Dust-free antistatic butyronitrile glove and production process thereof

Abstract

The invention relates to the technical field of butyronitrile gloves, and discloses a dust-free antistatic butyronitrile glove and a production process thereof.The butyronitrile glove is prepared by taking carboxylic butyronitrile latex as a main raw material, matching with auxiliary materials such as a modified antistatic additive, mixing into slurry, dipping a glove model into the slurry, and then performing drying and vulcanization processes. Wherein the modified antistatic additive is prepared by modifying the surface of carbon black with a polymer macromolecular substance which is connected through ether bonds and has an alternating structure, and the polymer macromolecular substance contains an unsaturated alkenyl substituent group and can participate in the vulcanization process of subsequent butyronitrile glove manufacturing; and thus, chemical connection between the carbon black and a nitrile rubber molecular chain is realized, the carbon black can efficiently exert own advantages, the mechanical strength of the butyronitrile gloves is improved, a stable conductive path is formed, and the butyronitrile gloves are endowed with a good antistatic effect.

Description

Technical Field

[0001] The present invention relates to the technical field of nitrile gloves, and particularly relates to a dust-free antistatic nitrile glove and its production process. Background Art

[0002] Nitrile rubber (NBR) is a synthetic rubber made by emulsion polymerization of butadiene and acrylonitrile. It has excellent resistance to chemical substances such as oils, fuels, solvents, acids and alkalis, and also has excellent elasticity and durability. Therefore, it is often used to make consumables such as gloves. As an important member of industrial protective supplies, nitrile gloves are widely used in the fields of electronics manufacturing, medical treatment, chemical industry, etc. due to their excellent chemical protection, mechanical properties and biocompatibility. However, with the improvement of the requirements for production environment cleanliness and electrostatic protection in modern industry, dust-free antistatic nitrile gloves have gradually become the core protective equipment in high-precision industries.

[0003] Since there are no freely moving electrons in the molecular structure of nitrile rubber, it naturally has a relatively low tendency to generate static electricity. This makes nitrile gloves have great limitations in antistatic performance. In industries sensitive to static electricity such as electronics manufacturing, ordinary nitrile gloves may generate static electricity accumulation due to friction, which may cause irreversible damage to electronic components. Therefore, improving the antistatic performance of nitrile gloves has become a key requirement for industry development.

[0004] The prior art generally realizes the antistatic modification of nitrile rubber by adding carbon-based conductive additives such as graphene. However, there are compatibility problems between inorganic materials and nitrile rubber, and simple blending may have a negative impact on the mechanical strength of the materials. Based on this, the present invention provides a nitrile glove that can solve the problems existing in the prior art. Summary of the Invention

[0005] (1) Technical Problems to be Solved

[0006] In view of the deficiencies of the prior art, the present invention provides a dust-free antistatic nitrile glove and its production process.

[0007] (2) Technical Solutions

[0008] A dust-free antistatic nitrile glove is made of the following raw materials by weight:

[0009] 85-95 parts of carboxylated nitrile latex, 3-6.5 parts of modified antistatic additive, 1-3 parts of zinc oxide, 2-5 parts of foaming agent, 1-2 parts of accelerator, 4-8 parts of vulcanizing agent, 1-2 parts of activator, 3-5 parts of thickener, 75-85 parts of deionized water;

[0010] The modified antistatic additive is carbon black with polymer macromolecules on its surface.

[0011] As a further solution of the present invention, the preparation method of the modified antistatic additive is as follows:

[0012] Step 1: Add carbon black into concentrated nitric acid. After dispersing evenly, heat up to 70-90 °C, keep warm and stir for 3-6 h, then separate the solid material, wash it until neutral, and then perform vacuum drying treatment to obtain acid-treated carbon black.

[0013] Step 2: Disperse the acid-treated carbon black in an ethanol aqueous solution with a volume fraction of 70%. Then add a halogen-containing silane coupling agent. After adding, heat up to 70-80 °C, keep warm for 6-9 h, then centrifuge the product, and through the post-treatment process, obtain organohalogenated carbon black.

[0014] Step 3: Ultrasonically disperse the organohalogenated carbon black in toluene. Then add an excessive amount of cycloalkanediol substances and a catalyst. After adding, stir evenly, stir at a temperature of 60-70 °C for 2-4 h, then continue to add a chain extender polymerization monomer. After adding, raise the temperature to 80-90 °C, stir for 12-18 h, then stop heating, cool down and discharge, centrifuge the solid material, and after washing and vacuum drying treatment, the modified antistatic additive can be obtained.

[0015] As a further solution of the present invention, the halogen-containing silane coupling agent is any one of 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, or 3-chloropropyltriethoxysilane.

[0016] As a further solution of the present invention, the cycloalkanediol substances are any one of 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or bicyclo[2.2.2]octane-1,4-dimethanol.

[0017] As a further solution of the present invention, the catalyst is an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution, with a mass fraction of 20-30%.

[0018] As a further solution of the present invention, the preparation method of the chain extender polymerization monomer is as follows:

[0019] Add diallylcarbamyl chloride into tetrahydrofuran. After stirring evenly, place it in an ice-water bath. Then add 2,3-dibromo-1-propanol and a promoter into the formed homogeneous solution. After adding, remove the ice bath, stir at a temperature of 30-40 °C for 4-8 h, then rotary evaporate to remove the solvent, and through the purification treatment process, the chain extender polymerization monomer can be obtained.

[0020] As a further solution of the present invention, the molar ratio of diallylcarbamyl chloride to 2,3-dibromo-1-propanol is 1:1.

[0021] As a further solution of the present invention, the promoter is triethylamine or pyridine.

[0022] In the above technical solution, concentrated nitric acid is first used to acidify carbon black, so that oxygen-containing functional groups such as hydroxyl groups appear on the surface of carbon black. Then, a halogen-containing silane coupling agent is used to modify its surface, and organohalogenated carbon black with halogen substituents on the surface is prepared. Then, with a diol substance as a linker, under the action of a catalyst, the substituted hydroxyl group at one end of its structure undergoes a substitution reaction with the organohalogenated carbon black, and the other end undergoes a substitution reaction with the halogen substituents in the structure of the chain extender polymerization monomer. The excessive diol substance in the system can continuously undergo substitution with the chain extender polymerization monomer, so as to modify a polymer macromolecular substance with an alternating structure connected by ether bonds on the surface of carbon black, that is, a modified antistatic additive.

[0023] Among them, the chain extender polymerization monomer is prepared by a condensation reaction of diallyl carbamyl chloride and 2,3-dibromo-1-propanol as reactants under the action of a promoter. Since the unsaturated alkenyl substituents in the structures of the reactants do not participate in the reaction, the prepared chain extender polymerization monomer structure contains two equivalents of unsaturated alkenyl substituents and two equivalents of halogen substituents.

[0024] As a further solution of the present invention, the foaming agent is at least one of potassium hydroxide, potassium ricinoleate or potassium oleate; the promoter is promoter BZ or promoter EZ; the vulcanizing agent is sulfur; the activator is at least one of sodium lauryl polyoxyethylene ether sulfate, sodium dodecylbenzenesulfonate, and glycerol monostearate; the thickener is sodium hydroxyethyl cellulose or sodium alginate.

[0025] A production process of a dust-free antistatic nitrile glove includes the following steps:

[0026] First step: According to parts by weight, carboxylated nitrile latex, modified antistatic additive, foaming agent, promoter, zinc oxide, vulcanizing agent, and activator are added to deionized water. After mechanical stirring and mixing evenly at a rotation speed of 1000 - 2000 r / min, the rotation speed is adjusted to 400 - 600 r / min. Under stirring conditions, a thickener is continuously added and stirred for 10 - 30 min to form a slurry.

[0027] Second step: The glove model that has undergone pickling, alkali washing, and rinsing steps is immersed in the coagulating liquid, taken out after soaking for 30 - 60 s at a temperature of 60 - 70 °C, and dried. Then, it is immersed in the slurry, taken out after soaking for 15 - 20 s at room temperature, immersed again for 20 - 30 s, taken out, allowed to drip, and then placed in a drying treatment at a temperature of 80 - 90 °C for 30 - 60 min. Finally, it is vulcanized at a temperature of 120 - 140 °C for 1 - 2 h, and demolded to obtain nitrile gloves.

[0028] (III) Beneficial technical effects

[0029] In the present invention, a polymer macromolecular substance with an alternating structure connected by ether bonds is used as a modified antistatic additive to modify the surface of carbon black. The polymer macromolecular substance is mixed with carboxylated nitrile latex and other additives. Since the polymer macromolecular substance contains unsaturated alkenyl substituents that do not participate in the substitution polymerization reaction, these unsaturated alkenyl groups can participate in the vulcanization process of subsequent nitrile glove production, thereby realizing the chemical connection between the carbon black and the nitrile rubber molecular chain and forming a composite with a crosslinked network structure with carbon black as the crosslinking core. On the one hand, carbon black can exert its own strengthening effect as an inorganic substance to improve the mechanical strength of nitrile gloves. On the other hand, the uniformly dispersed carbon black can form a stable conductive path, endowing nitrile gloves with good antistatic properties, and further preventing dust from being adsorbed on the gloves due to electrostatic action, thereby further expanding the application range of nitrile gloves. Detailed implementation mode

[0030] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below. Preferred embodiments of the present invention are given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] Example 1

[0032] A dust-free antistatic nitrile glove is made from the following raw materials by weight:

[0033] 85 parts of carboxylated nitrile latex, 3 parts of modified antistatic additive, 1 part of zinc oxide, 2 parts of potassium ricinoleate as foaming agent, 1 part of accelerator BZ, 4 parts of sulfur as vulcanizing agent, 1 part of sodium dodecylbenzenesulfonate as activator, 3 parts of sodium hydroxyethyl cellulose as thickener, 75 parts of deionized water;

[0034] The preparation method of the nitrile glove is as follows:

[0035] First step, according to the weight parts, carboxylated nitrile latex, modified antistatic additive, potassium ricinoleate as foaming agent, accelerator BZ, zinc oxide, sulfur as vulcanizing agent, and sodium dodecylbenzenesulfonate as activator are added to deionized water. After mechanical stirring and mixing evenly at a rotation speed of 1000 r / min, the rotation speed is adjusted to 400 r / min. Under the stirring condition, sodium hydroxyethyl cellulose as thickener is continuously added, and stirring is continued for 30 min to form a slurry.

[0036] Step 2: Immerse the glove model that has undergone pickling, alkali washing, and rinsing steps in the coagulating liquid, take it out after immersing for 60 s at a temperature of 60 °C, dry it. Then, immerse it in the slurry, take it out after immersing for 15 s at room temperature, immerse it again for 20 s, take it out, let it drip, and then place it in a drying treatment at a temperature of 80 °C for 60 min. Finally, perform a vulcanization treatment at a temperature of 120 °C for 2 h, demold, and then the nitrile gloves can be obtained.

[0037] Example 2

[0038] A dust-free antistatic nitrile glove is made of the following raw materials by weight:

[0039] 86 parts of carboxylated nitrile latex, 6 parts of modified antistatic additive, 2 parts of zinc oxide, 3 parts of oleate foaming agent, 1.5 parts of accelerator EZ, 6 parts of sulfur curing agent, 1.5 parts of surfactant glycerol monostearate, 4 parts of thickener sodium alginate, 80 parts of deionized water;

[0040] The preparation method of the nitrile glove is as follows:

[0041] Step 1: According to the weight parts, add carboxylated nitrile latex, modified antistatic additive, oleate foaming agent, accelerator EZ, zinc oxide, sulfur curing agent, and surfactant glycerol monostearate to deionized water, mechanically stir and mix evenly at a speed of 1500 r / min, then adjust the speed to 500 r / min, and continue to add the thickener sodium alginate under stirring conditions, and continuously stir for 20 min to form a slurry;

[0042] Step 2: Immerse the glove model that has undergone pickling, alkali washing, and rinsing steps in the coagulating liquid, take it out after immersing for 40 s at a temperature of 65 °C, dry it. Then, immerse it in the slurry, take it out after immersing for 18 s at room temperature, immerse it again for 25 s, take it out, let it drip, and then place it in a drying treatment at a temperature of 85 °C for 40 min. Finally, perform a vulcanization treatment at a temperature of 130 °C for 2 h, demold, and then the nitrile gloves can be obtained.

[0043] Example 3

[0044] A dust-free antistatic nitrile glove is made of the following raw materials by weight:

[0045] 95 parts of carboxylated nitrile latex, 6.5 parts of modified antistatic additive, 3 parts of zinc oxide, 5 parts of oleate foaming agent, 2 parts of accelerator EZ, 8 parts of sulfur curing agent, 2 parts of surfactant glycerol monostearate, 5 parts of thickener sodium alginate, 85 parts of deionized water;

[0046] The preparation method of the nitrile glove is as follows:

[0047] Step 1: According to the weight parts, carboxylated nitrile latex, modified antistatic additive, potassium oleate foaming agent, accelerator EZ, zinc oxide, sulfur curing agent, and monoglyceride stearate surfactant are added to deionized water. After mechanically stirring and mixing evenly at a rotation speed of 2000 r / min, the rotation speed is adjusted to 600 r / min. Under stirring conditions, sodium alginate thickener is continuously added and stirred for 10 min to form a slurry.

[0048] Step 2: The glove model that has undergone pickling, alkali washing, and rinsing steps is immersed in the coagulating liquid, taken out after soaking for 30 s at a temperature of 70 °C, and dried. Then, it is immersed in the slurry, taken out after soaking for 20 s at room temperature, immersed again for 30 s, taken out, and allowed to drip. Then, it is placed in a drying treatment at a temperature of 90 °C for 30 min, and finally vulcanized at a temperature of 140 °C for 1 h, and demolded to obtain nitrile gloves.

[0049] The modified antistatic additive in the above examples is prepared by the following method:

[0050] Step 1: Add 5 g of carbon black N330 to concentrated nitric acid. After dispersing evenly, heat up to 80 °C, keep stirring for 4 h, separate the solid material, wash it to neutral, and then perform vacuum drying treatment to obtain acid-treated carbon black.

[0051] Step 2: Disperse 1.8 g of acid-treated carbon black in an ethanol aqueous solution with a volume fraction of 70%. Then add 1.2 g of 3-bromopropyltriethoxysilane. After adding, heat up to 75 °C, keep stirring for 8 h, centrifuge the product, and through the post-treatment process, obtain organohalogenated carbon black.

[0052] Step 3: Ultrasonically disperse 1.5 g of organohalogenated carbon black in toluene. Then add 6 g of 1,4-cyclohexanedimethanol and 10 mL of a sodium hydroxide aqueous solution with a mass fraction of 20%. After adding, stir evenly, stir at a temperature of 65 °C for 3 h, then continue to add 5.4 g of chain extender polymerization monomer. After adding, raise the temperature to 85 °C, stir for 16 h, stop heating, cool down and discharge, centrifuge the solid material, and through washing and vacuum drying treatment, the modified antistatic additive can be obtained.

[0053] The preparation method of the chain extender polymerization monomer is as follows:

[0054] Add 0.4 g of diallylcarbamyl chloride to tetrahydrofuran. After stirring evenly, place it in an ice-water bath. Then add 0.55 g of 2,3-dibromo-1-propanol and 0.01 g of pyridine to the formed homogeneous solution. After adding, remove it from the ice bath and stir at a temperature of 35 °C for 6 h. Then rotary evaporate to remove the solvent, and through the purification process, the chain extender polymerization monomer can be obtained.

[0055] Comparative Example 1

[0056] A dust-free antistatic nitrile glove is made of the following raw materials by weight:

[0057] 86 parts of carboxylated nitrile latex, 6 parts of carbon black, 2 parts of zinc oxide, 3 parts of potassium oleate foaming agent, 1.5 parts of accelerator EZ, 6 parts of sulfur curing agent, 1.5 parts of monoglyceride stearate surfactant, 4 parts of sodium alginate thickener, 80 parts of deionized water;

[0058] The preparation method of the nitrile glove is as follows:

[0059] First step, according to the weight parts, add carboxylated nitrile latex, carbon black, potassium oleate foaming agent, accelerator EZ, zinc oxide, sulfur curing agent, and monoglyceride stearate surfactant to deionized water. After mechanically stirring and mixing evenly at a speed of 1500 r / min, adjust the speed to 500 r / min. Under the stirring condition, continue to add sodium alginate thickener and continuously stir for 20 min to form a slurry;

[0060] Second step, immerse the glove model that has undergone pickling, alkali washing, and rinsing steps in the coagulating liquid, take it out after soaking for 40 s at a temperature of 65 °C, and dry it. Then, immerse it in the slurry, take it out after soaking for 18 s at room temperature, immerse it again for 25 s, take it out, let it drip, and then place it in a drying treatment at a temperature of 85 °C for 40 min. Finally, vulcanize it at a temperature of 130 °C for 2 h, and demold to obtain the nitrile glove.

[0061] Comparative Example 2

[0062] A dust-free antistatic nitrile glove is made of the following raw materials by weight:

[0063] 86 parts of carboxylated nitrile latex, 2 parts of zinc oxide, 3 parts of potassium oleate foaming agent, 1.5 parts of accelerator EZ, 6 parts of sulfur curing agent, 1.5 parts of monoglyceride stearate surfactant, 4 parts of sodium alginate thickener, 80 parts of deionized water;

[0064] The preparation method of the nitrile glove is as follows:

[0065] First step, according to the weight parts, add carboxylated nitrile latex, potassium oleate foaming agent, accelerator EZ, zinc oxide, sulfur curing agent, and monoglyceride stearate surfactant to deionized water. After mechanically stirring and mixing evenly at a speed of 1500 r / min, adjust the speed to 500 r / min. Under the stirring condition, continue to add sodium alginate thickener and continuously stir for 20 min to form a slurry;

[0066] Step 2: Immerse the glove model that has undergone pickling, alkali washing, and rinsing steps in the coagulating liquid, take it out after soaking for 40 s at a temperature of 65 °C, and dry it. Then, immerse it in the slurry, take it out after soaking for 18 s at room temperature, soak it again for 25 s, take it out, let it drip, and then place it in a drying treatment at a temperature of 85 °C for 40 min. Finally, vulcanize it at a temperature of 130 °C for 2 h, and demold it to obtain nitrile gloves.

[0067] Performance test

[0068] According to the EN388 standard, the mechanical properties of the nitrile gloves in the examples and comparative examples were tested;

[0069] The surface resistivity was tested using a resistivity tester, and the test voltage was selected as 100 V;

[0070] The results are recorded in the following table:

[0071]

[0072]

[0073] According to the test results, when directly using carbon black as an additive, since it cannot form a cross-linked structure with the molecular chains of nitrile rubber, its compatibility with the nitrile rubber matrix is poor, it is difficult to efficiently exert its own strengthening advantages, and it is also difficult to uniformly disperse to form a stable conductive path. Therefore, all performances have decreased significantly.

[0074] In this article, specific examples are used to elaborate on the principle and implementation method of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of this invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within the scope of the claims.

[0075] Based on the inspiration of the preferred embodiments of the present invention, through the above description, relevant personnel can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and the technical scope must be determined according to the scope of the claims.

Claims

1. A dust-free antistatic nitrile glove, characterized in that, It is made from the following raw materials by weight parts: 85 - 95 parts of carboxylated nitrile latex, 3 - 6.5 parts of modified antistatic additive, 1 - 3 parts of zinc oxide, 2 - 5 parts of foaming agent, 1 - 2 parts of accelerator, 4 - 8 parts of vulcanizing agent, 1 - 2 parts of activator, 3 - 5 parts of thickener, 75 - 85 parts of deionized water; The modified antistatic additive is carbon black surface - modified with polymer macromolecules.

2. The dust-free antistatic nitrile glove according to claim 1, wherein The preparation method of the modified antistatic additive is as follows: Step 1: Acidify carbon black to obtain acid - treated carbon black. Step 2: Surface - modify the acid - treated carbon black with a halogen - containing silane coupling agent to obtain organohalogenated carbon black. Step 3: Use an excessive amount of cycloalkanediol as a linker. Under the action of a catalyst, first connect it with the organohalogenated carbon black, and then add a chain - extending polymerization monomer to carry out a continuous chain - extending substitution reaction to obtain the modified antistatic additive.

3. The dust-free antistatic nitrile glove according to claim 2, characterized in that, The halogen - containing silane coupling agent is any one of 3 - bromopropyltrimethoxysilane, 3 - bromopropyltriethoxysilane, or 3 - chloropropyltriethoxysilane.

4. The dust-free antistatic nitrile glove according to claim 2, characterized in that, The cycloalkanediol is any one of 1,4 - cyclohexanediol, 1,4 - cyclohexanedimethanol, or bicyclo[2.2.2]octane - 1,4 - dimethanol.

5. The dust-free antistatic nitrile glove according to claim 2, characterized in that, The catalyst is an aqueous solution of potassium hydroxide or sodium hydroxide with a mass fraction of 20 - 30%.

6. The dust-free antistatic nitrile glove according to claim 2, characterized in that, The preparation method of the chain - extending polymerization monomer is as follows: Add diallylcarbamyl chloride to tetrahydrofuran, stir evenly, place it in an ice - water bath, then add 2,3 - dibromo - 1 - propanol and an accelerator to the formed homogeneous solution. After adding, remove the ice - bath, stir at a temperature of 30 - 40 °C for 4 - 8 h, then rotary evaporate to remove the solvent, and through a purification process, the chain - extending polymerization monomer can be obtained.

7. The dust-free antistatic nitrile glove according to claim 6, characterized in that, The molar ratio of diallylcarbamyl chloride to 2,3 - dibromo - 1 - propanol is 1:

1.

8. The dust-free and antistatic nitrile glove according to claim 6, characterized in that, The accelerator is triethylamine or pyridine.

9. The dust-free antistatic nitrile glove according to claim 1, wherein, The foaming agent is at least one of potassium hydroxide, potassium ricinoleate, or potassium oleate; the accelerator is accelerator BZ or accelerator EZ; the vulcanizing agent is sulfur; the activator is at least one of sodium lauryl polyoxyethylene ether sulfate, sodium dodecylbenzenesulfonate, or glycerol monostearate; the thickener is sodium hydroxyethyl cellulose or sodium alginate.

10. The production process of a dust-free antistatic nitrile glove as described in claim 1, characterized in that, It includes the following steps: The first step: According to the weight parts, add carboxylated nitrile latex, modified antistatic additive, foaming agent, accelerator, zinc oxide, vulcanizing agent, and activator to deionized water. After mechanically stirring and mixing evenly at a speed of 1000 - 2000 r / min, adjust the speed to 400 - 600 r / min. Under the stirring condition, continue to add the thickener and continuously stir for 10 - 30 min to form a slurry. Step 2: Immerse the glove model that has undergone pickling, alkali washing, and rinsing steps in the coagulating liquid, take it out after soaking for 30 - 60 s under the temperature condition of 60 - 70 °C, and dry it. Then, immerse it in the slurry, take it out after soaking for 15 - 20 s at room temperature, soak it again for 20 - 30 s, take it out, let it drip, and then place it in a temperature environment of 80 - 90 °C for drying treatment for 30 - 60 min. Finally, perform vulcanization treatment at a temperature condition of 120 - 140 °C for 1 - 2 h, and demold to obtain nitrile gloves.

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