Preparation method and application of biogel antibacterial material

Abstract

The invention relates to the technical field of gel materials, and discloses a preparation method and application of a biogel antibacterial material.The preparation method comprises the steps that polyethylene glycol diimidazole phenoxy ethylene oxide serves as a cross-linking agent, in a sodium hydroxide alkaline catalytic system, double-end epoxy groups of the polyethylene glycol diimidazole phenoxy ethylene oxide can react with hydroxyl groups of cellulose, and the cross-linking agent can react with hydroxyl groups of cellulose; the preparation method comprises the following steps: carrying out chemical cross-linking on cellulose to obtain a biogel material with a porous cross-linked network structure, and finally carrying out quaternization reaction on a chloroalkyl compound and an imidazole group to introduce a large amount of quaternary ammonium salt groups into the cellulose biogel material. The water absorption rate and the antibacterial performance of the gel material are obviously improved. And moreover, the coating has very good coating performance on wormwood essential oil and artemisinin essential oil, and has better practical application in antibacterial hygienic products such as paper diapers, maintenance pads and the like.

Description

Technical Field

[0001] The invention relates to the technical field of gel materials, and in particular to a preparation method and application of a biogel antibacterial material. Background Art

[0002] Antibacterial materials are functional materials with bactericidal properties, mainly antibacterial plastics, antibacterial fibers, antibacterial ceramics, etc., which are widely used in sanitary products, medical fields, etc. Cellulose is a cheap and easily available natural biomass resource, non-toxic and pollution-free, with good biocompatibility. It can be made into materials such as fibers, films, gels, etc., and has broad application prospects in dressings, diapers, and nursing pads.

[0003] Using cellulose matrix to make gel, microspheres and other materials, it is possible to achieve the coating and sustained release of plant essential oils. Patent CN118063808A discloses a cinnamon essential oil-sugar bagasse cellulose microsphere with sustained-release antibacterial effect and its preparation method and application, which discloses that the bagasse cellulose microspheres obtained by using bagasse cellulose, maltodextrin, acrylic resin NE30D and the like as raw materials can better encapsulate the essential oil, with high embedding rate, long sustained-release time and good antibacterial effect. However, the bagasse cellulose microspheres do not show good water absorption, which is not conducive to their practical application in diapers, maintenance pads and the like. Summary of the invention

[0004] 1. Technical issues to be resolved In view of the shortcomings of the prior art, the present invention provides a method for preparing and applying a biogel antibacterial material, which solves the problem that the cellulose gel material has low water absorption and no antibacterial property.

[0005] (II) Technical solution A method for preparing a biogel antibacterial material comprises the following steps: Step S1, adding N,N-dimethylformamide, polyethylene glycol dichloride, 2-[(4-imidazolephenoxy)methyl]ethylene oxide, and triethylamine into a reaction container to react, adding saturated sodium chloride solution and dichloromethane, extracting and separating, adding anhydrous sodium sulfate to the dichloromethane organic layer to dry and remove water, filtering, distilling the filtrate under reduced pressure, washing with petroleum ether, and drying to obtain polyethylene glycol diimidazolephenoxyethylene oxide.

[0006] Step S2, adding deionized water, sodium hydroxide, urea, and cellulose into a reaction container, freezing at -20°C after stirring, then thawing at room temperature, adding polyethylene glycol diimidazole phenoxy ethylene oxide, performing a cross-linking reaction, filtering, washing with ethanol, then placing in a dialysis bag, dialyzing and purifying with deionized water, and drying to obtain a biogel material.

[0007] Step S3, adding N,N-dimethylformamide, gel material, and chloroalkyl compound into a reaction container to carry out quaternization reaction, filtering and washing with ethanol, then placing in a dialysis bag, dialyzing and purifying with deionized water, and drying to obtain a biogel antibacterial material.

[0008] Furthermore, in step S1, the molar ratio of polyethylene glycol dichloride, 2-[(4-imidazolephenoxy)methyl]ethylene oxide, and triethylamine is 1:(4-6):(4-6).

[0009] Furthermore, the reaction in step S1 is carried out at 50-70° C. for 12-18 h.

[0010] Furthermore, the mass ratio of cellulose to polyethylene glycol diimidazole phenoxy ethylene oxide in S2 is 1:(0.4-2).

[0011] Furthermore, in step S2, the cross-linking reaction is carried out at 60-85° C. for 6-12 hours.

[0012] Furthermore, in step S2, the mass ratio of the gel material to the chloroalkyl compound is 1:(0.12-0.7).

[0013] Further, the chloroalkyl compound structural formula is , n is any integer between 13 and 17.

[0014] Furthermore, the quaternization reaction in step S3 is carried out at 90-120° C. for 24-48 hours.

[0015] Furthermore, the preparation method of 2-[(4-imidazolephenoxy)methyl]ethylene oxide is as follows: toluene, 2-[(4-bromophenoxy)methyl]ethylene oxide (CAS No. 2212-06-8) in a molar ratio of 1: (1.1-1.2): (0.05-0.06): (2.6-3), imidazole-5-ylboric acid (CAS No. 943138-65-6), tetrakis(triphenylphosphine)palladium, potassium carbonate, and deionized water are added to a reaction container, heated to 100-110° C., condensed and refluxed for 18-24 hours, deionized water and dichloromethane are added, extracted and separated, anhydrous sodium sulfate is added to the organic layer to dry and remove water, filtered, the filtrate is distilled under reduced pressure, and recrystallized from dichloromethane to obtain 2-[(4-imidazolephenoxy)methyl]ethylene oxide.

[0016] Furthermore, the biogel antibacterial material is used in antibacterial hygiene products. The biogel antibacterial material can be embedded with wormwood essential oil and artemisinin essential oil and used in antibacterial hygiene products.

[0017] (III) Technical effect: The present invention conducts a Suzuki coupling reaction between 2-[(4-bromophenoxy)methyl]oxirane and imidazole-5-boronic acid, and then reacts with the terminal acyl chloride group of polyethylene glycol dichloride to obtain polyethylene glycol diimidazolephenoxyoxirane containing epoxy groups and imidazole groups at both ends.

[0018] The invention uses polyethylene glycol diimidazole phenoxy ethylene oxide as a crosslinking agent. In a sodium hydroxide alkaline catalytic system, the double-end epoxy groups can react with the hydroxyl groups of cellulose, thereby chemically crosslinking the cellulose to obtain a biogel material with a porous crosslinked network structure. Finally, a quaternization reaction is carried out with an alkyl chloride compound and an imidazole group, thereby introducing a large number of quaternary ammonium salt groups into the cellulose biogel material.

[0019] The cellulose of the present invention is cross-linked with polyethylene glycol diimidazole phenoxy ethylene oxide to form a porous spatial network structure, and hydrophilic polyethylene glycol molecular chains and quaternary ammonium salt hydrophilic groups are introduced into the cellulose gel matrix, which significantly improves the water absorption rate of the gel material. In addition, the cellulose of the present invention contains a large amount of quaternary ammonium salt antibacterial groups, so that the biogel antibacterial material exhibits high antibacterial performance against Escherichia coli, Staphylococcus aureus and Candida albicans. The biogel antibacterial material has broad application prospects in antibacterial materials such as sanitary products and medical products.

[0020] The biogel antibacterial material of the present invention has a porous spatial structure and a large specific surface area, and exhibits good coating performance for wormwood essential oil and artemisinin essential oil, with the coating amount reaching 0.294-0.575 g / g and 0.252-0.480 g / g, respectively. The biogel antibacterial material has better practical applications in antibacterial sanitary products such as diapers and nursing pads. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the reaction formula for preparing 2-[(4-imidazolephenoxy)methyl]oxirane.

[0022] Figure 2 This is the reaction formula for preparing polyethylene glycol diimidazole phenoxy ethylene oxide.

[0023] Figure 3 It is the reaction formula for preparing biogel antibacterial material. DETAILED DESCRIPTION

[0024] In order to make the purpose, implementation mode and advantages of the present application clearer, the exemplary implementation mode of the present application will be clearly and completely described below in conjunction with the drawings in the exemplary embodiments of the present application. Obviously, the exemplary embodiments described are only part of the embodiments of the present application, rather than all of the embodiments. It should be noted that the brief description of the terms in this application is only for the convenience of understanding the implementation mode described below, and is not intended to limit the implementation mode of the present application. Unless otherwise specified, these terms should be understood according to their ordinary and usual meanings.

[0025] Polyethylene glycol dichloride was prepared according to the method of the journal "Synthetic Resins and Plastics", 2012, 29 (4): 38; the literature "Synthesis of Multi-arm Star-shaped Polyethylene Glycol". The structural formula is as follows: .

[0026] Example 1 (1) Add 150 mL of toluene, 40 mmol of 2-[(4-bromophenoxy)methyl]oxirane, 44 mmol of imidazole-5-ylboric acid, 2.4 mmol of tetrakis(triphenylphosphine)palladium, 120 mmol of potassium carbonate, and 20 mL of deionized water into a reaction vessel, heat to 110°C, condense and reflux for 24 h, add deionized water and dichloromethane, extract and separate, add anhydrous sodium sulfate to the organic layer, dry and remove water, filter, distill the filtrate under reduced pressure, and recrystallize from dichloromethane to obtain 2-[(4-imidazolephenoxy)methyl]oxirane.

[0027] (2) Add 150 mL of N,N-dimethylformamide, 10 mmol of polyethylene glycol dichloride, 60 mmol of 2-[(4-imidazolephenoxy)methyl]ethylene oxide, and 60 mmol of triethylamine to a reaction vessel, react at 70°C for 12 h, add saturated sodium chloride solution and dichloromethane, extract and separate, add anhydrous sodium sulfate to the dichloromethane organic layer to dry and remove water, filter, distill the filtrate under reduced pressure, wash with petroleum ether, and dry to obtain polyethylene glycol diimidazolephenoxyethylene oxide.

[0028] (3) Add 700 mL of deionized water, 45 g of sodium hydroxide, 32 g of urea, and 20 g of cellulose to a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 8 g of polyethylene glycol diimidazole phenoxy ethylene oxide, and carry out a cross-linking reaction at 60°C for 12 h. After filtering, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0029] (4) Add 2 L of N,N-dimethylformamide, 50 g of gel material, and 6 g of 1-chlorotetradecane into a reaction container, and carry out quaternization reaction at 90 °C for 36 h. Filter and wash with ethanol, then place in a dialysis bag, dialyze and purify with deionized water, and dry to obtain a biogel antibacterial material.

[0030] Example 2 (1) Add 150 mL of toluene, 40 mmol of 2-[(4-bromophenoxy)methyl]oxirane, 48 mmol of imidazole-5-ylboric acid, 2 mmol of tetrakis(triphenylphosphine)palladium, 104 mmol of potassium carbonate, and 20 mL of deionized water into a reaction vessel, heat to 100°C, condense and reflux for 18 h, add deionized water and dichloromethane, extract and separate, add anhydrous sodium sulfate to the organic layer, dry and remove water, filter, distill the filtrate under reduced pressure, and recrystallize from dichloromethane to obtain 2-[(4-imidazolephenoxy)methyl]oxirane.

[0031] (2) Add 100 mL of N,N-dimethylformamide, 10 mmol of polyethylene glycol dichloride, 40 mmol of 2-[(4-imidazolephenoxy)methyl]ethylene oxide, and 40 mmol of triethylamine to a reaction vessel, react at 70°C for 18 h, add saturated sodium chloride solution and dichloromethane, extract and separate, add anhydrous sodium sulfate to the dichloromethane organic layer to dry and remove water, filter, distill the filtrate under reduced pressure, wash with petroleum ether, and dry to obtain polyethylene glycol diimidazolephenoxyethylene oxide.

[0032] (3) Add 700 mL of deionized water, 35 g of sodium hydroxide, 28 g of urea, and 20 g of cellulose to a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 18 g of polyethylene glycol diimidazole phenoxy ethylene oxide, and perform a cross-linking reaction at 65°C for 12 h. After filtering, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0033] (4) Add 2 L of N,N-dimethylformamide, 50 g of gel material, and 16 g of 1-chlorohexadecane into a reaction container, and carry out quaternization reaction at 120° C. for 24 h. Filter and wash with ethanol, then place in a dialysis bag, dialyze and purify with deionized water, and dry to obtain a biogel antibacterial material.

[0034] Example 3 (1) Add 650 mL of deionized water, 40 g of sodium hydroxide, 28 g of urea, and 20 g of cellulose into a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 29 g of polyethylene glycol diimidazole phenoxy ethylene oxide (prepared according to the method of Example 1), carry out cross-linking reaction at 85°C for 6 h, filter, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0035] (2) Add 2.5 L N,N-dimethylformamide, 50 g gel material, and 25 g 1-chlorohexadecane into a reaction container, and carry out quaternization reaction at 120° C. for 24 h. Filter and wash with ethanol, then place in a dialysis bag, dialyze and purify with deionized water, and dry to obtain a biogel antibacterial material.

[0036] Example 4 (1) Add 650 mL of deionized water, 40 g of sodium hydroxide, 35 g of urea, and 20 g of cellulose into a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 40 g of polyethylene glycol diimidazole phenoxy ethylene oxide (prepared according to the method of Example 1), carry out cross-linking reaction at 85°C for 8 h, filter, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0037] (2) Add 3 L of N,N-dimethylformamide, 50 g of gel material, and 35 g of 1-chlorooctadecane into a reaction container, and carry out quaternization reaction at 110° C. for 48 h. Filter and wash with ethanol, then place in a dialysis bag, dialyze and purify with deionized water, and dry to obtain a biogel antibacterial material.

[0038] Comparative Example 1 (1) Add 700 mL of deionized water, 45 g of sodium hydroxide, 32 g of urea, and 20 g of cellulose into a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 8 g of ethylene glycol diglycidyl ether, and perform cross-linking reaction at 60°C for 12 h. After filtering, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0039] Comparative Example 2 (1) Add 700 mL of deionized water, 45 g of sodium hydroxide, 32 g of urea, and 20 g of cellulose into a reaction container, stir, freeze at -20°C, and then thaw at room temperature. Then add 8 g of polyethylene glycol diimidazole phenoxy ethylene oxide (prepared according to the method of Example 1), carry out cross-linking reaction at 60°C for 12 h, filter, wash with ethanol, place in a dialysis bag, dialyze with deionized water for purification, and dry to obtain a biogel material.

[0040] Antibacterial performance test: The gel material was pressed into a circular film material with a thickness of 2 mm. It was sterilized by ultraviolet irradiation. Escherichia coli, Staphylococcus aureus, and Candida albicans were used as experimental bacteria.

[0041] The experimental bacteria were activated in an incubator at 37°C for 24 h, then graded diluted and 0.1 mL of 10 7 cfu / mL was evenly coated on the surface of the agar medium, and the circular membrane material was closely attached to the surface of the agar medium, and then cultured in an incubator at 37°C for 24 hours, and finally the diameter of the inhibition zone was measured. The test results are shown in the table below.

[0042]

[0043] Water absorption test. Weigh a certain mass of gel material, soak it in deionized water for 12 hours, take out the gel material, wipe off the surface moisture and weigh it, and calculate the water absorption rate. Water absorption rate = (m1-m0) / m0. m1 is the mass of the gel material after absorbing water. m0 is the mass of the gel material before absorbing water. The test results are shown in the table below.

[0044]

[0045] As can be seen from the above table, the biogel antibacterial materials of Examples 1-4 contain hydrophilic polyethylene glycol molecular chains and quaternary ammonium salt hydrophilic groups, which significantly improve the water absorption rate of the gel material. In addition, the biogel antibacterial material contains quaternary ammonium salt antibacterial groups, so that the biogel antibacterial material exhibits high antibacterial properties against Escherichia coli, Staphylococcus aureus and Candida albicans.

[0046] In Comparative Example 1, ethylene glycol diglycidyl ether is used as a cross-linking agent to cross-link cellulose. The cross-linked biogel material does not contain hydrophilic polyethylene glycol molecular chains and quaternary ammonium salt hydrophilic groups, has a low water absorption rate, and does not show an inhibition zone diameter for Escherichia coli, Staphylococcus aureus and Candida albicans, and does not have antibacterial properties.

[0047] The biogel material of Comparative Example 2 has not undergone quaternization reaction of chloroalkyl compounds, does not contain quaternary ammonium salt antibacterial groups, and does not show an inhibition zone diameter against Escherichia coli, Staphylococcus aureus and Candida albicans, and has no antibacterial properties.

[0048] Add 5-15g of wormwood essential oil, 0.2g of emulsifier (hydrogenated castor oil polyoxyethylene ether HEL-40), and 5g of biogel antibacterial material to 1L of deionized water, stir for 12h, take out the gel material, wet the paper towel with 70% ethanol aqueous solution, and then wipe the wormwood essential oil remaining on the surface of the gel material, dry the gel material in a blast drying mechanism at 80℃ to remove water, weigh it, and calculate the amount of wormwood essential oil coated by the gel material. The test results are shown in the table below.

[0049]

[0050] Add 5-15g artemisinin essential oil, 0.2g emulsifier (hydrogenated castor oil polyoxyethylene ether HEL-40), and 5g biogel antibacterial material to 1L deionized water, stir for 12h, take out the gel material, wet a paper towel with 70% ethanol aqueous solution, and then wipe the artemisinin essential oil remaining on the surface of the gel material, dry the gel material in a forced air drying mechanism at 80°C to remove water, weigh it, and calculate the amount of artemisinin essential oil coated by the gel material.

[0051]

[0052] After testing, when the dosage of wormwood essential oil was 15g, the coating amount of wormwood essential oil by the biogel antibacterial material reached 0.294-0.575g / g. When the dosage of artemisinin essential oil was 15g, the coating amount of artemisinin essential oil by the biogel antibacterial material reached 0.252-0.480g / g.

[0053] The above content is a further detailed description of the present invention. It cannot be determined that the specific implementation methods of the present invention are limited to these. For ordinary technicians in the technical field to which the present invention belongs, without departing from the concept of the present invention, they can also make several simple deductions or substitutions, which should be regarded as belonging to the protection scope of the present invention determined by the submitted claims.

Claims

1. A method for preparing a biogel antibacterial material, characterized in that: The preparation method comprises the following steps: Step S1, adding N,N-dimethylformamide, polyethylene glycol dichloride, 2-[(4-imidazolephenoxy)methyl]ethylene oxide, and triethylamine into a reaction container, reacting, adding saturated sodium chloride solution and dichloromethane, extracting and separating, drying to remove water, washing, and drying to obtain polyethylene glycol diimidazolephenoxyethylene oxide; Step S2, adding deionized water, sodium hydroxide, urea, and cellulose into a reaction container, freezing at -20°C after stirring, then thawing at room temperature, adding polyethylene glycol diimidazole phenoxy ethylene oxide, performing a cross-linking reaction, filtering and washing, then placing in a dialysis bag, dialyzing and purifying, and drying to obtain a biogel material; Step S3, adding N,N-dimethylformamide, gel material, and chloroalkyl compound into a reaction container, performing quaternization reaction, filtering and washing, and then placing in a dialysis bag, dialyzing and purifying, and drying to obtain a biogel antibacterial material.

2. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: In the step S1, the molar ratio of polyethylene glycol dichloride, 2-[(4-imidazolephenoxy)methyl]ethylene oxide and triethylamine is 1:(4-6):(4-6).

3. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: In step S1, the reaction is carried out at 50-70° C. for 12-18 hours.

4. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: The mass ratio of cellulose to polyethylene glycol diimidazole phenoxy ethylene oxide in the S2 is 1:(0.4-2).

5. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: The cross-linking reaction in step S2 is carried out at 60-85° C. for 6-12 hours.

6. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: In the step S2, the mass ratio of the gel material to the chloroalkyl compound is 1:(0.12-0.7).

7. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: The structural formula of the chloroalkyl compound is , n is any integer between 13 and 17.

8. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: The quaternization reaction in step S3 is carried out at 90-120° C. for 24-48 hours.

9. The method for preparing the biogel antibacterial material according to claim 1, characterized in that: The preparation method of 2-[(4-imidazolephenoxy)methyl]oxirane is as follows: toluene, 2-[(4-bromophenoxy)methyl]oxirane in a molar ratio of 1:(1.1-1.2):(0.05-0.06):(2.6-3), imidazole-5-ylboric acid, tetrakis(triphenylphosphine)palladium, potassium carbonate, and deionized water are added into a reaction container, heated to 100-110° C., condensed and refluxed for 18-24 hours, deionized water and dichloromethane are added, extracted and separated, anhydrous sodium sulfate is added to the organic layer for drying and water removal, filtered, the filtrate is distilled under reduced pressure, and recrystallized from dichloromethane to obtain 2-[(4-imidazolephenoxy)methyl]oxirane.

10. An application of the biogel antibacterial material obtained by the preparation method according to any one of claims 1 to 9 in antibacterial sanitary products, wherein the biogel antibacterial material can be embedded with wormwood essential oil and artemisinin essential oil and used in antibacterial sanitary products.

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