Preparation method of antibacterial PVC glove material

Abstract

The invention discloses a preparation method of an antibacterial PVC glove material, and belongs to the technical field of glove materials. Comprising the following raw materials in parts by weight: 116-133 parts of PVC resin, 17-26 parts of thermoplastic polyurethane, 6-10 parts of cinnamon oil, 12-24 parts of an auxiliary agent, 0.05-0.15 part of an initiator and 5-9 parts of a processing auxiliary agent. Wherein the thermoplastic polyurethane enhances the heat resistance and the mechanical property of the glove material; the cinnamon oil in the raw materials belongs to a natural antibacterial component and can enhance the antibacterial property of the PVC glove material to a certain extent; wherein the auxiliary agent contains a large number of functional groups, the antibacterial property, the mechanical property and the heat resistance of the glove material can be further enhanced, the performance is long and stable, and the glove material is not prone to falling off; therefore, the prepared PVC glove material has stable and efficient heat resistance, mechanical property and antibacterial property, and has important application value in the technical field of glove materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of glove materials, and specifically relates to a preparation method of an antibacterial PVC glove material. Background Art

[0002] Gloves are hand warmers or labor protection supplies. Common types of gloves include: rubber gloves, nitrile gloves, and PVC gloves. Among them, rubber gloves have good elasticity and fit the hands well, but have a slight odor and may cause allergies. Nitrile gloves are more skin-friendly than rubber, have slightly worse abrasion resistance, are hypoallergenic, and are suitable for medical, food industries, and household use. PVC gloves are semi-transparent, have a thin touch, are safe and odorless, and can provide basic protection against contamination and contact with chemical substances. Therefore, they are widely used in medical, food processing, cleaning, and industrial fields.

[0003] From biomedicine to daily life, how to resist the attachment of non-specific biomolecules, microorganisms, etc. on the surface of gloves and improve the anti-bioadhesion ability of the surface is a great challenge. Therefore, in actual use, PVC gloves will come into contact with a large number of bacteria and germs, and the gloves themselves are also a hotbed for bacteria to breed. This greatly increases the risk of infection for users.

[0004] Traditional antibacterial PVC gloves add antibacterial agents during the preparation process. Due to the poor compatibility between the antibacterial agents and PVC molecules, during the blending process of the antibacterial agents and PVC molecules, a large amount of antibacterial agents cannot be compatible with polyvinyl chloride paste resin, resulting in a significant reduction in the antibacterial effect of PVC gloves. Moreover, after long-term use of PVC gloves, due to the poor compatibility between the antibacterial agents and the raw materials, the antibacterial effect of PVC gloves disappears, affecting the use of antibacterial PVC gloves. Therefore, it is urgent to solve the above problems to meet the higher requirements in the technical field of glove materials. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a preparation method of an antibacterial PVC glove material.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of an antibacterial PVC glove material includes the following steps:

[0008] After drying PVC resin and thermoplastic polyurethane, add cinnamon oil, additives, initiators, and processing aids into a mixer, stir at 300 - 400 rpm for 15 - 30 minutes to make the raw materials evenly mixed, then put them into a twin-screw extruder, after melt blending, and then extrude to obtain the antibacterial PVC glove material.

[0009] Further, the raw materials are as follows by weight parts: 116 - 133 parts of PVC resin, 17 - 26 parts of thermoplastic polyurethane, 6 - 10 parts of cinnamon oil, 12 - 24 parts of auxiliary agent, 0.05 - 0.15 parts of initiator, and 5 - 9 parts of processing aid.

[0010] Further, the drying condition is drying in an oven at 80 - 90 °C for 12 - 24 h.

[0011] Further, the initiator is one of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

[0012] Further, the processing aid is one of sodium methylene bisnaphthalene sulfonate and sodium dibutylnaphthalene sulfonate.

[0013] Further, the auxiliary agent is prepared through the following steps:

[0014] Step 1: Dissolve isocyanuric acid in acetone in a flask, add anhydrous potassium carbonate (acid-binding agent), heat up to 60 °C, reflux for 1 h, then add 1,3 - dichloropropane, continue heating to 75 °C, reflux and react for 4 h. After the reaction is completed, filter through a diatomaceous earth column chromatography, and then wash with ethyl acetate 2 - 3 times to obtain intermediate product 1; the dosage ratio of isocyanuric acid, acetone, anhydrous potassium carbonate, and 1,3 - dichloropropane is 12.9 g:100 mL:13.8 g:11.1 g;

[0015] Under the catalysis of anhydrous potassium carbonate, isocyanuric acid and 1,3 - dichloropropane undergo an S N nucleophilic substitution reaction. By controlling the molar ratio of the two to be close to 1:1, intermediate product 1 is obtained; the specific reaction process is as follows:

[0016]

[0017] Step 2: Add intermediate product 1 to a flask, then add N,N - dimethylformamide (DMF), stir, and then successively add ethylenediamine and triethylamine to the device using a constant pressure dropping funnel. Then place the device in a water bath, control the temperature at 55 °C, react for 4 h. After the reaction is completed, distill off the solvent under reduced pressure, and then wash with distilled water 3 - 4 times and dry to obtain intermediate product 2; the dosage ratio of intermediate product 1, N,N - dimethylformamide, ethylenediamine, and triethylamine is 20.5 g:100 mL:8.2 g:15 mL;

[0018] Under the action of triethylamine, ethylenediamine and intermediate product 1 undergo a nucleophilic substitution reaction. By controlling the molar ratio of the two to be close to 1:1 and ethylenediamine being slightly in excess, intermediate product 2 is obtained; the specific reaction process is as follows:

[0019]

[0020] Step 3: Mix 4-hydroxystyrene with toluene and add them into a three-necked round-bottom flask equipped with a thermometer, a magnetic stirring system and a spherical condenser. Under the condition of an ice bath at 5 °C, slowly add the formaldehyde solution drop by drop while continuously stirring until the addition is complete. Then add Intermediate 2 to the device, control the reaction temperature at 60 °C, and reflux for 5 h. After the reaction is completed, cool to room temperature, rotary evaporate to remove the solvent, and then purify by column chromatography (the eluent uses a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 2:3). Rotary evaporate to remove the eluent to obtain Intermediate 3; the dosage ratio of 4-hydroxystyrene, toluene, formaldehyde solution, and Intermediate 2 is 11.9 g: 100 mL: 15 mL: 22.9 g;

[0021] 4-Hydroxystyrene, Intermediate 2 and formaldehyde underwent a Mannich condensation reaction to obtain Intermediate 3; the specific reaction process is as follows:

[0022]

[0023] Step 4: In a three-necked flask equipped with a stirring device, add Intermediate 3 to a mixed solvent of tert-butanol and water (the volume ratio of tert-butanol to water is 3:2), continuously stir, and after mixing evenly, add sodium hypochlorite, and react at room temperature for 8 h under light-shielded conditions. After the reaction is completed, remove the solvent by vacuum distillation and dry in vacuum to obtain the additive; the dosage ratio of Intermediate 3, the mixed solvent of tert-butanol and water, and sodium hypochlorite is 37.3 g: 100 mL: 32 mL;

[0024] Under the action of sodium hypochlorite, the N-H bond in the molecule of Intermediate 3 is transformed into an N-Cl bond to obtain the additive;

[0025] The prepared additive molecule contains multiple chloramine groups. As an excellent antibacterial structure, chloramine can release strongly oxidizing Cl + to destroy the bacterial structure and has a certain regenerability, which can improve the antibacterial performance of the PVC matrix. In addition, the additive molecule also contains a benzoxazine structure. Benzoxazine contains a special six-membered oxazine ring structure, which can greatly enhance the heat resistance of the matrix. In addition, the benzene ring structure in benzoxazine can also improve the mechanical strength of the matrix; finally, one end of the additive molecule contains a carbon-carbon double bond, which can crosslink with the PVC matrix under the action of a trace initiator, not only improving the stability of the additive molecule and making it not easy to fall off, but also enhancing the compatibility between the additive and the PVC matrix. And the additive also contains multiple chlorine groups, further improving the compatibility between the additive and the PVC matrix, so that the antibacterial and heat resistance of the additive can be fully exerted.

[0026] Advantages of the present invention:

[0027] 1. The PVC glove material prepared by the present invention adds thermoplastic polyurethane to the raw materials, enhancing the heat resistance and mechanical properties of the glove material;

[0028] 2. The cinnamon oil in the raw materials belongs to natural antibacterial components, which can enhance the antibacterial performance of the PVC glove material to a certain extent;

[0029] 3. The auxiliary agent is prepared through a series of reactions. The auxiliary agent contains a large number of functional groups, which can further enhance the antibacterial, mechanical and heat resistance properties of the glove material, and the properties are long-term stable and not easy to fall off;

[0030] Therefore, the PVC glove material prepared by the present invention has stable and efficient heat resistance, mechanical properties and antibacterial properties, and has important application value in the technical field of glove materials. Specific Embodiments

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0032] Example 1

[0033] Preparation of Auxiliary Agent:

[0034] Step 1: Dissolve 12.9 g of isocyanuric acid in 100 mL of acetone in a flask, add 13.8 g of anhydrous potassium carbonate, heat up to 60 °C, reflux for 1 h, then add 11.1 g of 1,3-dichloropropane, continue to heat until the temperature reaches 75 °C, reflux and react for 4 h. After the reaction is completed, filter through a diatomaceous earth column chromatography, and wash with ethyl acetate 2 - 3 times to obtain Intermediate Product 1;

[0035] Step 2: Add 20.5 g of Intermediate Product 1 to the flask, then add 100 mL of N,N-dimethylformamide, stir, and then sequentially add 8.2 g of ethylenediamine and 15 mL of triethylamine to the device with a constant pressure dropping funnel. Then place the device in a water bath, control the temperature at 55 °C, react for 4 h. After the reaction is completed, distill off the solvent under reduced pressure, and wash with distilled water 3 times, and dry to obtain Intermediate Product 2;

[0036] Step 3: Mix 11.9 g of 4-hydroxystyrene with 100 mL of toluene, add them to a three-necked round-bottom flask equipped with a thermometer, a magnetic stirring system, and a spherical condenser. Under the condition of an ice bath at 5 °C, slowly add 15 mL of formaldehyde solution drop by drop while continuously stirring until the addition is complete. Then add 22.9 g of intermediate 2 to the device, control the reaction temperature at 60 °C, and reflux for 5 h. After the reaction is completed, cool to room temperature, rotary evaporate to remove the solvent, and then purify by column chromatography (the eluent uses a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 2:3). Rotary evaporate to remove the eluent to obtain intermediate 3;

[0037] Step 4: In a three-necked flask equipped with a stirring device, add 37.3 g of intermediate 3 to a mixed solvent of 100 mL of tert-butanol and water (the volume ratio of tert-butanol to water is 3:2), stir continuously. After mixing evenly, add 32 mL of sodium hypochlorite, and react at room temperature for 8 h under light-shielded conditions. After the reaction is completed, remove the solvent by vacuum distillation and dry under vacuum to obtain the additive.

[0038] Example 2

[0039] Preparation of the additive:

[0040] Step 1: Dissolve 25.8 g of isocyanuric acid in 200 mL of acetone in a flask, add 27.6 g of anhydrous potassium carbonate, heat to 60 °C, reflux for 1 h, then add 22.2 g of 1,3-dichloropropane, continue heating until the temperature reaches 75 °C, and reflux for 4 h. After the reaction is completed, filter through a diatomaceous earth column chromatography, and wash with ethyl acetate 3 times to obtain intermediate 1;

[0041] Step 2: Add 41.0 g of intermediate 1 to the flask, then add 200 mL of N,N-dimethylformamide, stir, and then sequentially add 16.4 g of ethylenediamine and 30 mL of triethylamine to the device using a constant pressure dropping funnel. Then place the device in a water bath, control the temperature at 55 °C, and react for 4 h. After the reaction is completed, remove the solvent by vacuum distillation, wash with distilled water 3 times, and dry to obtain intermediate 2;

[0042] Step 3: Mix 23.8 g of 4-hydroxystyrene with 200 mL of toluene, add them to a three-necked round-bottom flask equipped with a thermometer, a magnetic stirring system, and a spherical condenser. Under the condition of an ice bath at 5 °C, slowly add 30 mL of formaldehyde solution drop by drop while continuously stirring until the addition is complete. Then add 45.8 g of intermediate 2 to the device, control the reaction temperature at 60 °C, and reflux for 5 h. After the reaction is completed, cool to room temperature, rotary evaporate to remove the solvent, and then purify by column chromatography (the eluent uses a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 2:3). Rotary evaporate to remove the eluent to obtain intermediate 3;

[0043] Step 4: In a three-necked flask equipped with a stirring device, add 74.6 g of intermediate 3 to 200 mL of a mixed solvent of tert-butanol and water (the volume ratio of tert-butanol to water is 3:2). Stir continuously. After mixing evenly, add 64 mL of sodium hypochlorite, and react at room temperature for 8 h under light-shielded conditions. After the reaction is completed, remove the solvent by vacuum distillation and dry in vacuo to obtain the auxiliary agent.

[0044] Example 3

[0045] Put 116 g of PVC resin and 17 g of thermoplastic polyurethane into an 80 °C drying oven and dry for 12 h. Then add 6 g of cinnamon oil, 12 g of the auxiliary agent prepared in Example 1, 0.05 g of diisopropyl peroxydicarbonate, and 5 g of methylene bisnaphthalenesulfonic acid sodium to a mixer. Stir at 300 rpm for 15 min to make the raw materials mix evenly, and then put them into a twin-screw extruder. After melt blending, extrude to obtain the antibacterial PVC glove material.

[0046] Example 4

[0047] Put 124 g of PVC resin and 22 g of thermoplastic polyurethane into a 90 °C drying oven and dry for 24 h. Then add 8 g of cinnamon oil, 18 g of the auxiliary agent prepared in Example 1, 0.1 g of dicyclohexyl peroxydicarbonate, and 7 g of dibutylnaphthalenesulfonic acid sodium to a mixer. Stir at 400 rpm for 30 min to make the raw materials mix evenly, and then put them into a twin-screw extruder. After melt blending, extrude to obtain the antibacterial PVC glove material.

[0048] Example 5

[0049] Put 133 g of PVC resin and 26 g of thermoplastic polyurethane into a 90 °C drying oven and dry for 24 h. Then add 10 g of cinnamon oil, 24 g of the auxiliary agent prepared in Example 1, 0.15 g of dicyclohexyl peroxydicarbonate, and 9 g of dibutylnaphthalenesulfonic acid sodium to a mixer. Stir at 400 rpm for 30 min to make the raw materials mix evenly, and then put them into a twin-screw extruder. After melt blending, extrude to obtain the antibacterial PVC glove material.

[0050] Comparative Example 1

[0051] Use a commercially available chloramine antibacterial agent of the same mass to replace the auxiliary agent in Example 5, and the remaining steps are the same as those in Example 5.

[0052] Comparative Example 2

[0053] Use a commercially available PVC material.

[0054] Make the corresponding shapes of Example 3, 4, 5, Comparative Example 1 and 2 according to different test standards, and conduct the following performance tests:

[0055] The tensile strength was determined according to the national standard GB / T 1040.2 "Determination of Tensile Properties of Plastics"; the specimen was placed in an environment of 140 °C and thermally oxidized in hot air for 24 h, then the tensile strength was measured (test standard GB / T 1040.2), and the retention rate of the tensile strength was calculated; the retention rate of the tensile strength = tensile strength after testing / tensile strength before testing × 100%;

[0056] The antibacterial rate was determined according to the national standard GB / T 31402-2015 "Test Method for Antibacterial Properties of Plastic Surfaces"; then the antibacterial rates of Examples 3, 4, 5 and Comparative Example 1 after standing at room temperature for 100 days were measured;

[0057] The measured results are shown in the following table:

[0058]

[0059]

[0060] As can be seen from the above table, the PVC glove material prepared in the examples of the present invention has higher heat resistance, mechanical properties and antibacterial properties than the comparative examples, and the properties are long-term stable, having important application value in the technical field of glove materials.

[0061] In the description of the specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0062] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

Claims

1. A method for preparing an antibacterial PVC glove material, characterized in that: The following steps are involved: After the PVC resin and thermoplastic polyurethane are dried, they are added into a mixer together with cinnamon oil, additives, initiators and processing aids to mix the raw materials evenly, and then put into a twin-screw extruder for melt blending and extrusion to obtain an antibacterial PVC glove material.

2. The method for preparing an antibacterial PVC glove material according to claim 1, characterized in that: The auxiliary agent is prepared by the following steps: Step 1, dissolve isocyanuric acid in acetone in a flask, add anhydrous potassium carbonate, heat to 60°C, reflux for 1 hour, add 1,3-dichloropropane, continue heating to 75°C, reflux for 4 hours, the reaction is complete, filter by column chromatography, and wash to obtain intermediate 1; Step 2, add the intermediate product 1 to a flask, then add N,N-dimethylformamide, stir, then add ethylenediamine and triethylamine in sequence, then place the device in a water bath, control the temperature to 55°C, react for 4 hours, and after the reaction is completed, distill under reduced pressure, wash, and dry to obtain the intermediate product 2; Step 3, 4-hydroxystyrene and toluene were mixed, added to a three-necked round-bottom flask, and formaldehyde solution was added dropwise under an ice bath condition of 5°C, and stirring was continued until the addition was completed, and then the intermediate product 2 was added to the device, and refluxed at 60°C for 5h. After the reaction was completed, the mixture was cooled to room temperature, rotary evaporated, purified by column chromatography, and rotary evaporated to obtain the intermediate product 3; Step 4: add the intermediate product 3 to a mixed solvent of tert-butanol and water, stir continuously, and after mixing evenly, add sodium hypochlorite, react at room temperature for 8 hours under light-proof conditions, and after the reaction is completed, perform reduced pressure distillation and vacuum drying to obtain an auxiliary agent.

3. The method for preparing an antibacterial PVC glove material according to claim 2, characterized in that: In step 1, the ratio of isocyanuric acid, acetone, anhydrous potassium carbonate and 1,3-dichloropropane is 12.9 g:100 mL:13.8 g:11.1 g.

4. The method for preparing an antibacterial PVC glove material according to claim 2, characterized in that: In step 2, the ratio of the amount of intermediate product 1, N,N-dimethylformamide, ethylenediamine and triethylamine is 20.5g:100mL:8.2g:15mL.

5. The method for preparing an antibacterial PVC glove material according to claim 2, characterized in that: In step 3, the ratio of the amount of 4-hydroxystyrene, toluene, formaldehyde solution and intermediate product 2 is 11.9 g: 100 mL: 15 mL: 22.9 g.

6. The method for preparing an antibacterial PVC glove material according to claim 2, characterized in that: In step 4, the ratio of the intermediate product 3, the mixed solvent of tert-butyl alcohol and water, and the sodium hypochlorite is 37.3 g:100 mL:32 mL.

7. The method for preparing an antibacterial PVC glove material according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 116-133 parts of PVC resin, 17-26 parts of thermoplastic polyurethane, 6-10 parts of cinnamon oil, 12-24 parts of additives, 0.05-0.15 parts of initiator, and 5-9 parts of processing aid.

8. The method for preparing an antibacterial PVC glove material according to claim 1, characterized in that: The drying condition is to dry in a drying oven at 80-90°C for 12-24 hours.

9. The method for preparing an antibacterial PVC glove material according to claim 1, characterized in that: The initiator is one of diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

10. The method for preparing an antibacterial PVC glove material according to claim 1, characterized in that: The processing aid is one of sodium methylene bis naphthalene sulfonate and sodium dibutyl naphthalene sulfonate.

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