An antistatic protective glove and its preparation method

Abstract

The present invention discloses an antistatic protective glove and a preparation method thereof, relating to the technical field of protective gloves. The antistatic protective glove 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, Peregal 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, antioxidant: 1.2 - 1.8 parts; the antistatic agent is first obtained by reacting 1,3,5-tris(2,3-epoxypropoxy)benzene with N1,N7-dimethylheptane-1,7-diamine to obtain a hyperbranched polymer, and then quaternized with chlorooctadecane. The antistatic protective glove provided by the present invention has excellent antistatic performance and anti-aging performance.

Description

Technical Field

[0001] The present invention relates to the technical field of protective gloves, and particularly relates 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 dynamic stress and friction, affecting the performance of natural latex gloves. Especially in highly sensitive environments, such as the electronics manufacturing industry, even a tiny electrostatic discharge can break through the internal circuit of electronic components, resulting in component damage; in the chemical industry, the generation and accumulation of static electricity may trigger static sparks, and when encountering flammable and explosive chemical substances, the consequences are unimaginable; in the medical field, static electricity may interfere with the normal operation of medical equipment, affecting the accuracy of diagnosis and treatment. Antistatic latex gloves can enable 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 between the antistatic agent and latex, or easy precipitation and shedding, the stability of the antistatic performance of latex gloves is not good. Therefore, it is necessary to develop an antistatic latex glove.

[0004] Chinese Patent Application Publication No. CN117534883A discloses an antistatic latex glove and a preparation method thereof. The prepared antistatic latex glove uses MOFs-carbon quantum dot composite as an antistatic agent, which has good antistatic performance, but has poor compatibility with latex and is easy to precipitate, resulting in poor stability of the antistatic performance of latex gloves. Summary of the Invention

[0005] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide an antistatic protective glove.

[0006] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0007] An antistatic protective glove, comprising the following raw materials in parts by weight:

[0008] Natural latex: 50 - 60 parts;

[0009] Chloroprene latex: 40 - 50 parts;

[0010] Potassium hydroxide: 0.4 - 2 parts;

[0011] Perganol O: 1.2 - 1.8 parts;

[0012] Sulfur: 1.5 - 3 parts;

[0013] Accelerator BZ: 1 - 2 parts;

[0014] Antistatic agent: 3.5 - 5 parts;

[0015] Sodium carboxymethyl cellulose: 0.5 - 1 part;

[0016] Antioxidant: 1.2 - 1.8 parts;

[0017] The antistatic agent is first obtained by reacting 1,3,5 - tris(2,3 - epoxypropoxy)benzene with N1,N7 - dimethylheptane - 1,7 - diamine to get a hyperbranched polymer, and then quaternized with octadecyl chloride.

[0018] The antistatic agent is prepared by the following method:

[0019] S1: Under nitrogen protection, 1,3,5 - tris(2,3 - epoxypropoxy)benzene, N1,N7 - dimethylheptane - 1,7 - diamine and salicylic acid are stirred and mixed evenly, heated to 140 - 160 °C, and reacted for 40 - 50 h. After post - treatment, a hyperbranched polymer is obtained. The reaction equation is shown as follows:

[0020] ;

[0021] It should be noted that the structural formula of the above - mentioned hyperbranched polymer is only used to represent the reaction between functional groups in this step.

[0022] S2: Dichloromethane and the hyperbranched polymer are mixed evenly, octadecyl chloride is added dropwise. After the addition is complete, the temperature is raised to reflux and reacted for 6 - 10 h. After post - treatment, an antistatic agent is obtained. The reaction equation is shown as follows:

[0023] ;

[0024] 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).

[0025] In step S1, the mass ratio of the hyperbranched polymer and octadecyl chloride is 1:(7 - 10).

[0026] The antioxidant is prepared by the following method:

[0027] S1: Under nitrogen protection, 2 - [(3 - aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid are mixed evenly, heated to 140 - 160 °C, and reacted for 15 - 20 h. After post - treatment, intermediate 1 is obtained. The reaction equation is shown as follows:

[0028] ;

[0029] S2: Mix intermediate 1, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol, p-toluenesulfonic acid and toluene evenly, heat up to 100 - 120 °C, remove the generated water through a water separator, react for 6 - 10 h, and perform post-treatment to obtain the antioxidant. The reaction equation is shown as follows:

[0030] ;

[0031] In step S1, the molar ratio of the feed of 2-[(3-aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid is (2 - 2.5):1:(0.1 - 0.2).

[0032] In step S2, the molar ratio of the feed of 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).

[0033] The potassium hydroxide is an aqueous solution with a concentration of 5 - 15 wt%.

[0034] The solid contents of the natural rubber latex and the chloroprene rubber latex are 50 wt%; the Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano-abrasive machine until the D90 of the dispersion is not more than 3 microns, and 0.4 - 1.0 wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.

[0035] A method for preparing an antistatic protective glove, comprising the following steps:

[0036] S1: Mix the natural rubber latex, chloroprene rubber latex, potassium hydroxide, Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant evenly, keep it warm and stir at 40 °C, pre-vulcanize for 2 h, and then stand still at room temperature for 48 h to obtain a cured latex;

[0037] S2: Clean the mold, dry it at 80 °C for 5 min;

[0038] S3: Immerse the mold in a 20 wt% aqueous solution of calcium nitrate, dry it at 90 °C for 5 min;

[0039] S4: Immerse the mold in the cured latex, stay for 30 s, and dry the latex at 80 °C for 5 min;

[0040] S5: Pass the mold through a hemming machine to hem the opening of the latex;

[0041] S6: Leach at 60 ± 5 °C;

[0042] S7: Dry and vulcanize at 110 °C for 25 min;

[0043] S8: Demold, wash with hot water at 60 °C to obtain the protective gloves.

[0044] Due to the above technical solutions, the beneficial effects of the present invention include:

[0045] (1) In the present invention, a hyperbranched polymer is obtained by reacting 1,3,5-tris(2,3-epoxypropoxy)benzene with N1,N7-dimethylheptane-1,7-diamine, and then quaternized with octadecyl chloride to prepare an antistatic agent.

[0046] (2) In the present invention, intermediate 1 is obtained by reacting 2-[(3-aminophenyl)amino]benzoic acid with tetraethylene glycol diglycidyl ether, and then an antioxidant is obtained by reacting with 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol.

[0047] (3) The antistatic agent prepared in the present invention preferentially adsorbs the 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) adsorbs moisture in the environment by hygroscopicity, which can provide an ion migration channel to accelerate the dissipation of charges; the long alkyl chain structure combines with the polymer matrix through van der Waals forces, promoting the oriented arrangement of the polar ends to the surface to form a conductive monolayer molecule, and continuously repairing the loss layer through dynamic migration, thereby improving the antistatic performance of the protective gloves.

[0048] (4) The antioxidant prepared in the present invention has excellent anti-aging performance through the synergistic effect of hindered phenol and aromatic amine; the flexible chain segment endows the molecular chain with dynamic adaptability, which can improve the compatibility of the material, and the higher molecular weight improves the migration resistance of the antioxidant. Specific embodiments

[0049] The following is further described in conjunction with embodiments, but the present invention is not limited to these embodiments.

[0050] Example 1 Preparation of antistatic agent:

[0051] S1: Under nitrogen protection, 1 mol of 1,3,5-tris(2,3-epoxypropoxy)benzene, 2 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.1 mol of salicylic acid are sequentially added to the reaction flask, heated to 140 °C, reacted for 50 h, cooled to room temperature, 500 g of dichloromethane is added and stirred evenly, the organic phase is washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 2 h, and dried in vacuum at 80 °C for 10 h to obtain the hyperbranched polymer;

[0052] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, dropwise add 700 g of octadecyl chloride, finish dropping in 30 min, heat up to reflux, react for 6 h, carry out reduced-pressure distillation at 40 °C for 2 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0053] Example 2 Preparation of antistatic agent:

[0054] S1: Under nitrogen protection, add 1 mol of 1,3,5-tris(2,3-epoxypropoxy)benzene, 2.2 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.3 mol of salicylic acid into a reaction flask, heat up to 150 °C, react for 48 h, cool to room temperature, add 500 g of dichloromethane and stir to mix evenly. Wash the organic phase successively with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), carry out reduced-pressure distillation at 40 °C for 2 h, and dry in vacuum at 80 °C for 10 h to obtain the hyperbranched polymer;

[0055] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, dropwise add 900 g of octadecyl chloride, finish dropping in 30 min, heat up to reflux, react for 8 h, carry out reduced-pressure distillation at 40 °C for 2 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0056] Example 3 Preparation of antistatic agent:

[0057] S1: Under nitrogen protection, add 1 mol of 1,3,5-tris(2,3-epoxypropoxy)benzene, 2.5 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.5 mol of salicylic acid into a reaction flask, heat up to 160 °C, react for 40 h, cool to room temperature, add 500 g of dichloromethane and stir to mix evenly. Wash the organic phase successively with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), carry out reduced-pressure distillation at 40 °C for 2 h, and dry in vacuum at 80 °C for 10 h to obtain the hyperbranched polymer;

[0058] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, dropwise add 1000 g of octadecyl chloride, finish dropping in 30 min, heat up to reflux, react for 6 - 10 h, carry out reduced-pressure distillation at 40 °C for 2 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0059] Example 4 Preparation of antioxidant:

[0060] 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 evenly, heated to 140 °C, reacted for 20 h, cooled to room temperature, 500 g of dichloromethane was added and stirred evenly. The organic phase was successively extracted and washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 2 h, and dried in vacuo at 80 °C for 10 h to obtain Intermediate 1. The nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H 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).

[0061] S2: 3000 ml of toluene, 1 mol of Intermediate 1, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-1-propanol and 0.1 mol of p-toluenesulfonic acid were successively added to the reaction flask, heated to 100 °C, and the generated water was removed through a water separator. The reaction was carried out for 10 h, cooled to room temperature, toluene was removed by distillation under reduced pressure at 70 °C for 3 h. The residue was dissolved in 800 ml of ethyl acetate and successively washed with 200 ml of 5 wt% aqueous sodium bicarbonate solution and 200 ml of saturated brine, rotary evaporated at 60 °C for 2 h, and dried in vacuo at 80 °C for 10 h to obtain the antioxidant. The nuclear magnetic resonance hydrogen spectrum data are as follows: 11H 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).

[0062] Example 5 Preparation of Antioxidant:

[0063] 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 evenly, heated to 150 °C, reacted for 18 h, cooled to room temperature, 500 g of dichloromethane was added and stirred evenly. The organic phase was successively extracted and washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 2 h, and dried in vacuum at 80 °C for 10 h to obtain Intermediate 1;

[0064] 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 successively added to the reaction flask, heated to 110 °C, the generated water was removed through a water separator, reacted for 8 h, cooled to room temperature, toluene was removed by distillation under reduced pressure at 70 °C for 3 h. The residue was dissolved in 800 ml of ethyl acetate, successively washed with 200 ml of 5 wt% aqueous sodium bicarbonate solution and 200 ml of saturated brine, rotary evaporated at 60 °C for 2 h, and dried in vacuum at 80 °C for 10 h to obtain the antioxidant.

[0065] Example 6 Preparation of Antioxidant:

[0066] 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 evenly, heated to 160 °C, reacted for 15 h, cooled to room temperature, 500 g of dichloromethane was added and stirred evenly. The organic phase was successively extracted and washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 2 h, and dried in vacuo at 80 °C for 10 h to obtain Intermediate 1.

[0067] 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 successively added to the reaction flask, heated to 120 °C, and the generated water was removed through a water separator. The reaction was carried out for 6 h, cooled to room temperature, and toluene was removed by distillation under reduced pressure at 70 °C for 3 h. The residue was dissolved in 800 ml of ethyl acetate, successively washed with 200 ml of 5 wt% aqueous sodium bicarbonate solution and 200 ml of saturated brine, rotary evaporated at 60 °C for 2 h, and dried in vacuo at 80 °C for 10 h to obtain the antioxidant.

[0068] Example 7

[0069] An antistatic protective glove is composed of the following raw materials in parts by weight:

[0070] Natural latex: 50 parts; Chloroprene latex: 40 parts; 5 wt% 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 part; Antioxidant (prepared in Example 4): 1.2 parts;

[0071] Among the above raw materials, the solid contents of natural latex and chloroprene latex are 50 wt%; the Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose and antioxidant are all aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano-abrasive machine to a dispersion D90 not greater than 3 μm, and 0.4 wt% of sodium methylene bisnaphthalenesulfonate is added as a surfactant to the ground aqueous dispersion.

[0072] Example 8

[0073] An antistatic protective glove is composed of the following raw materials in parts by weight:

[0074] Natural rubber latex: 56 parts; Chloroprene rubber 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 part; Antioxidant (prepared in Example 5): 1.6 parts;

[0075] Among the above raw materials, the solid content of natural rubber latex and chloroprene rubber latex is 50wt%; the Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all aqueous dispersions with a total solid content of 50wt%; the aqueous dispersions are all ground by a nano-abrasive machine until the D90 of the dispersion is not more than 3 microns, and 0.8wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.

[0076] Example 9

[0077] An antistatic protective glove is composed of the following raw materials in parts by weight:

[0078] Natural rubber latex: 60 parts; Chloroprene rubber latex: 50 parts; 15wt% potassium hydroxide solution: 0.4 part; 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; Antioxidant (prepared in Example 6): 1.8 parts;

[0079] Among the above raw materials, the solid content of natural rubber latex and chloroprene rubber latex is 50wt%; the Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all aqueous dispersions with a total solid content of 50wt%; the aqueous dispersions are all ground by a nano-abrasive machine until the D90 of the dispersion is not more than 3 microns, and 1.0wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.

[0080] Comparative Example 1

[0081] The raw material components and ratios of the protective glove are basically the same as those in Example 8, the difference is that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent prepared by the following method with the same mass:

[0082] S1: Under nitrogen protection, add 1 mol of 1,3,5-tris(2,3-epoxypropoxy)benzene, 2.2 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.3 mol of salicylic acid into a reaction flask, heat up to 150 °C, react for 48 h, cool to room temperature, add 500 g of dichloromethane and stir evenly. The organic phase is successively washed with 5wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 2 h, and dried in vacuum at 80 °C for 10 h to obtain a hyperbranched polymer;

[0083] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, dropwise add 200 g of octadecyl chloride, finish dropping in 30 min, heat up to reflux, react for 8 h, carry out vacuum distillation at 40 °C for 2 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0084] Comparative Example 2

[0085] The raw material components and their ratios of the protective gloves are basically the same as those in Example 8, the difference is that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent prepared by the following method with the same mass:

[0086] S1: Under nitrogen protection, add 1 mol of glycidyl ether, 2.2 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.3 mol of salicylic acid into a reaction flask, heat up to 150 °C, react for 48 h, cool to room temperature, add 500 g of dichloromethane and stir to mix evenly. The organic phase is successively washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), carry out vacuum distillation at 40 °C for 2 h, and dry in vacuum at 80 °C for 10 h to obtain the hyperbranched polymer;

[0087] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, slowly dropwise add 450 g of octadecyl chloride, finish dropping in 30 min, heat up to reflux, react for 8 h, carry out vacuum distillation at 40 °C for 2 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0088] Comparative Example 3

[0089] The raw material components and their ratios of the protective gloves are basically the same as those in Example 8, the difference is that the antistatic agent (prepared in Example 2) is replaced with an antistatic agent prepared by the following steps with the same mass:

[0090] S1: Under nitrogen protection, add 1 mol of 1,3,5-tris(2,3-epoxypropoxy)benzene, 2.3 mol of N1,N7-dimethylheptane-1,7-diamine, and 0.3 mol of salicylic acid into a reaction flask, heat up to 150 °C, react for 48 h, cool to room temperature, add 500 g of dichloromethane and stir to mix evenly. The organic phase is successively washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), carry out vacuum distillation at 40 °C for 1 h, and dry in vacuum at 80 °C for 10 h to obtain the hyperbranched polymer;

[0091] S2: Add 1000 ml of dichloromethane and 100 g of hyperbranched polymer into a reaction flask, stir to mix evenly, slowly dropwise add 900 g of 1-chlorooctane, finish dropping in 30 min, heat up to reflux, react for 8 h, carry out vacuum distillation at 40 °C for 3 h, wash with 500 ml of toluene, filter, and dry in vacuum at 80 °C for 10 h to obtain the antistatic agent.

[0092] Comparative Example 4

[0093] The raw material components and their ratios of the protective gloves are basically the same as those in Example 8, the difference is that the antioxidant (prepared in Example 5) is replaced with an equal mass of Intermediate 1 (prepared in Example 5) as the antioxidant.

[0094] Comparative Example 5

[0095] The raw material components and their ratios of the protective gloves are basically the same as those in Example 8, the difference is that the antioxidant (prepared in Example 5) is replaced with an equal mass of the modified antioxidant prepared by the following steps:

[0096] S1: Under nitrogen protection, mix 1.1 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of 2-(2,5,8,11,14-pentaoxapentadecyl)ethylene oxide and 0.1 mol of salicylic acid evenly, heat up to 150 °C, react for 18 h, cool to room temperature, add 500 g of dichloromethane and stir to mix evenly, extract and wash the organic phase successively with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), carry out vacuum distillation at 40 °C for 1 h, and dry in vacuum at 80 °C for 10 h to obtain Intermediate 1;

[0097] S2: Add 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 into a reaction flask in sequence, heat up to 110 °C, remove the generated water through a water separator, react for 8 h, cool to room temperature, carry out vacuum distillation at 70 °C for 3 h to remove toluene, dissolve the residue in 800 ml of ethyl acetate, wash successively with 200 ml of 5 wt% aqueous sodium bicarbonate solution and 200 ml of saturated brine, carry out rotary evaporation at 60 °C for 2 h, and dry in vacuum at 80 °C for 10 h to obtain the antioxidant.

[0098] Comparative Example 6

[0099] The raw material components and their ratios of the protective gloves are basically the same as those in Example 8, the difference is that the antioxidant (prepared in Example 5) is replaced with an equal mass of the modified antioxidant prepared by the following steps:

[0100] S1: Under nitrogen protection, 3.2 mol of 2-[(3-aminophenyl)amino]benzoic acid, 1 mol of glycerol propoxytriepoxy glycidyl ether and 0.3 mol of salicylic acid were mixed evenly, heated to 150 °C, reacted for 18 h, cooled to room temperature, 500 g of dichloromethane was added and stirred evenly. The organic phase was successively extracted and washed with 5 wt% aqueous sodium bicarbonate solution (120 g × 3 times) and deionized water (200 g × 3 times), distilled under reduced pressure at 40 °C for 1 h, and dried in vacuum at 80 °C for 10 h to obtain Intermediate 1;

[0101] 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 successively added to the reaction flask, heated to 110 °C, the generated water was removed through a water separator, reacted for 8 h, cooled to room temperature, toluene was removed by distillation under reduced pressure at 70 °C for 3 h. The residue was dissolved in 800 ml of ethyl acetate, successively washed with 200 ml of 5 wt% aqueous sodium bicarbonate solution and 200 ml of saturated brine, rotary evaporated at 60 °C for 2 h, and dried in vacuum at 80 °C for 10 h to obtain the antioxidant.

[0102] The protective gloves of Examples 7-9 and Comparative Examples 1-6 were prepared by the following process:

[0103] S1: Natural rubber latex, chloroprene rubber latex, potassium hydroxide, Peregal O, sulfur, accelerator BZ, antistatic agent, carboxymethyl cellulose sodium and antioxidant were stirred evenly, kept warm and stirred at 40 °C, pre-vulcanized for 2 h, and then left standing at room temperature for 48 h to obtain the cured latex;

[0104] S2: The mold was cleaned and dried at 80 °C for 5 min;

[0105] S3: The mold was immersed in a 20 wt% aqueous calcium nitrate solution and dried at 90 °C for 5 min;

[0106] S4: The mold was immersed in the cured latex, left for 30 s, and the latex was dried at 80 °C for 5 min;

[0107] S5: The mold was passed through a crimper to crimp the opening of the latex;

[0108] S6: Leaching was carried out at 60 ± 5 °C;

[0109] S7: Drying and vulcanizing were carried out at 110 °C for 25 min;

[0110] S8: Demolding and washing with 60 °C hot water to obtain the protective gloves.

[0111] Raw materials used in the examples and comparative examples of this application: The natural latex grade is SCR WF, purchased from Yunnan Guangken Rubber Co., Ltd.; the neoprene latex grade is 750, purchased from Lisen Noko (China) Investment Co., Ltd.; sulfur is the special sulfur powder of type S-80 produced by Qingdao Luchuan Chemical Co., Ltd., mesh number: 400 mesh; sodium carboxymethylcellulose is purchased from Hebei Yanxing Chemical Co., Ltd., with a content greater than 98%.

[0112] The protective gloves of Examples 4-6 and Comparative Examples 1-6 of this application were subjected to tensile strength, elongation at break, antistatic performance, and aging tests. The tensile strength and elongation at break were carried out according to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber and Thermoplastic Rubber", temperature 23°C, 1B type specimen, tensile speed 100 mm / min; the antistatic performance was tested according to the BS EN16350-2014 standard, balanced for 24 h under the conditions of 25°C and 45% humidity, and the vertical resistance was measured; the aging test was to place the protective gloves in a hot air aging oven and age them at 100°C for 4 days, and then carry out relevant performance tests. The test results are shown in Table 1.

[0113] Table 1 Performance Test Table

[0114]

[0115] 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 (tensile strength of the test piece, elongation at break of the test piece), antistatic performance (resistance value), and anti-aging performance (aging experiment).

[0116] The antistatic performance of the protective gloves prepared in Comparative Example 1 is poor, and the vertical resistance is 2.1 MΩ. The reason may be that when the addition amount of octadecyl chloride drops from 900 g to 200 g, less quaternary ammonium salt is formed, and the antistatic agent usually adsorbs the negative charges on the material surface preferentially through the positively charged polar group quaternary ammonium salt of the antistatic agent to form an electrostatic shielding layer, so as to achieve the purpose of antistatic. In the case of insufficient quaternization degree, the electrostatic shielding layer cannot be formed, resulting in a decrease in antistatic performance.

[0117] Comparative Example 2 is an antistatic agent prepared by replacing 1,3,5-tris(2,3-epoxypropoxy)benzene with glycidyl ether, and the vertical resistance is 1.2 MΩ. The possible reason is that the antistatic agent generally adsorbs environmental moisture through the hygroscopicity of hydroxyl groups (-OH) and forms H + and OH -The water film of the ions provides an ion migration channel to accelerate the dissipation of charges; the flexible chain segments of the fatty chains cause some hydroxyl groups to be wrapped, with an insufficient exposure ratio, making it difficult to form a continuous conductive water film, resulting in a decline in antistatic performance; while the antistatic agent prepared from 1,3,5-tris(2,3-epoxypropoxy)benzene has a rigid benzene ring skeleton, which can form a three-dimensional network structure with a high degree of branching, significantly increasing the density of terminal hydroxyl groups and forming a continuous conductive water film.

[0118] Comparative Example 3 uses an antistatic agent prepared by replacing octadecyl chloride with 1-chlorooctane. From the data in Table 1, it can be seen that its elongation at break and antistatic performance are poor. The reasons are as follows: The long-chain alkyl group is closer to the solubility parameter of the rubber, reducing the phase separation tendency and internal defects. The long-chain alkyl antistatic agent has a longer molecular chain and higher compatibility with the rubber matrix. It can slowly migrate to the surface and align directionally to form a continuous and stable conductive layer; at the same time, the long-chain structure physically entangles with the rubber through stronger van der Waals forces, reducing the loss caused by friction or cleaning and significantly prolonging the durability of the antistatic effect. The long-chain alkyl group can be embedded between the rubber molecular chains, weakening the rigid interaction, improving flexibility (increasing the elongation at break) and dispersing stress.

[0119] Comparative Example 4 is a comparative example different from Example 8. It is a protective glove prepared using Intermediate 1 (prepared in Example 5) as an antioxidant. Its anti-aging performance is worse than that of this application. After aging, the loss rates of tensile strength and elongation at break are relatively large. The reason is that the antioxidant prepared in Comparative Example 4 only contains the N-H structure in Intermediate 1 to inhibit the chain reaction process to play an anti-aging role. Its molecular weight is small, the diffusion resistance is low, and the migration resistance is poor, resulting in the loss of the antioxidant and poor anti-aging ability.

[0120] Comparative Examples 5 and 6 are comparative examples different from Example 8. The antioxidants prepared by replacing tetraethylene glycol diglycidyl ether with 2-(2,5,8,11,14-pentaoxapentadecyl)ethylene oxide and glycerol propoxytriepoxypropyl ether respectively. From the data in Table 1, it can be seen that their anti-aging performance is poor. The antioxidants used in Comparative Examples 5 and 6 both achieve the anti-aging purpose through the synergistic effect of hindered phenols and aromatic amines to form a stable antioxidant structure; however, for the antioxidant used in Comparative Example 5, the functional groups of hindered phenols and hindered amines are fewer and the molecular weight is also smaller, making it easy to migrate out, resulting in a decrease in anti-aging performance; the antioxidant used in Comparative Example 6 contains 3 epoxy groups, and the formed antioxidant molecule contains three functional groups of hindered phenols, with a larger molecular weight. Although it has good migration resistance, the uniformity of the antioxidant distribution in the material decreases, and it is easy to form local high-concentration regions, while the low-concentration regions become weak points of aging due to lack of protection. The antioxidant used in this application contains an ether bond (-O-), which gives the molecular chain flexibility, is easy to disperse in the latex, and improves the compatibility of the antioxidant in the rubber.

[0121] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. However, for those of ordinary skill in the art, within the scope of the technical solution of the present invention, any equivalent changes made by using the technical content disclosed above, such as slight modifications, decorations, and evolutions, 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 substantial technology of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. An antistatic protective glove, characterized in that, Comprising the following raw materials in parts by weight: Natural latex: 50 - 60 parts; Neoprene latex: 40 - 50 parts; Potassium hydroxide: 0.4 - 2 parts; Peregal 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; Antioxidant: 1.2 - 1.8 parts; The antistatic agent is first obtained by reacting 1,3,5 - tris(2,3 - epoxypropoxy)benzene with N1,N7 - dimethylheptane - 1,7 - diamine to get a hyperbranched polymer, and then quaternized with chlorooctadecane; The antistatic agent is prepared by the following method: S1: Under nitrogen protection, 1,3,5 - tris(2,3 - epoxypropoxy)benzene, N1,N7 - dimethylheptane - 1,7 - diamine and salicylic acid are stirred and mixed evenly, heated to 140 - 160 °C, reacted for 40 - 50 h, and then post - treated to obtain the hyperbranched polymer; S2: Dichloromethane and the hyperbranched polymer are mixed evenly, chlorooctadecane is added dropwise, heated to reflux, reacted for 6 - 10 h, and then post - treated to obtain the antistatic agent.

2. The antistatic protective glove according to claim 1, 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 in the feed is 1:(2 - 2.5):(0.1 - 0.5).

3. An antistatic protective glove according to claim 1, characterized in that, In step S1, the mass ratio of the hyperbranched polymer to chlorooctadecane in the feed is 1:(7 - 10).

4. An antistatic protective glove 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 are mixed evenly, heated to 140 - 160 °C, reacted for 15 - 20 h, and then post - treated to obtain intermediate 1; S2: Intermediate 1, 3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl)-1 - propanol, p - toluenesulfonic acid and toluene are mixed evenly, heated to 100 - 120 °C, the generated water is removed through a water separator, reacted for 6 - 10 h, and then post - treated to obtain the antioxidant.

5. An antistatic protective glove according to claim 4, characterized in that, In step S1, the molar ratio of 2 - [(3 - aminophenyl)amino]benzoic acid, tetraethylene glycol diglycidyl ether and salicylic acid in the feed is (2 - 2.5):1:(0.1 - 0.2).

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

7. An antistatic protective glove according to claim 1, characterized in that, The potassium hydroxide is a 5 - 15 wt% aqueous solution.

8. An antistatic protective glove according to claim 1, characterized in that, The solid content of the natural latex and neoprene latex is 50 wt%; Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant are all aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano - abrasive machine to a dispersion D90 not greater than 3 microns, and 0.4 - 1.0 wt% of sodium methylene dinaphthalene sulfonate is added as a surfactant to the ground aqueous dispersions.

9. A method for preparing the antistatic protective glove according to any one of claims 1-8, characterized in that, Comprising the following steps: S1: Mix natural latex, neoprene latex, potassium hydroxide, Peregal O, sulfur, accelerator BZ, antistatic agent, sodium carboxymethyl cellulose, and antioxidant evenly, keep stirring at 40 °C for heat preservation, pre-vulcanize for 2 h, and then stand still at room temperature for 48 h to obtain the cured latex. S2: Clean the mold and dry it at 80 °C for 5 min. S3: Immerse the mold in a 20 wt% aqueous solution of calcium nitrate and dry it at 90 °C for 5 min. S4: Immerse the mold in the cured latex, stay for 30 s, and dry the latex at 80 °C for 5 min. S5: Pass the mold through a hemming machine to hem the opening of the latex. S6: Leach at 60 ± 5 °C. S7: Dry and vulcanize at 110 °C for 25 min. S8: Demold and wash with 60 °C hot water to obtain the protective gloves.

Images