 (ddd, J=7.6, 2.2, 1.3 Hz,2H), 6.87 (t, J=0.9 Hz, 4H), 6.61 (ddd, J=7.8, 2.1, 1.1 Hz, 2H), 6.36 (t, J=2.2 Hz, 2H), 5.86 (t, J=6.3 Hz, 2H), 4.69 (s, 2H), 4.30 (t, J=6.2 Hz, 4H),4.02 (d, J=5.7 Hz, 2H), 3.96 (dp, J=6.1, 5.0 Hz, 2H), 3.95-3.85 (m, 4H), 3.77-3.61 (m, 14H), 3.52-3.42 (m, 4H), 3.21 (ddd, J=13.5, 6.2, 5.0 Hz, 2H), 2.73 (tt, J=8.5, 1.0 Hz, 4H), 2.02 (tt, J=8.7, 6.3 Hz, 4H), 1.41 (s, 36H). Example 5 Preparation of antioxidant: S1: Under nitrogen protection, 2.3 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of tetraethylene glycol diglycidyl ether and 0.16 mol of salicylic acid were mixed, heated to 150°C, reacted for 18 hours, cooled to room temperature, 500 g of dichloromethane was added and stirred, the organic phase was extracted and washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain intermediate 1; S2: 3000 ml of toluene, 1 mol of intermediate 1, 2.3 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.18 mol of p-toluenesulfonic acid were added to a reaction bottle in sequence, the temperature was raised to 110°C, the generated water was removed through a water separator, the reaction was carried out for 8 hours, the mixture was cooled to room temperature, and the toluene was removed by reduced pressure distillation at 70°C for 3 hours. The residue was dissolved in 800 ml of ethyl acetate, washed with 200 ml of 5 wt% sodium bicarbonate aqueous solution and 200 ml of saturated brine in sequence, rotary evaporated at 60°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain an antioxidant.

[0024] Example 6 Preparation of antioxidant: S1: Under nitrogen protection, 2.5 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of tetraethylene glycol diglycidyl ether and 0.2 mol of salicylic acid were mixed, heated to 160°C, reacted for 15 h, cooled to room temperature, 500 g of dichloromethane was added and stirred, the organic phase was extracted and washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 h, and vacuum dried at 80°C for 10 h to obtain intermediate 1; S2: 3000 ml of toluene, 1 mol of intermediate 1, 2.5 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.2 mol of p-toluenesulfonic acid were added to a reaction bottle in sequence, the temperature was raised to 120°C, the generated water was removed through a water separator, the reaction was carried out for 6 hours, the mixture was cooled to room temperature, and the toluene was removed by reduced pressure distillation at 70°C for 3 hours. The residue was dissolved in 800 ml of ethyl acetate, washed with 200 ml of 5 wt% sodium bicarbonate aqueous solution and 200 ml of saturated brine in sequence, rotary evaporated at 60°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain an antioxidant.

[0025] Example 7

[0026] An antistatic protective glove, composed of the following raw materials in parts by weight: Natural latex: 50 parts; chloroprene latex: 40 parts; 5wt% potassium hydroxide solution: 2 parts; peregal O: 1.2 parts; sulfur: 1.5 parts; accelerator BZ: 1 part; antistatic agent (prepared in Example 1): 3.5 parts; sodium carboxymethyl cellulose: 0.5 parts; antioxidant (prepared in Example 4): 1.2 parts; Among the above raw materials, the solid content of natural latex and chloroprene latex is 50wt%; the peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all in an aqueous dispersion with a total solid content of 50wt%; the aqueous dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 0.4wt% of disodium methylene dinaphthalene sulfonate is added to the ground aqueous dispersion as a surfactant.

[0027] Example 8

[0028] An antistatic protective glove, composed of the following raw materials in parts by weight: Natural latex: 56 parts; Chloroprene latex: 48 parts; 12wt% potassium hydroxide solution: 1.2 parts; Peregal O: 1.6 parts; Sulfur: 2.4 parts; Accelerator BZ: 1.6 parts; Antistatic agent (prepared in Example 2): 4.2 parts; Sodium carboxymethyl cellulose: 0.7 parts; Antiaging agent (prepared in Example 5): 1.6 parts; Among the above raw materials, the solid content of natural latex and chloroprene latex is 50wt%; the peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all in an aqueous dispersion with a total solid content of 50wt%; the aqueous dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 0.8wt% of disodium methylene dinaphthalene sulfonate is added to the ground aqueous dispersion as a surfactant.

[0029] Example 9

[0030] An antistatic protective glove, composed of the following raw materials in parts by weight: Natural latex: 60 parts; Chloroprene latex: 50 parts; 15wt% potassium hydroxide solution: 0.4 parts; Peregal O: 1.8 parts; Sulfur: 3 parts; Accelerator BZ: 2 parts; Antistatic agent (prepared in Example 3): 5 parts; Sodium carboxymethyl cellulose: 1 part; Antiaging agent (prepared in Example 6): 1.8 parts; Among the above raw materials, the solid content of natural latex and chloroprene latex is 50wt%; the peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all in an aqueous dispersion with a total solid content of 50wt%; the aqueous dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 1.0wt% of disodium methylene dinaphthalene sulfonate is added to the ground aqueous dispersion as a surfactant.

[0031] Comparative Example 1 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent of equal mass prepared by the following method: S1: Under nitrogen protection, 1 mol 1,3,5-tri(2,3-epoxypropoxy)benzene, 2.2 mol N1,N7 dimethylheptane-1,7-diamine, and 0.3 mol salicylic acid were added to a reaction bottle, heated to 150°C, reacted for 48 hours, cooled to room temperature, added 500 g dichloromethane and stirred to mix well, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, add 200 g of chlorooctadecane dropwise for 30 minutes, raise the temperature to reflux, react for 8 hours, distill at 40°C under reduced pressure for 2 hours, wash with 500 ml of toluene, filter, and vacuum dry at 80°C for 10 hours to obtain an antistatic agent.

[0032] Comparative Example 2 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent of equal mass prepared by the following method: S1: Under nitrogen protection, 1 mol of glycidyl ether, 2.2 mol of N1,N7 dimethylheptane-1,7-diamine, and 0.3 mol of salicylic acid were added to a reaction bottle, heated to 150°C, reacted for 48 hours, cooled to room temperature, 500 g of dichloromethane was added and stirred to mix, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, slowly drop 450 g of chlorooctadecane, add for 30 minutes, heat to reflux, react for 8 hours, distill at 40 ° C under reduced pressure for 2 hours, wash with 500 ml of toluene, filter, and vacuum dry at 80 ° C for 10 hours to obtain an antistatic agent.

[0033] Comparative Example 3 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent prepared in the following steps of equal mass: S1: Under nitrogen protection, 1 mol 1,3,5-tri(2,3-epoxypropoxy)benzene, 2.3 mol N1,N7 dimethylheptane-1,7-diamine, and 0.3 mol salicylic acid were added to a reaction bottle, heated to 150°C, reacted for 48 hours, cooled to room temperature, added 500 g of dichloromethane and stirred to mix, the organic phase was washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 1 hour, and vacuum dried at 80°C for 10 hours to obtain a hyperbranched polymer; S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction bottle, stir to mix, slowly drop 900 g of 1-chlorooctane, add for 30 min, raise the temperature to reflux, react for 8 h, distill at 40 ° C under reduced pressure for 3 h, wash with 500 ml of toluene, filter, and vacuum dry at 80 ° C for 10 h to obtain an antistatic agent.

[0034] Comparative Example 4 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antioxidant (prepared in Example 5) is replaced by an equal mass of intermediate 1 (prepared in Example 5) as the antioxidant.

[0035] Comparative Example 5 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antioxidant (prepared in Example 5) is replaced with an equal mass of a modified antioxidant prepared in the following steps: S1: Under nitrogen protection, 1.1 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of 2-(2,5,8,11,14-pentaoxapentadecyl)oxirane and 0.1 mol of salicylic acid were mixed, heated to 150°C, reacted for 18 hours, cooled to room temperature, 500 g of dichloromethane was added and stirred, the organic phase was extracted and washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 1 hour, and vacuum dried at 80°C for 10 hours to obtain intermediate 1; S2: 3000 ml of toluene, 1 mol of intermediate 1, 1.1 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.1 mol of p-toluenesulfonic acid were added to a reaction flask in sequence, the temperature was raised to 110°C, the generated water was removed through a water separator, the reaction was carried out for 8 hours, the mixture was cooled to room temperature, and the toluene was removed by reduced pressure distillation at 70°C for 3 hours. The residue was dissolved in 800 ml of ethyl acetate, washed with 200 ml of 5 wt% sodium bicarbonate aqueous solution and 200 ml of saturated brine in sequence, rotary evaporated at 60°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain an antioxidant.

[0036] Comparative Example 6 The raw material components and proportions of the protective gloves are basically the same as those of Example 8, except that the antioxidant (prepared in Example 5) is replaced with an equal mass of a modified antioxidant prepared in the following steps: S1: Under nitrogen protection, 3.2 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of glyceryl propoxy triglycidyl ether and 0.3 mol of salicylic acid were mixed, heated to 150°C, reacted for 18 hours, cooled to room temperature, 500 g of dichloromethane was added and stirred, the organic phase was extracted and washed with 5 wt% sodium bicarbonate aqueous solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40°C for 1 hour, and vacuum dried at 80°C for 10 hours to obtain intermediate 1; S2: 3000 ml of toluene, 1 mol of intermediate 1, 3.2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.25 mol of p-toluenesulfonic acid were added to a reaction bottle in sequence, the temperature was raised to 110°C, the generated water was removed through a water separator, the reaction was carried out for 8 hours, the mixture was cooled to room temperature, and the toluene was removed by reduced pressure distillation at 70°C for 3 hours. The residue was dissolved in 800 ml of ethyl acetate, washed with 200 ml of 5 wt% sodium bicarbonate aqueous solution and 200 ml of saturated brine in sequence, rotary evaporated at 60°C for 2 hours, and vacuum dried at 80°C for 10 hours to obtain an antioxidant.

[0037] The protective gloves of Examples 7-9 and Comparative Examples 1-6 were prepared by the following process: S1: Natural rubber latex, chloroprene latex, potassium hydroxide, peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant were stirred and mixed, kept at 40°C for 2 hours, and then kept at room temperature for 48 hours to obtain matured latex; S2: Clean the mold and dry it at 80°C for 5 minutes; S3: immersing the mold in a 20wt% calcium nitrate aqueous solution and drying at 90°C for 5 minutes; S4: immersing the mold in the matured latex for 30 seconds, and drying the latex at 80°C for 5 minutes; S5: passing the mold through a curling machine to curl the opening of the latex; S6: leaching at 60±5℃; S7: Drying and vulcanization at 110°C for 25 minutes; S8: demoulding, washing with hot water at 60°C to obtain protective gloves.

[0038] The raw materials used in the examples and comparative examples of the present application are as follows: natural rubber latex of brand SCR WF, purchased from Yunnan Guangken Rubber Co., Ltd.; chloroprene rubber latex of brand 750, purchased from Lisennoko (China) Investment Co., Ltd.; sulfur is S-80 type special sulfur powder produced by Qingdao Luchuan Chemical Co., Ltd., with a mesh size of 400 mesh; sodium carboxymethyl cellulose is purchased from Hebei Yanxing Chemical Co., Ltd., with a content greater than 98%.

[0039] The protective gloves of Examples 4-6 and Comparative Examples 1-6 of the present application were subjected to tensile strength, elongation at break, antistatic performance, and aging tests. The tensile strength and elongation at break were tested in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber and thermoplastic rubber", at a temperature of 23°C, 1B type test specimen, and a tensile speed of 100mm / min; the antistatic performance was tested in accordance with BS EN16350-2014, balancing at 25°C and 45% humidity for 24 hours, and the vertical resistance was tested; the aging test was to place the protective gloves in a hot air aging box and age them at 100°C for 4 days, and then conduct relevant performance tests. The test results are shown in Table 1.

[0040] Table 1 Performance test table

[0041] It can be seen from Examples 7, 8 and 9 in Table 1 that the protective gloves of the present invention have excellent mechanical properties (test piece tensile strength, test piece elongation at break), antistatic properties (resistance value) and anti-aging properties (aging test).

[0042] The protective gloves prepared in Comparative Example 1 have poor antistatic performance, and the vertical resistance is 2.1MΩ. The reason may be that when the addition amount of octadecane is reduced from 900g to 200g, less quaternary ammonium salt is formed, and the quaternary ammonium salt of the positively charged polar group of the antistatic agent preferentially adsorbs the negative charge on the surface of the material to form an electrostatic shielding layer, thereby achieving the purpose of antistatic. When the degree of quaternization is insufficient, the electrostatic shielding layer cannot be formed, resulting in a decrease in the antistatic performance.

[0043] Comparative Example 2 is an antistatic agent prepared by replacing 1,3,5-tri(2,3-epoxypropoxy)benzene with glycidyl ether. The vertical resistance is 1.2MΩ. The possible reason is that the antistatic agent generally absorbs environmental moisture through the hygroscopicity of hydroxyl (-OH) and forms H-containing + and OH - The ionic water film provides an ion migration channel to accelerate charge dissipation; the flexible segments of the fatty chain cause some hydroxyl groups to be wrapped, and the exposure ratio is insufficient, making it difficult to form a continuous conductive water film, resulting in a decrease in antistatic performance; and the antistatic agent prepared from 1,3,5-tri(2,3-epoxypropoxy)benzene has a rigid benzene ring skeleton, which can form a highly branched three-dimensional network structure, and the density of terminal hydroxyl groups is significantly improved to form a continuous conductive water film.

[0044] Comparative Example 3 is an antistatic agent prepared by replacing chlorooctadecane with 1-chlorooctane. It can be seen from the data in Table 1 that its elongation at break and antistatic performance are poor. The reason is that the solubility parameters of long-chain alkyl and rubber are closer, the phase separation tendency is reduced, and internal defects can be reduced. Long-chain alkyl antistatic agents have higher compatibility with the rubber matrix due to their longer molecular chains. They can slowly migrate to the surface and arrange in a directional manner to form a continuous and stable conductive layer; at the same time, the long-chain structure is physically entangled with the rubber through stronger van der Waals forces, reducing the loss caused by friction or cleaning, and can also significantly extend the durability of the antistatic effect. Long-chain alkyl can be embedded between rubber molecular chains, weakening rigid interactions, improving flexibility (increasing elongation at break) and dispersing stress.

[0045] Comparative Example 4 is a comparative example different from Example 8. The protective gloves prepared by using Intermediate 1 (prepared in Example 5) as an antioxidant have poor anti-aging performance compared with the present application. After aging, the loss rate of tensile strength and elongation at break is large. The reason is that the antioxidant prepared in Comparative Example 4 only contains the process of inhibiting the chain reaction by the NH structure in Intermediate 1 to play an anti-aging role, has a small molecular weight, low diffusion resistance, and poor migration resistance, resulting in loss of the antioxidant, making its anti-aging ability poor.

[0046] Comparative Examples 5 and 6 are different from Example 8. The antioxidants prepared by replacing tetraethylene glycol diglycidyl ether with 2-(2,5,8,11,14-pentaoxapentadecanyl)ethylene oxide and glycerol propoxy triglycidyl ether, respectively, can be seen from the data in Table 1 that their anti-aging performance is poor. The antioxidants used in Comparative Examples 5 and 6 are all formed by the synergistic effect of hindered phenols and aromatic amines to form a stable antioxidant structure to achieve the purpose of anti-aging; however, the antioxidant used in Comparative Example 5 has fewer functional groups of hindered phenols and hindered amines, and the molecular weight is also small, which is easy to migrate out, resulting in reduced anti-aging performance; the antioxidant used in Comparative Example 6 contains 3 epoxy groups, and the antioxidant molecules formed contain three functional groups of hindered phenols, and the molecular weight is large. Although it is resistant to migration, the uniformity of the distribution of the antioxidant inside the material is reduced, and it is easy to form a local high concentration area, while the low concentration area becomes an aging weak point due to lack of protection. The antioxidant used in the present application contains an ether bond (-O-), which gives the molecular chain flexibility, facilitates dispersion in latex, and improves the compatibility of the antioxidant in rubber.

[0047] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. An antistatic protective glove, characterized in that: The invention comprises the following raw materials in parts by weight: Natural latex: 50-60 parts; Chloroprene latex: 40-50 parts; Potassium hydroxide: 0.4-2 parts; Pingpingjia O: 1.2-1.8 parts; Sulfur: 1.5-3 parts; Accelerator BZ: 1-2 parts; Antistatic agent: 3.5-5 parts; Sodium carboxymethyl cellulose: 0.5-1 part; Anti-aging agent: 1.2-1.8 parts; The antistatic agent is firstly prepared by reacting 1,3,5-tri(2,3-epoxypropoxy)benzene with N1,N7 dimethylheptane-1,7-diamine to obtain a hyperbranched polymer, which is then quaternized with chlorooctadecane.

2. The antistatic protective gloves according to claim 1, characterized in that: The antistatic agent is prepared by the following method: S1: Under nitrogen protection, 1,3,5-tri(2,3-epoxypropoxy)benzene, N1,N7 dimethylheptane-1,7-diamine and salicylic acid were stirred and mixed, the temperature was raised to 140-160° C., the reaction was carried out for 40-50 hours, and a hyperbranched polymer was obtained by post-treatment; S2: Mix dichloromethane and hyperbranched polymer, add octadecane chloride dropwise, raise the temperature to reflux, react for 6-10 hours, and perform post-treatment to obtain an antistatic agent.

3. The antistatic protective gloves according to claim 2, characterized in that: In step S1, the molar ratio of 1,3,5-tris(2,3-epoxypropoxy)benzene, N1,N7 dimethylheptane-1,7-diamine and salicylic acid is 1:(2-2.5):(0.1-0.5).

4. The antistatic protective gloves according to claim 2, characterized in that: In step S1, the mass ratio of the hyperbranched polymer to octadecane is 1:(7-10).

5. The antistatic protective gloves according to claim 1, characterized in that: The antioxidant is prepared by the following method: S1: Under nitrogen protection, 2-[(3-aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid were mixed, heated to 140-160° C., reacted for 15-20 h, and post-treated to obtain intermediate 1; S2: Mix the intermediate 1, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol, p-toluenesulfonic acid and toluene, heat to 100-120°C, remove the generated water through a water separator, react for 6-10 hours, and post-treat to obtain an antioxidant.

6. The antistatic protective gloves according to claim 5, characterized in that: In step S1, the molar ratio of 2-[(3-aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid is (2-2.5):1:(0.1-0.2).

7. The antistatic protective gloves according to claim 5, characterized in that: In step S2, the molar ratio of the intermediate 1, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and p-toluenesulfonic acid is 1:(2-2.5):(0.1-0.2).

8. The antistatic protective gloves according to claim 1, characterized in that: The potassium hydroxide is a 5-15wt% aqueous solution.

9. The antistatic protective gloves according to claim 1, characterized in that: The solid content of the natural latex and the chloroprene latex is 50wt%; the peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant are all in an aqueous dispersion with a total solid content of 50wt%; the aqueous dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 0.4-1.0wt% of disodium methylene dinaphthalene sulfonate is added to the ground aqueous dispersion as a surfactant.

10. A method for preparing the antistatic protective gloves according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: natural rubber latex, chloroprene latex, potassium hydroxide, peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant are mixed, stirred at 40°C, pre-vulcanized for 2 hours, and then kept at room temperature for 48 hours to obtain matured latex; S2: Clean the mold and dry it at 80°C for 5 minutes; S3: immersing the mold in a 20wt% calcium nitrate aqueous solution and drying at 90°C for 5 minutes; S4: immersing the mold in the matured latex for 30 seconds, and drying the latex at 80°C for 5 minutes; S5: passing the mold through a curling machine to curl the opening of the latex; S6: leaching at 60±5℃; S7: Drying and vulcanization at 110°C for 25 minutes; S8: demoulding, washing with hot water at 60°C to obtain protective gloves.

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