An antistatic medical isolation film and a method for preparing the same

Abstract

The application discloses an antistatic medical isolation film and a preparation method thereof, and belongs to the technical field of film materials. The raw materials of the medical isolation film include 15-25 parts of low-density polyethylene, 50-60 parts of metallocene low-density polyethylene, 0.8-2 parts of an antioxidant, 0.8-2 parts of an ultraviolet absorber, 0.8-2 parts of an additive, 0.6-1 part of a waterproof and oil-proof agent, and 0.05-0.1 part of a crosslinking agent. The additive contains carvacol, a sulfonamide structure and a quaternary ammonium salt structure, the alkyl long chain of the quaternary ammonium salt structure contains 14 carbons, the oil-soluble benzene ring and long carbon chain promote the compatibility between the additive and the remaining raw materials, and the additive and polyethylene have chemical action, therefore, the additive can be uniformly dispersed and stably exist in the isolation film, fully play its own role, and make the medical isolation film of the application have stable and excellent antibacterial property and antistatic property.

Description

Technical Field

[0001] The present invention belongs to the technical field of membrane materials, and in particular relates to an antistatic medical isolation membrane and a preparation method thereof. Background Art

[0002] Hospitals are prone to cross-infection due to the high concentration of viruses and bacteria, necessitating the use of isolation membranes for protection. Existing isolation membranes are typically made of ordinary polyethylene film. While these films have a certain isolation effect, they are different from ordinary protective films in that they require very high barrier properties for medical isolation and protection. Furthermore, these existing medical isolation membranes have a short antibacterial effect and poor antibacterial effect. Therefore, there is a need to develop a medical isolation membrane material with long-term antibacterial properties.

[0003] Furthermore, during storage, transportation, and use, separators are susceptible to static electricity, causing charge accumulation or discharge, which can adversely affect the performance and service life of the separator. For example, static discharge can ionize tiny gas molecules on or within the separator, causing chemical reactions and damaging the separator's structure and performance. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide an antistatic medical isolation membrane and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antistatic medical isolation film comprises the following raw materials in parts by weight: 15-25 parts of low-density polyethylene, 50-60 parts of metallocene low-density polyethylene, 0.8-2 parts of antioxidant, 0.8-2 parts of ultraviolet absorber, 0.8-2 parts of auxiliary agent, 0.6-1 parts of waterproof and oil-proof agent, and 0.05-0.1 parts of cross-linking agent.

[0007] Furthermore, the ultraviolet absorber is one or more of ultraviolet absorber UV-P, ultraviolet absorber UV-9, ultraviolet absorber UV-531, and ultraviolet absorber UV-327.

[0008] Furthermore, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant DLTP.

[0009] Furthermore, the auxiliary agent is prepared by the following steps:

[0010] S1. Under nitrogen protection, a fully dried three-necked flask was placed in an ice bath, and chlorosulfonic acid was slowly added. The chlorosulfonic acid was stirred in the ice bath and cooled to below 15°C. After stirring for 15 minutes, carvacrol was slowly added. The temperature was maintained at 10°C and stirred for 0.5 hours. The temperature was then raised to 60°C and reacted for 2 hours. After the reaction, the mixture was slowly diluted with ice water to precipitate. The precipitate was filtered, washed with ice water, and dried to obtain intermediate 1; the molar ratio of carvacrol to chlorosulfonic acid was 1:6;

[0011] Under heating conditions, chlorosulfonic acid sulfonates carvacrol to obtain intermediate 1. The reaction equation is shown below:

[0012]

[0013] S2. First, place the three-necked flask in an ice bath, and then blow nitrogen for 30 minutes to drive out the air in the flask. Then, add intermediate 1, triethylamine and DMSO (dimethyl sulfoxide). After stirring and dissolving, cool the system to 10°C in an ice bath. Slowly add 1,3-propylenediamine to the above flask under nitrogen protection. After the addition is complete, stir and react at 50°C for 6 hours. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, 1,3-propylenediamine, triethylamine and DMSO is 12.4g:4.3mL:10.4mL:120mL;

[0014] Under heating, intermediate 1 and 1,3-propylenediamine undergo amidation reaction to generate intermediate 2 containing a sulfonamide group. Triethylamine is used as an acid binding agent to remove the hydrogen chloride produced in the reaction and promote the forward reaction. The reaction process is shown below:

[0015]

[0016] S3. Under nitrogen protection, intermediate 2, pyridine and DMSO were added to a three-necked flask, and 4-chloro-1-butene was slowly added after stirring. The temperature was then raised to 60° C. and the reaction was kept warm for 2 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure. Purification was performed by column chromatography (a mixed solvent of benzene and ethyl acetate was selected as the eluent, and the volume ratio of benzene and ethyl acetate was 8:2). Distillation under reduced pressure gave intermediate 3; the usage ratio of intermediate 2, 4-chloro-1-butene, pyridine and DMSO was 0.035 mol:0.072 mol:8.5 mL:100 mL;

[0017] Pyridine acts as an acid-binding agent, and the -NH2 of intermediate 2 and the -Cl of 4-chloro-1-butene undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0018]

[0019] S4. Under nitrogen, add intermediate 3, triethylamine, and DMF (N,N-dimethylformamide) to a dry four-necked flask. Stir thoroughly, then slowly add tetradecane chloride. Heat to 70°C and allow to react for 3 hours. After completion of the reaction, cool to room temperature and evaporate under reduced pressure. Purify by column chromatography (using a mixed solvent of benzene and acetone in a volume ratio of 9:1 as the eluent). Evaporate under reduced pressure to obtain the auxiliary agent. The ratio of intermediate 3, tetradecane chloride, triethylamine, and DMF used is 0.03 mol:0.032 mol:6.3 mL:120 mL.

[0020] Triethylamine acts as an acid-binding agent, and the tertiary amine group of intermediate 3 and the -Cl of chlorotetradecane undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0021]

[0022] The adjuvant contains carvacrol, sulfonamide structure and quaternary ammonium salt structure. Carvacrol has an inhibitory effect on both Gram-positive and Gram-negative bacteria, and can effectively inhibit the growth of Bacillus subtilis, Clostridium perfringens, Enterobacter cloacae, Escherichia coli, Salmonella typhi, Cronobacter sakazakii, etc. Sulfonamide structure exists in many active compounds and is the pharmacophore of antibacterial, anti-tumor and analgesic compounds. Introducing sulfonamide group into carvacrol structure can enhance the antibacterial activity of carvacrol, especially the anti-Staphylococcus aureus activity. The quaternary ammonium salt structure with a long carbon chain (14 carbons) dissociates into a positively charged quaternary ammonium cation - N + Ions can adsorb onto the cell walls of negatively charged bacteria, destroying the bacterial cell membrane and denaturing its proteins, hindering DNA replication and reproduction, thereby achieving an antibacterial effect. Furthermore, the antibacterial effect is optimal when the alkyl chain of the quaternary ammonium salt structure has 14 carbon atoms. The synergistic effect of carvacrol, sulfonamide structure, and quaternary ammonium salt structure gives the additive excellent antibacterial activity, thereby imparting excellent antibacterial efficacy to the medical isolation membrane.

[0023] The quaternary ammonium salt structure carries positive ions, which can neutralize the charge on the surface of the material to form a thin charge layer to work, so that the charge can be easily removed, thereby giving the isolation membrane antistatic properties; in addition, the quaternary ammonium salt structure can not only reduce the surface charge, but also inhibit the adsorption of dust and oil.

[0024] The additive contains a terminal carbon-carbon double bond, which can produce a chemical reaction with the unreacted carbon-carbon double bond at the end of polyethylene under the action of the cross-linking agent. As a result, the additive can be stably present in the isolation membrane, is not easy to migrate and fall out, and can give full play to the long-lasting and stable antibacterial and antistatic effects.

[0025] Furthermore, the water-proof and oil-proof agent is one or both of organic fluorine resin TG-528A and organic fluorine resin TG-521B.

[0026] Furthermore, the cross-linking agent is one or both of dicumyl peroxide and dibenzoyl peroxide.

[0027] A method for preparing an antistatic medical isolation membrane comprises the following steps:

[0028] The raw materials are weighed by weight and put into a high-speed mixer. After being fully mixed, they are put into a twin-screw extruder for extrusion granulation. The granules are crushed by a pellet mill, dried, and put into a single-axis screw conveyor for film blowing to obtain an antistatic medical isolation film.

[0029] The beneficial effects of the present invention are as follows: the auxiliary agent of the present invention contains carvacrol, a sulfonamide structure and a quaternary ammonium salt structure; the long alkyl chain of the quaternary ammonium salt structure contains 14 carbon atoms; the oil-soluble benzene ring and the long carbon chain promote the compatibility between the auxiliary agent and the remaining raw materials; and there is a chemical reaction between the auxiliary agent and the polyethylene; therefore, the auxiliary agent can be uniformly dispersed and stably present in the isolation membrane, giving full play to its own function, so that the medical isolation membrane of the present invention has stable and excellent antibacterial and antistatic properties. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0031] Example 1

[0032] Preparation of auxiliary agent, the specific steps are as follows:

[0033] S1. First, place a 100 mL three-necked flask in an ice bath, then slowly add 23.9 mL of chlorosulfonic acid, and stir the chlorosulfonic acid in the ice bath to cool to below 15°C. After 15 minutes, slowly add 9 g of carvacrol while stirring, maintain the temperature at 10°C and react for 0.5 h, then raise the temperature to 60°C and react for 2 h. After the reaction, slowly dilute the mixture with ice water to precipitate, filter, wash the precipitate with ice water, and dry to obtain intermediate 1;

[0034] S2. First, place a 250 mL three-necked flask in an ice bath, and then blow nitrogen for 30 minutes to drive out the air in the flask. Then, add 12.4 g of intermediate 1, 10.4 mL of triethylamine, and 120 mL of DMSO. After stirring and dissolving, cool the system to 10°C in an ice bath. Under nitrogen protection, slowly add 4.3 mL of 1,3-propylenediamine to the above flask. After the addition is complete, stir and react at 50°C for 6 hours. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 2.

[0035] S3. Under nitrogen protection, 10 g of intermediate 2, 8.5 mL of pyridine and 100 mL of DMSO were added to a 250 mL three-necked flask. After stirring, 7.3 mL of 4-chloro-1-butene was slowly added, and the temperature was raised to 60° C. and kept for 2 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure. Purification was performed by column chromatography (a mixed solvent of benzene and ethyl acetate was selected as the eluent, and the volume ratio of benzene and ethyl acetate was 8:2). Distillation under reduced pressure gave intermediate 3.

[0036] S4. Under nitrogen protection, 11.8 g of intermediate 3, 6.3 mL of triethylamine and 120 mL of DMF were added to a 250 mL dry four-necked flask. After stirring evenly, 8.7 mL of chlorotetradecane was slowly added, and the temperature was raised to 70°C. The reaction was kept warm for 3 h. After the reaction was completed, the mixture was cooled to room temperature and distilled under reduced pressure. The mixture was purified by column chromatography (a mixed solvent of benzene and acetone was selected as the eluent, and the volume ratio of benzene and acetone was 9:1). The auxiliary agent was obtained by distillation under reduced pressure.

[0037] Example 2

[0038] Preparation of medical isolation membrane, the specific steps are as follows:

[0039] The raw materials were weighed by weight and 15 parts of low-density polyethylene, 50 parts of metallocene low-density polyethylene, 0.6 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.8 parts of ultraviolet absorber UV-P, 0.8 parts of the additive prepared in Example 1, 0.6 parts of organic fluorine resin TG-528A, and 0.05 parts of dicumyl peroxide were put into a high-speed mixer. After thorough mixing, the mixture was put into a twin-screw extruder for extrusion granulation, crushed by a pellet mill, dried, and put into a single-axis screw conveyor for film blowing to obtain a medical isolation membrane.

[0040] Example 3

[0041] Preparation of medical isolation membrane, the specific steps are as follows:

[0042] The raw materials were weighed by weight and 20 parts of low-density polyethylene, 56 parts of metallocene low-density polyethylene, 0.8 parts of antioxidant 1076, 0.2 parts of antioxidant 168, 1 part of ultraviolet absorber UV-9, 1.5 parts of the additive prepared in Example 1, 0.8 parts of organic fluorine resin TG-521B, and 0.08 parts of dibenzoyl peroxide were put into a high-speed mixer. After thorough mixing, the mixture was put into a twin-screw extruder for extrusion granulation, crushed by a pellet mill, dried, and put into a uniaxial screw conveyor for film blowing to obtain a medical isolation membrane.

[0043] Example 4

[0044] Preparation of medical isolation membrane, the specific steps are as follows:

[0045] The raw materials were weighed by weight and 25 parts of low-density polyethylene, 60 parts of metallocene low-density polyethylene, 1 part of antioxidant 1010, 0.5 parts of antioxidant 168, 0.5 parts of antioxidant DLTP, 1 part of ultraviolet absorber UV-531, 1 part of ultraviolet absorber UV-327, 2 parts of the auxiliary agent prepared in Example 1, 0.5 parts of organic fluorine resin TG-528A, 0.5 parts of organic fluorine resin TG-521B, and 0.1 parts of diisopropylbenzene peroxide were put into a high-speed mixer. After thorough mixing, the mixture was put into a twin-screw extruder, extruded into granules, crushed by a pellet mill, dried, and put into a single-axis screw conveyor for film blowing to obtain a medical isolation membrane.

[0046] Comparative Example 1

[0047] Preparation of medical isolation membrane, the specific steps are as follows:

[0048] The remaining steps remain unchanged, and the auxiliary agent of Example 4 is removed to prepare a medical isolation membrane.

[0049] Comparative Example 2

[0050] Preparation of medical isolation membrane, the specific steps are as follows:

[0051] The remaining steps remained unchanged, and the auxiliary agent in Example 4 was replaced by 1 part of tetramethylammonium oxalate and 1 part of carvacrol to prepare a medical isolation membrane.

[0052] Performance Testing

[0053] The mechanical properties, antibacterial properties, and antistatic properties of the medical isolation membranes prepared in Examples 2 to 4 and Comparative Examples 1 to 2 were tested, and the test results are shown in the following table:

[0054]

[0055] “ / ” indicates no antibacterial effect.

[0056] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0057] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. An antistatic medical isolation film, characterized in that: The invention comprises the following raw materials in parts by weight: 15 to 25 parts of low-density polyethylene, 50 to 60 parts of metallocene low-density polyethylene, 0.8 to 2 parts of antioxidant, 0.8 to 2 parts of ultraviolet absorber, 0.8 to 2 parts of auxiliary agent, 0.6 to 1 part of waterproof and oil-proof agent, and 0.05 to 0.1 part of cross-linking agent; Wherein, the auxiliary agent is prepared by the following steps: S1. Place the flask in an ice bath under nitrogen protection, add chlorosulfonic acid, and cool to below 15°C with stirring. Add carvacrol, react at 10°C for 0.5 h, then at 60°C for 2 h, and place in ice water for precipitation. Filter, wash, and dry to obtain intermediate 1. The reaction equation is as follows: S2. Place the flask in an ice bath, purge with nitrogen, add intermediate 1, triethylamine, and DMSO, cool to 10°C, add 1,3-propylenediamine, react at 50°C for 6 h, cool, and distill under reduced pressure to obtain intermediate 2. The reaction equation is as follows: S3. Under nitrogen protection, intermediate 2, pyridine and DMSO were added to a flask, stirred, and 4-chloro-1-butene was added. The mixture was reacted at 60° C. for 2 h, cooled, and distilled under reduced pressure. The mixture was purified by column chromatography and distilled under reduced pressure to obtain intermediate 3. The reaction equation is shown below: S4. Under nitrogen protection, add intermediate 3, triethylamine and DMF to the flask, stir, add tetradecane chloride, and react at 70°C for 3h. The reaction equation is as follows: After the reaction, the product is cooled, distilled under reduced pressure, purified by column chromatography, and distilled under reduced pressure to obtain an auxiliary agent.

2. The antistatic medical isolation film according to claim 1, characterized in that: The molar ratio of carvacrol to chlorosulfonic acid in step S1 is 1:

6.

3. The antistatic medical isolation film according to claim 1, characterized in that: The usage ratio of the intermediate 1, 1,3-propylenediamine, triethylamine and DMSO in step S2 is 12.4 g:4.3 mL:10.4 mL:120 mL.

4. The antistatic medical isolation film according to claim 1, characterized in that: The usage ratio of the intermediate 2 in step S3, 4-chloro-1-butene, pyridine, and DMSO is 0.035 mol:0.072 mol:8.5 mL:100 mL.

5. The antistatic medical isolation film according to claim 1, characterized in that: The usage ratio of intermediate 3, tetradecane chloride, triethylamine and DMF in step S4 is 0.03 mol:0.032 mol:6.3 mL:120 mL.

6. The antistatic medical isolation film according to claim 1, characterized in that: The ultraviolet absorber is one or more of ultraviolet absorber UV-P, ultraviolet absorber UV-9, ultraviolet absorber UV-531, and ultraviolet absorber UV-327.

7. The antistatic medical isolation film according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant DLTP.

8. The antistatic medical isolation film according to claim 1, characterized in that: The waterproof and oil-proof agent is one or both of organic fluorine resin TG-528A and organic fluorine resin TG-521B.

9. The antistatic medical isolation film according to claim 1, characterized in that: The cross-linking agent is one or both of dicumyl peroxide and dibenzoyl peroxide.

10. The method for preparing an antistatic medical isolation membrane according to claim 1, characterized in that: The following steps are involved: The raw materials are weighed by weight and put into a high-speed mixer. After being fully mixed, they are put into a twin-screw extruder for extrusion granulation. The materials are crushed by a pellet mill, dried, and put into a single-axis screw conveyor for film blowing to obtain a medical isolation membrane.

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