A hydrophilic antibacterial functional material and its preparation method and application

Abstract

The present invention belongs to the technical field of antibacterial modification of fiber materials, and relates to a method for synthesizing a hydrophilic antibacterial organosilicon quaternary ammonium salt and its use as a raw material to prepare a functional material with hydrophilic antibacterial properties in the fields of medical protective equipment, medical dressings, household textiles, sanitary products, etc. The hydrophilic antibacterial organosilicon quaternary ammonium salt provided by the present invention is simple to prepare, has good antibacterial properties, can form a polymer with a three-dimensional interpenetrating network structure on the surface of a substrate through a self-polymerization reaction, and the polymer does not fall off freely, so that the substrate has super-hydrophilic and long-lasting antibacterial functions. After washing 50 times, the antibacterial rates of Escherichia coli, Staphylococcus aureus, and Candida albicans are maintained at more than 99%; it has excellent hydrophilicity, and the water droplet wetting time of the material is less than 0.1s. The method of use is simple and easy to industrialize. The post-processing amount is small, and the hydrophilic antibacterial modification of the substrate can be achieved when the molar concentration is 0.1-1 mmol / L, thereby reducing production costs.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial modification of fiber materials, and relates to a method for synthesizing a hydrophilic antibacterial organosilicon quaternary ammonium salt compound and its application as a raw material in preparing a functional material with hydrophilic antibacterial properties in the fields of medical protective equipment, medical dressings, household textiles, sanitary products, etc. Background Art

[0002] Textile products are closely intertwined with our daily lives. Clothing, bedding, and other textile products are indispensable. Commonly used materials include cellulose (cotton, linen, etc.), chemical fibers (polyester, polypropylene, nylon, spandex, acrylic, etc.), and natural silk. Over the years, the broad definition of woven products has expanded beyond traditional clothing and bedding to include nonwoven products, or products produced using nonwoven technology. Nonwoven fabrics, also known as non-woven fabrics or nonwovens, are made from oriented or random fibers that are needle-punched or hydroentangled. They are a new generation of environmentally friendly materials that are moisture-resistant, breathable, flexible, lightweight, non-toxic, non-irritating, colorful, affordable, and recyclable, making them widely used in our daily lives. Non-woven fabrics are called cloth because they resemble cloth and possess certain properties. Depending on their intended use, non-woven fabrics can be composed of one or a combination of the following materials: polyolefins (polypropylene, polyethylene, polyvinyl chloride, polyester, etc.), chemical fibers (polyester, spandex, nylon, acrylic, nylon, etc.), and natural polymers (chitosan, alginate, etc.). For example, in the production of diapers, diaper pads, sanitary napkins, and other products, these materials lack hydrophilic groups, resulting in poor hydrophilic properties. Therefore, hydrophilic treatment is required during production. Currently, the hydrophilizing agents used in industrial production are mostly fatty alcohol polyoxyethylene ethers, which are applied using a simple impregnation and drying process, making them easily detached from the non-woven fabric. These substances have certain biotoxicity characteristics and can cause environmental pollution during their preparation and use.

[0003] Currently, most antimicrobial products on the market (such as antimicrobial clothing and bedding) are zinc ion-based. Zinc ions are heavy metal salts, and most are treated using an impregnation and drying process. This process can easily lead to the dissolution and shedding of the zinc ion antimicrobial agent, gradually weakening its antimicrobial properties with long-term use. Furthermore, nonwoven fabrics are initially treated with a hydrophilic treatment during production to increase their hydrophilicity. If this is followed by an impregnation treatment, the hydrophilicity is significantly reduced. There are also reports of using PVA cross-linked with glutaraldehyde to achieve hydrophilicity. While this method can prevent the hydrophilic agent from shedding, the presence of the coating can alter some material properties, such as softness and comfort. Furthermore, glutaraldehyde is a toxic chemical that can cause environmental pollution, and residual glutaraldehyde in the coating after treatment can pose a health risk.

[0004] In summary, it is necessary to develop a safe, non-toxic, low-cost, self-polymerizing treatment agent with both hydrophilic and antibacterial functions suitable for medical, household, sanitary and other fields, and use it as the main raw material to prepare a functional material with hydrophilic and antibacterial properties for application in medical protective equipment, medical dressings, household textiles, sanitary products and other fields. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to provide a hydrophilic antibacterial organosilicon quaternary ammonium salt compound and a preparation method thereof, and further provide a hydrophilic antibacterial functional material using the quaternary ammonium salt for antibacterial treatment.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a hydrophilic antibacterial organosilicon quaternary ammonium salt having the following general structural formula, wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , where n is a positive integer of 1-30 or any one of CHOH(CH2OH)2; R2 is a saturated alkane with a carbon chain of 1-16; X is fluorine, chlorine, bromine or iodine;

[0008]

[0009] Furthermore, the present invention provides a method for preparing a hydrophilic antibacterial organosilicon quaternary ammonium salt, which mainly comprises the following steps:

[0010] Step A: a certain amount of polyol is placed in a reaction vessel, and a solvent is added to form a polyol solution; a certain amount of chlorinated compound is weighed and added to the polyol solution, heated to a certain temperature, reacted for a period of time, and the reaction progress is determined by thin layer chromatography. After the reaction is complete, the solvent is removed, and a chlorine-substituted polyol is obtained by sedimentation method; the addition ratio of the polyol, solvent and chlorinated compound is 1:10-15:0.9-1; the reaction temperature is set to 70-110°C, and the reaction time is set to 4-8 hours.

[0011] The polyol includes any one of polyethylene glycol, polyvinyl alcohol, and glycerol; the solvent includes any one of tetrahydrofuran and toluene; and the chlorinated compound includes any one of phosphorus oxychloride POCl3, phosphorus trichloride PCl3, and N-chlorosuccinimide NClS.

[0012] Step B: a certain amount of silane coupling agent is placed in a reaction vessel, a solvent, a base and a certain amount of the chlorine-substituted polyol prepared in step A are added, the mixture is heated to a certain temperature, reacted for a period of time, and the progress of the reaction is determined by thin-layer chromatography. After the reaction is complete, the solvent is removed, and an organosilicon compound containing the polyol is obtained by a sedimentation method; the addition ratio of the silane coupling agent, the solvent, the base and the chlorine-substituted polyol is 1:10-15:2-6:2-4; the reaction temperature is set at 70-110°C, and the reaction time is set at 6-10 hours.

[0013] The silane coupling agent includes any one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, and 3-aminopropyltriisopropoxysilane; the solvent includes any one of tetrahydrofuran and toluene; and the base includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.

[0014] Step C: taking a certain amount of the polyol-containing organosilicon compound prepared in step B and placing it in a reaction vessel, adding a solvent, a base and a certain amount of halogenated alkane, heating to a certain temperature, reacting for a period of time, determining the progress of the reaction by thin layer chromatography, and after the reaction is complete, removing the solvent and obtaining a hydrophilic antibacterial organosilicon quaternary ammonium salt by a sedimentation method; the addition ratio of the hydrophilic antibacterial organosilicon compound, the solvent, the base and the halogenated alkane is 1:10-15:1-3:1-3; the reaction temperature is set at 70-110°C, and the reaction time is set at 6-10 hours.

[0015] The solvent includes any one of tetrahydrofuran, toluene, and acetonitrile; the base includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; and the halogenated alkane includes any one of saturated halogenated hydrocarbons having 1 to 16 carbon atoms. The polyol-containing organosilicon compound in step B has the following structural formula, wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30 or any one of CHOH(CH2OH)2;

[0016]

[0017] The present invention provides a hydrophilic antibacterial functional material with long-lasting antibacterial properties. After washing 50 times, the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are maintained above 99%; it has excellent hydrophilicity, and the time it takes for a water drop to wet the material is less than 0.1s.

[0018] like Figure 1 and Figure 2As shown, a hydrophilic antibacterial organosilicon quaternary ammonium salt with a concentration of 0.1-1 mmol / L is prepared and allowed to stand for a period of time under acidic conditions, a substrate is immersed in the above solution, and the solution is dried at 100-150°C to form a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate; the acidic solution is any one of hydrochloric acid, sulfuric acid or acetic acid.

[0019] The hydrophilic antibacterial organosilicon quaternary ammonium salt is allowed to stand for 1-6 hours under acidic conditions of pH 4-6 to undergo hydrolysis, thereby forming an organosilicon quaternary ammonium salt containing silanol groups. The organosilicon quaternary ammonium salt containing silanol groups undergoes polymerization through heating to form a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate. The organosilicon quaternary ammonium salt containing silanol groups has the following structural formula: wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30 or any one of CHOH(CH2OH)2; R2 is a saturated alkane with a carbon chain of 1-16; X is fluorine, chlorine, bromine or iodine;

[0020]

[0021] like Figure 1 As shown, the process of forming a Si-O-Si three-dimensional interpenetrating network polymer on the surface of the substrate after the organic silicon quaternary ammonium salt compound containing silanol is polymerized by heating reaction is achieved in situ by a one-step self-polymerization reaction of silanol. This is because the silanol has high reactivity. Under heating conditions, a condensation reaction occurs between the silanols. During the condensation reaction, the OH groups and H ions in the two silanols can be separated to form a Si-O-Si bond and release a water molecule. Since the above-mentioned organic silicon quaternary ammonium salt containing hydroxyl groups contains multiple silanols, a condensation reaction occurs between the silanols and the silanols to finally form a Si-O-Si three-dimensional interpenetrating network polymer. The structural formula of the polymer is shown below, where R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30, or one of CHOH(CH2OH)2; R2 is a saturated alkane with a carbon chain of 1-16; X is fluorine, chlorine, bromine, or iodine;

[0022]

[0023] Furthermore, the substrate includes any one or more of polyolefin materials, chemical fiber materials or natural polymer materials; the polyolefin materials include any one of polypropylene, polyethylene, polyvinyl chloride or polyester; the chemical fiber materials include any one of polyester, spandex, nylon, acrylic or nylon; the natural polymer materials include any one of chitosan, cotton, linen, alginate, etc.

[0024] The present invention further provides an application of a functional material as a raw material in the fields of medical protective products, medical dressings, household textiles, sanitary products, etc.

[0025] The beneficial effects of the present invention are:

[0026] 1. This invention provides a hydrophilic antibacterial functional material with long-lasting antibacterial properties. After 50 washes, the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans remain above 99%. Furthermore, the material exhibits excellent hydrophilicity, with water droplets instantly wetting the treated material in less than 0.1 seconds. This material has promising applications in medical protective equipment, medical dressings, household textiles, and sanitary products.

[0027] 2. The present invention provides a hydrophilic antibacterial organosilicon quaternary ammonium salt compound for use in the preparation of hydrophilic antibacterial functional materials, having excellent antibacterial properties. A three-dimensional Si-O-Si interpenetrating network polymer can be formed through a self-polymerization reaction and attached to a substrate. The resulting polymer does not release or detach, imparting super-hydrophilicity and long-lasting antibacterial properties to the substrate. The method of use is simple and amenable to industrial production. Post-processing requires minimal dosage, and hydrophilic antibacterial modification of the substrate can be achieved at a molar concentration of 0.1-1 mmol / L, reducing production costs.

[0028] 3. The present invention provides a method for preparing a hydrophilic antibacterial organosilicon quaternary ammonium salt compound for use in the preparation of hydrophilic antibacterial functional materials. The method has abundant raw materials, is simple and easy to operate, and can achieve batch preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solution of the present invention, the following briefly introduces the drawings required for use in the embodiments or descriptions of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Attachment Figure 1 This is a schematic diagram of the hydrophilic antibacterial organosilicon quaternary ammonium salt polymer intermediate in the hydrophilic antibacterial functional material acting on the surface of the substrate, causing the substrate surface to be entangled by Si-O-Si bonds to produce a hydrophilic antibacterial effect.

[0031] Attachment Figure 2 Schematic diagram of the preparation of hydrophilic antibacterial organosilicon quaternary ammonium salts and their hydrolysis to intermediates.

[0032] Attachment Figure 3 These are test diagrams of the hydrophilicity of polypropylene non-woven fabrics, where (a) (b) (c) (d) are the water contact angles of PP, PP-A, PP-B, and PP-C, respectively.

[0033] Attachment Figure 4 The hydrophilic performance test diagram of chitosan non-woven fabric, where (a) (b) (c) (d) are the water contact angles of CS, CS-A, CS-B, and CS-C, respectively.

[0034] Attachment Figure 5 This is the hydrogen spectrum of compound PEG-200-Cl.

[0035] Attachment Figure 6 This is the carbon spectrum of compound PEG-200-Cl.

[0036] Attachment Figure 7 This is the hydrogen spectrum of compound PEG-600-Cl.

[0037] Attachment Figure 8 This is the carbon spectrum of compound PEG-600-Cl.

[0038] Attachment Figure 9 This is the hydrogen spectrum of compound PEG-1000-Cl.

[0039] Attachment Figure 10 This is the carbon spectrum of compound PEG-1000-Cl.

[0040] Attachment Figure 11 This is the hydrogen spectrum of compound Si-PEG-200.

[0041] Attachment Figure 12 This is the carbon spectrum of compound Si-PEG-200.

[0042] Attachment Figure 13 This is the hydrogen spectrum of compound Si-PEG-600.

[0043] Attachment Figure 14 This is the carbon spectrum of compound Si-PEG-600.

[0044] Attachment Figure 15 This is the hydrogen spectrum of compound Si-PEG-1000.

[0045] Attachment Figure 16 This is the carbon spectrum of compound Si-PEG-1000.

[0046] Attachment Figure 17 It is the hydrogen spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound A.

[0047] Attachment Figure 18 This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound A.

[0048] Attachment Figure 19 It is the hydrogen spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound B.

[0049] Attachment Figure 20This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound B.

[0050] Attachment Figure 21 It is the hydrogen spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound C.

[0051] Attachment Figure 22 This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound C.

[0052] Attachment Figure 23 It is the hydrogen spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound D.

[0053] Attachment Figure 24 This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound D.

[0054] Attachment Figure 25 It is a hydrophilic antibacterial organosilicon quaternary ammonium salt compound E hydrogen spectrum.

[0055] Attachment Figure 26 This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound E.

[0056] Attachment Figure 27 It is the hydrogen spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound F.

[0057] Attachment Figure 28 This is the carbon spectrum of hydrophilic antibacterial organosilicon quaternary ammonium salt compound F. DETAILED DESCRIPTION

[0058] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. The embodiments mentioned are all implemented based on the technical solutions of the present invention, and detailed implementation processes are given. However, it should be noted that the scope of protection of the present invention is not limited to the following embodiments. Example

[0059] 1. Preparation of chlorine-substituted polyethylene glycol:

[0060] Take a Schrank flask, add 50 mL of dry tetrahydrofuran, add PEG-200 and phosphorus oxychloride, control the molar ratio of polyethylene glycol to phosphorus oxychloride to be 1:0.9, heat to 80°C, react for 4 hours, and add ice water to quench the reaction after the reaction is completed. At this time, a white solid is produced in the reaction flask. The white solid is recrystallized from ethanol to obtain the final product PEG-200-Cl with a yield of 90%.

[0061] The same method was used to modify PEG-600 and PEG-1000 to obtain PEG-600-Cl and PEG-1000-Cl, respectively. The reaction process is shown in the following diagram:

[0062]

[0063] Its structural characterization is as follows:

[0064] Compound PEG-200-Cl (C8H 17 ClO4)

[0065] 1H NMR (400 MHz, DMSO) δ5.4(s, 1 H), 3.8(t, 2 H), δ3.7(t, 2 H), 3.53(m, 12H).

[0066] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3

[0067] HRMS(ESI) m / z: calc for[C8H 18 ClO4]+:213.0984; Found:213.0988.

[0068] Compound PEG-600-Cl (C 28 H 57 ClO 14 )

[0069] 1H NMR (400 MHz, DMSO) δ5.4(s, 1 H), δ3.83(t, 2 H), δ3.7(t, 2 H), 3.53(m, 32H).

[0070] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3

[0071] HRMS(ESI) m / z: calc for[C 28 H 58 ClO 14 ]+ :653.3515; Found:653.3518.

[0072] Compound PEG-1000-Cl (C 46 H 93 ClO 23 )

[0073] 1H NMR (400 MHz, DMSO) δ5.4(s, 1 H), δ3.83(t, 2 H), δ3.7(t, 2 H), 3.53(m, 88H).

[0074] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 69.6, 69.2, 61.3, 43.3

[0075] HRMS(ESI) m / z: calc for[C 46 H 94 ClO 23 ]+ :1049.5874; Found:1049.5877.

[0076] When phosphorus oxychloride is replaced by PCl3 or NClS, the above compounds can also be prepared under the same conditions.

[0077] 2. Preparation of organosilicon compounds containing polyols:

[0078] In a Schrank flask, add 50 mL of dry tetrahydrofuran, a 1:3 molar ratio of 3-aminopropyltriethoxysilane and PEG-200-Cl, and potassium carbonate (4 times the amount of 3-aminopropyltriethoxysilane). Heat to 80°C and allow to react for 8 hours. The reaction progress was confirmed by thin-layer chromatography. After completion, the solvent was removed, and a polyol-containing organosilicon compound, named Si-PEG-200, was obtained by sedimentation.

[0079] Using the same method, organosilicon compounds containing PEG-600 and PEG-1000 were prepared and named as compound Si-PEG-600 and compound Si-PEG-1000, respectively. Their structural formulas are shown in the following figure:

[0080]

[0081] Its structural characterization is as follows:

[0082] Compound Si-PEG-200 (C 21 H 47 NO9Si)

[0083] 1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 16 H), 2.48(m, 6H), 1.35(f, 2 H), 1.21(t,9 H), 0.56(t, 2H).

[0084] 13C NMR (101 MHz, DMSO) δ 70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4, 58.4, 18.4, 14.4.

[0085] HRMS(ESI) m / z: calc for [C 21 H 48 NO9Si]+ : 486.3098; Found: 486.3095.

[0086] Compound Si-PEG-6OO (C 66 H 137 NO 31 Si)

[0087] 1H NMR (400 MHz, DMSO) δ 5.4(s, 2 H), δ 3.83(m, 6 H), δ 3.7(m, 4 H), δ 3.53(m, 106 H), 2.48(m, 6H), 1.35(m, 2 H), 1.21(t, 9 H), 0.56(t, 2 H).

[0088] 13C NMR (101 MHz, DMSO) δ 70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4, 58.4, 18.4, 14.4.

[0089] HRMS(ESI) m / z: calc for [C 66 H 138 NO 31 Si]+ : 1468.9022; Found: 1468.9027.

[0090] Compound Si-PEG-1000 (C 103 H 211 NO 49 Si)

[0091] 1H NMR (400 MHz, DMSO) δ 5.4(s, 2 H), δ 3.83(m, 6 H), δ 3.7(m, 4 H), δ 3.53(m, 180 H), 2.48(m, 6H), 1.35(m, 2 H), 1.21(t, 9 H), 0.56(t, 2 H).

[0092] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.458.4, 18.4, 14.4.

[0093] HRMS(ESI) m / z: calc for[C 103 H 212 NO 49 Si]+:1468.9022; Found:1468.9027.

[0094] When 3-aminopropyltriethoxysilane is replaced by 3-aminopropyltrimethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltriisopropoxysilane or 3-aminopropyltributoxysilane, the reaction can also occur under the same conditions to prepare the corresponding organosilicon compounds.

[0095] 3. Preparation of hydrophilic antibacterial organosilicon quaternary ammonium salt compounds:

[0096] Compound Si-PEG-200 (1 mmol, 619 mg) was weighed into a round-bottom flask and 30 mL of acetonitrile was added. Hexadecane chloride (1.2 mmol) was weighed and added to the flask. The mixture was heated under reflux for 6 h, and the reaction progress was confirmed by thin-layer chromatography. After the reaction, the solvent was removed, and a hydrophilic organosilicon quaternary ammonium salt was obtained by sedimentation with a yield of 94%. This product was designated Compound A.

[0097] The same method was used to prepare organosilicon quaternary ammonium salts containing PEG-600 and PEG-1000, which were named as compound B and compound C respectively.

[0098]

[0099] Its structural characterization is as follows:

[0100] Compound A (C 37 H 80 ClNO9Si)

[0101] 1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 16 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).

[0102] 13C NMR (101 MHz, DMSO) δ 70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.4, 58.4, 18.4, 14.4.

[0103] HRMS(ESI) m / z: calc for [C 37 H 80 ClNO9Si]: 745.5291; Found: 745.5296.

[0104] Compound B (C 82 H[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.458.4, 18.4, 14.4.

[0111] HRMS(ESI) m / z: calc for[C 119 H 244Cl NO 49 Si]:2534.6090; Found:2534.6096

[0112] When chlorohexadecane was replaced by chlorododecane, compounds D, E, and F were prepared using the same method. The structural formulas are shown in the figure below:

[0113]

[0114] Its structural characterization is as follows:

[0115] Compound D (C 33 H 72 ClNO9Si)

[0116] 1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m, 8 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).

[0117] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.458.4, 18.4, 14.4.

[0118] HRMS(ESI) m / z: calc for[C 33 H 72 ClNO9Si]:689.4665; Found:745.5296.689.4668

[0119] Compound E (C 78 H 162 ClNO 31 Si)

[0120] 1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,98 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t,12 H), 0.56(t, 2H).

[0121] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.458.4, 18.4, 14.4.

[0122] HRMS(ESI) m / z: calc for[C 78 H 162 ClNO 31 Si]:1672.0589; Found:1672.0693.

[0123] Compound F (C 115 H 236 ClNO 49 Si)

[0124] 1H NMR (400 MHz, DMSO) δ5.4(s, 2 H), δ3.83(m, 6 H), δ3.7(m, 4 H), δ3.53(m,172 H), 2.48(m, 8H), 1.35(m, 30 H), 1.21(t, 12 H), 0.56(t, 2 H).

[0125] 13C NMR (101 MHz, DMSO) δ70.4, 70.3, 70.1, 69.8, 69.2, 61.3, 60.458.4, 18.4, 14.4.

[0126] HRMS(ESI) m / z: calc for[C 115 H 236 ClNO 49 Si]:2478.5464; Found:2478.5468

[0127] Performance test of hydrophilic antibacterial organosilicon quaternary ammonium salt compounds:

[0128] The minimum inhibitory concentrations of compounds A, B, C, D, E, and F synthesized in the examples were tested as follows:

[0129] Test steps: Staphylococcus aureus was tested according to Section 2.1.8.4 Minimum Inhibitory Concentration Determination Test (nutrient broth dilution method) of the Technical Specifications for Disinfection (Ministry of Health 2002 edition).

[0130] The minimum inhibitory concentration of each compound is shown in Table 1.

[0131] Table 1

[0132] Compound Minimum inhibitory concentration (MIC) of Staphylococcus aureus (mg / L) A 45.3 B 78.6 C 146.8 D 98.6 E 128.6 F 184.5

[0133] The minimum inhibitory concentration of the compounds was tested and it was found that the minimum inhibitory concentration of the compounds containing hexadecane was better than that of the compounds containing dodecane. Therefore, the samples treated with compounds A, B, and C containing hexadecane were subsequently selected as preferred samples to test the hydrophilic and antibacterial properties of the samples.

[0134] 4. Preparation of hydrophilic antibacterial functional materials

[0135] Bacteria and fungi tested included Staphylococcus aureus, Escherichia coli, and Candida albicans. The experiments were conducted in accordance with GB / T 20944.3-2008—Evaluation of Antimicrobial Properties of Textiles—Part 3: Oscillation Method. Escherichia coli 8099, Staphylococcus aureus ATCC 6538, and Candida albicans ATCC 10231 were purchased from the American Type Culture Collection (ATCC). The experimental culture medium was purchased from Qingdao Haibo Biotechnology Co., Ltd. All other reagents were of analytical grade.

[0136] Compound A was prepared into a 0.25 mmol / L aqueous solution. Hydrochloric acid was added to adjust the solution's pH to 6, and the solution was allowed to stand at room temperature for 1 hour. A nonwoven fabric made of polypropylene (PP) was immersed in the solution, excess liquid was squeezed out, and the fabric was dried at 120°C. This material was designated PP-A. Compounds B and C were treated in the same manner to obtain samples PP-B and PP-C, respectively.

[0137] Functional chitosan materials were prepared using the same method and named CS-A, CS-B, and CS-C.

[0138] Hydrophilic and antibacterial functional material performance test: The samples PP-A, PP-B, PP-C, CS-A, CS-B, and CS-C prepared in the examples were tested for hydrophilicity and antibacterial properties:

[0139] First, the hydrophilic performance test results are as follows Figure 3 and Figure 4 As shown:

[0140] Water contact angle tests were conducted on blank PP and CS nonwovens, as well as PP and CS nonwovens treated with compounds A, B, and C (PP-A, PP-B, PP-C, CS-A, CS-B, and CS-C). The untreated PP and CS nonwovens exhibited water contact angles of 117° and 106°, respectively. This is due to the large water contact angles of PP and CS, which are hydrophobic materials. Water contact angle tests on PP and CS nonwovens treated with compounds A, B, and C revealed that the treated PP and CS nonwovens exhibited water contact angles of 82°, 61°, and 32°, respectively, representing decreases of 35°, 56°, and 85°, respectively. The treated CS nonwovens exhibited water contact angles of 72°, 57°, and 23°, respectively, representing decreases of 34°, 49°, and 83°, respectively. Through the water contact angle experiment, it can be found that with the increase of PEG molecular weight, the water contact angle of the treated sample gradually decreases and its hydrophilicity gradually increases.

[0141] Second, antibacterial performance test:

[0142] Sample Preparation: Prepare six samples (PP-A, PP-B, PP-C, CS-A, CS-B, and CS-C) (weigh 0.75 ± 0.05 g each). Wash 50 times according to the test conditions specified in GB / T 20944.3-2008, and dry at 50°C before use. Prepare control samples (PP and CS) using the same method.

[0143] Test Procedure: After sterilization, place the above sample in an Erlenmeyer flask. Add PBS buffer and inoculate with Escherichia coli, Staphylococcus aureus, or Candida albicans. After incubation on a constant temperature shaker for 18 hours, 1 mL of the bacterial suspension is sampled and serially diluted. The appropriate serial dilution is then added to a Petri dish. Add 15-20 mL of tryptic soy agar to the plate. After solidification at room temperature, invert the plate and incubate at 37°C ± 1°C for 24-48 hours (48-72 hours for Candida albicans). Record the number of colonies on each plate and calculate the inhibition rate according to the standard formula. The inhibition rates are shown in Table 2.

[0144] Table 2

[0145] Through the minimum inhibitory concentration test results of each compound in Table 1, combined with the antibacterial rate test results of each sample in Table 2, it can be concluded that:

[0146] The hydrophilic organosilicon quaternary ammonium salt compound provided by the present invention has excellent antimicrobial properties. The PP nonwoven fabric processed with the compound also has good antimicrobial properties and still has a good antibacterial effect after 50 washings. This is because the antimicrobial agent has a good antimicrobial effect, and the silanol group has a high reactivity. Under heating conditions, a condensation reaction occurs between the silanol groups. In the condensation reaction, the OH group and the H ion in the two silanol groups combine to break away from the bond, forming a Si-O-Si bond and releasing a water molecule. The condensation reaction between the silanol groups is not limited to the reaction of the two silanol groups, but can also occur between multiple silanol groups. The Si-O-Si chain finally formed can be cross-linked with other Si-O-Si chains to form a three-dimensional interpenetrating network structure of a three-dimensional silicon oxide compound. Therefore, the modified material of the present invention has long-lasting hydrophilic antimicrobial properties.

[0147] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein, but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A hydrophilic antibacterial functional material, characterized in that: The invention relates to a method for preparing a hydrophilic antibacterial organosilicon quaternary ammonium salt by immersing a substrate in a solution of a hydrophilic antibacterial organosilicon quaternary ammonium salt after acid hydrolysis at a certain concentration, fully wetting the substrate, drying the substrate at a certain temperature, and forming a Si-O-Si three-dimensional interpenetrating network on the surface of the substrate. The method has long-lasting antibacterial properties, and the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans are maintained above 99% after washing 50 times. The method also has excellent hydrophilicity, and the time it takes for a water droplet to wet the material is less than 0.1s. The hydrophilic antibacterial organosilicon quaternary ammonium salt has the following general structural formula: wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30 or any one of -CHOH(CH2OH)2; R2 is a saturated alkane with a carbon chain of 1-16; X is fluorine, chlorine, bromine or iodine; 。 2. The hydrophilic antibacterial functional material according to claim 1, characterized in that: The substrate includes any one or more of chemical fiber materials or natural polymer materials; the chemical fiber material includes any one of polyester, spandex, nylon, and acrylic fiber; the natural polymer material includes any one of chitosan, cotton, linen, and alginate; the hydrophilic antibacterial organosilicon quaternary ammonium salt solution is an aqueous solution with a concentration of 0.1-1 mmol / L, the immersion time is 10s-60s, and the drying temperature is 100-150°C.

3. The hydrophilic antibacterial functional material according to claim 1, characterized in that: The hydrophilic antibacterial organosilicon quaternary ammonium salt is hydrolyzed under acidic conditions to form an organosilicon quaternary ammonium salt containing silanol groups. The organosilicon quaternary ammonium salt containing silanol groups has the following structural formula, and after heating and polymerization, a Si-O-Si three-dimensional interpenetrating network is formed on the surface of the substrate; wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30 or any one of -CHOH(CH2OH)2; R2 is a saturated alkane with a carbon chain of 1-16; X is fluorine, chlorine, bromine, or iodine; 。 4. The hydrophilic antibacterial functional material according to claim 3, characterized in that: The acidic conditions include an acidic solution with a pH of 4-6, and the hydrophilic antibacterial organosilicon quaternary ammonium salt is allowed to stand in the acidic solution for 1-6 hours for hydrolysis; the acidic solution is any one of hydrochloric acid, sulfuric acid or acetic acid.

5. A method for preparing a hydrophilic antibacterial organosilicon quaternary ammonium salt for use in preparing the hydrophilic antibacterial functional material according to any one of claims 1 to 4, characterized in that: The following steps are involved: Step A: a certain amount of polyol is placed in a reaction vessel, and a solvent is added to form a polyol solution; a certain amount of chlorinated compound is weighed and added to the polyol solution, and the solution is heated to a certain temperature, reacted for a period of time, and the progress of the reaction is determined by thin layer chromatography. After the reaction is complete, the solvent is removed, and a chlorine-substituted polyol is obtained by sedimentation method; the addition ratio of the polyol, solvent, and chlorinated compound is 1:10-15:0.9-1; the reaction temperature is set at 70-110° C., and the reaction time is set at 4-8 hours; Step B: a certain amount of silane coupling agent is placed in a reaction vessel, a solvent, a base, and a certain amount of the chlorine-substituted polyol prepared in Step A are added, the mixture is heated to a certain temperature, reacted for a period of time, and the progress of the reaction is determined by thin-layer chromatography. After the reaction is complete, the solvent is removed, and an organosilicon compound containing the polyol is obtained by a sedimentation method; the addition ratio of the silane coupling agent, the solvent, the base, and the chlorine-substituted polyol is 1:10-15:2-6:2-4; the reaction temperature is set at 70-110° C., and the reaction time is set at 6-10 h; Step C: taking a certain amount of the polyol-containing organosilicon compound prepared in step B and placing it in a reaction vessel, adding a solvent, a base and a certain amount of halogenated alkane, heating to a certain temperature, reacting for a period of time, determining the progress of the reaction by thin layer chromatography, and after the reaction is complete, removing the solvent and obtaining a hydrophilic antibacterial organosilicon quaternary ammonium salt by a sedimentation method; the addition ratio of the hydrophilic antibacterial organosilicon compound, the solvent, the base and the halogenated alkane is 1:10-15:1-3:1-3; the reaction temperature is set at 70-110°C, and the reaction time is set at 6-10 hours.

6. The preparation method according to claim 5, characterized in that The polyol in step A includes any one of polyethylene glycol, polyvinyl alcohol, and glycerol; the solvent includes any one of tetrahydrofuran and toluene; and the chlorinated compound includes any one of phosphorus oxychloride POCl3, phosphorus trichloride PCl3, and N-chlorosuccinimide.

7. The preparation method according to claim 5, characterized in that The silane coupling agent in step B includes any one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyltributoxysilane, and 3-aminopropyltriisopropoxysilane; the solvent includes any one of tetrahydrofuran and toluene; and the base includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.

8. The preparation method according to claim 5, characterized in that The solvent in step C includes any one of tetrahydrofuran, toluene, and acetonitrile; the base includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; and the halogenated alkane includes any one of saturated halogenated hydrocarbons having 1 to 16 carbon atoms.

9. The preparation method according to any one of claims 6 to 8, characterized in that: The organosilicon compound containing polyol in step B has the following structural formula, wherein R1 is -(OCH2CH2) n OH, -(CH2CHOH) n , n is a positive integer of 1-30 or any one of -CHOH(CH2OH)2; 。 10. Use of any one of the functional materials according to claims 1 to 4 as a raw material in the fields of medical protective products, medical dressings, household textiles, and sanitary products.

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