Preparation method and application of multifunctional antibacterial organic silicon coating

Abstract

The invention discloses a preparation method and application of a multifunctional antibacterial organic silicon coating. The multifunctional antibacterial organic silicon coating is prepared by taking a double-bond-containing silane coupling agent, a double-bond-containing flame-retardant monomer and a double-bond-containing quaternary ammonium salt as main raw materials through free radical polymerization. The prepared multifunctional antibacterial organic silicon coating solution can be sprayed, spin-coated or brushed on the surface of a material, and a long-acting antibacterial multifunctional organic silicon coating material is formed after drying. The multifunctional coating material has the advantages of being excellent in hydrophobicity, fireproof, flame-retardant, long-acting and lasting in antibiosis and the like, and is widely applied to medical protection articles, medical dressings, hygienic products, electronic medical treatment and textiles. The multifunctional antibacterial organic silicon coating provided by the invention can be applied to long-acting antibiosis of the surfaces of natural materials, high polymer materials and metal materials, the preparation method of the coating has small damage to a base material, the base material adaptability is wide, and the antibacterial effect is excellent, durable and stable.

Description

Technical Field

[0001] The invention belongs to the technical field of functional material modification, and specifically relates to a preparation method and application of a multifunctional antibacterial organic silicon coating. Background Art

[0002] With the progress of the times and the development of science and technology, people have put forward higher requirements for green and healthy working and living environments. In the human living environment, microbial pollution such as bacteria poses a major threat to human health. Among bacterial pathogens, such as plague bacteria and Vibrio cholerae can cause major infectious diseases. The use of antibacterial coatings in public places and construction fields can effectively reduce contact with pathogenic infectious sources and prevent cross-infection. In the home environment, the use of multifunctional antibacterial coatings can not only effectively reduce the number of bacteria on household items, but also play a self-cleaning role to reduce stain accumulation, inhibit the growth of harmful microorganisms, and also have flame retardant functions to prevent fire hazards. Therefore, the development of coatings with antibacterial functions that also have important environmental protection and fire safety properties has also become one of the important directions for the development of the coatings industry.

[0003] Antibacterial materials can be divided into natural antibacterial materials, inorganic antibacterial materials and organic antibacterial materials according to their components. Among them, organic antibacterial agents have a high density of active functional groups, excellent antibacterial properties, and can kill bacteria through direct contact with bacteria without the need to release active substances. They have long-lasting and stable antibacterial properties, low residual toxicity and high safety. According to the different active functional groups, organic antibacterial agents are mainly divided into quaternary ammonium salts, quaternary phosphonium salts, pyridinium salts, halogenated amines, guanidine salts, chitosan, etc. Quaternary ammonium salt antibacterial agents have a simple production process, low toxicity, and can achieve a fast and efficient contact sterilization effect through electrostatic adsorption. They are currently a type of organic antibacterial agent that is widely used. Its disadvantage is that it is not firmly bonded to the substrate. In actual application, it is generally used in combination with a cross-linking agent to improve the bonding strength.

[0004] At present, the method of fixing quaternary ammonium salt organic antibacterial agents on base materials has problems such as low adhesion to the substrate, high requirements on the substrate type, unstable antibacterial effect, and single function. Summary of the invention

[0005] The present invention aims at the problems existing in the prior art and provides a method for preparing a multifunctional antibacterial organosilicon coating and its application. The present invention can not only solve the technical problems of low substrate adhesion, high requirements on substrate type and unstable antibacterial effect in the preparation method of the existing quaternary ammonium salt antibacterial material, but also has excellent hydrophobic, fire retardant and long-lasting antibacterial properties, and can be applied in the fields of medical protective equipment, medical dressings, sanitary products, textiles, etc.

[0006] The preparation method of the multifunctional antibacterial organosilicon coating of the present invention comprises the following steps: Dissolve a double-bond flame retardant monomer, methacryloyloxyethyl trimethylammonium chloride, a double-bond silane coupling agent and a free radical initiator in a solvent, and stir at 60-80° C. for 6-10 hours; after the reaction is completed, add a solvent for dilution to obtain a multifunctional antibacterial silicone coating solution with a solid content of 0.02-0.08 g / mL.

[0007] The raw materials are composed of 5-50 parts of double-bond flame retardant monomer, 5-50 parts of methacryloyloxyethyl trimethyl ammonium chloride, 5-50 parts of double-bond silane coupling agent, 0.5-1.5 parts of free radical initiator and 100-300 parts of solvent in parts by mass.

[0008] The double bond-containing silane coupling agent is selected from one or more of γ-methacryloxypropyltrimethoxysilane (KH570), vinyltrimethoxysilane (A171), vinyltri(b-methoxyethoxy)silane (A172), and vinyltriethoxysilane (A151). The corresponding structural formula is shown below: .

[0009] The free radical initiator is selected from one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptanenitrile.

[0010] The solvent is selected from one or more of ethanol, methanol, N,N-dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, and 1,4-dioxane. The mass fraction of the above solvents is the total amount of solvents used in the preparation process.

[0011] The double-bond-containing flame-retardant monomer is prepared by reacting hydroxyethyl acrylate or hydroxyethyl methacrylate with a phosphorus-containing flame-retardant small molecule.

[0012] The phosphorus-containing flame retardant small molecule is selected from one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diphenylphosphinyl chloride (DC), diphenyl chlorophosphate (DPC), etc. The corresponding structural formula is as follows: .

[0013] Specifically, the preparation route of the double bond-containing flame retardant monomer includes: Route 1: Add DOPO to the solvent, stir, and heat to 40-60°C. After DOPO is completely dissolved, add hydroxyethyl acrylate and triethylamine, and stir at this temperature for 30 minutes. Then add carbon tetrachloride dropwise and react for 4-8 hours. After the reaction is completed, cool to room temperature, wash with hydrochloric acid, saturated brine and sodium bicarbonate solution, remove water with anhydrous magnesium sulfate, filter and evaporate to recover the solvent, and obtain the product DHA (DOPO grafted hydroxyethyl acrylate).

[0014] The synthetic route is as follows: .

[0015] Route 2: Add hydroxyethyl methacrylate and triethylamine to a solvent, stir, and heat to 40-60°C. After they are evenly dispersed, add diphenylphosphinyl chloride dropwise to the above solution and react for 4-8 hours. After the reaction is completed, cool to room temperature, wash with hydrochloric acid, saturated brine and sodium bicarbonate solution, remove water with anhydrous magnesium sulfate, filter and rotary evaporate to recover the solvent, and obtain the product DCHA (diphenylphosphinyl chloride grafted hydroxyethyl methacrylate).

[0016] The synthetic route is as follows: .

[0017] Route 3: Add hydroxyethyl acrylate and triethylamine to a solvent, stir, and heat to 40-60°C. After they are evenly dispersed, add diphenyl chlorophosphate dropwise to the above solution and react for 4-8 hours. After the reaction is completed, cool to room temperature, wash with hydrochloric acid, saturated brine and sodium bicarbonate solution, remove water with anhydrous magnesium sulfate, filter and rotary evaporate to recover the solvent, and obtain the product HDPP (diphenyl phosphate grafted hydroxyethyl methacrylate).

[0018] The synthetic route is as follows: .

[0019] The multifunctional antibacterial organic silicon coating of the present invention is used in preparing a multifunctional coating having hydrophobic, flame retardant and antibacterial properties.

[0020] Specifically, the prepared multifunctional antibacterial silicone coating solution is coated on the surface of the substrate by conventional methods such as spraying and spin coating, and can be used for long-term antibacterial applications in the fields of medical protective equipment, medical dressings, sanitary products, textiles, etc.

[0021] The substrate comprises one of natural materials, polymer materials and metal materials.

[0022] The invention provides a polymer flame retardant, antibacterial and hydrophobic coating obtained by free radical polymerization of a double-bond phosphorus-containing flame retardant monomer, a double-bond quaternary ammonium salt and a double-bond siloxane. The prepared polymer flame retardant, antibacterial and hydrophobic coating retains a large amount of siloxane groups, and the large amount of siloxane groups makes the polymer coating have strong adhesion to the substrate and higher adhesion. In addition, the different contents of the double-bond phosphorus-containing flame retardant monomer, the double-bond quaternary ammonium salt and the double-bond siloxane in the invention can change their corresponding flame retardant, antibacterial and hydrophobic properties.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention uses phosphorus-containing flame retardant small molecules to react with hydroxyethyl acrylate structures to obtain double-bond flame retardant monomers, which are copolymerized with double-bond hydrophobic monomers and double-bond antibacterial monomers through random free radicals to obtain a novel multifunctional antibacterial silicone coating. The obtained multifunctional antibacterial silicone coating solution can be sprayed, spin-coated or brushed on the surface of natural materials, polymer materials and metal materials, and can be used for long-term antibacterial applications in the fields of medical protective equipment, medical dressings, sanitary products, textiles, etc.

[0024] (2) The antibacterial coating formed by the present invention is colorless and transparent, and has no obvious effect on the color of the substrate. The antibacterial film material formed by the coating through the solution has extremely strong adhesion. The polar groups in the molecular structure can form hydrogen bonds with the coated substance, and the siloxane in the molecular structure is connected to the coated substance through Si-O bonds, which can be firmly attached to the substrate. It has very excellent biocompatibility and long-lasting antibacterial activity, and is an antibacterial coating with excellent performance, safety and reliability.

[0025] (3) The preparation process and equipment of the present invention are simple, no complicated organic synthesis process is required, the process parameters are flexible, the preparation cycle is short, the conditions are mild, and it is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The hydrogen spectrum (a) and phosphorus spectrum (b) of DHA.

[0027] Figure 2 The hydrogen spectrum (a) and phosphorus spectrum (b) of DCHA.

[0028] Figure 3 The hydrogen spectrum (a) and phosphorus spectrum (b) of HDPP.

[0029] Figure 4 This is the preparation process of QAS-1.

[0030] Figure 5 The hydrogen spectrum (a), phosphorus spectrum (b) and silicon spectrum (c) of QAS-1.

[0031] Figure 6 SEM images of FPUF (a, b) and FPUF / QAS-1 (d, e); water contact angle images of FPUF (c) and FPUF / QAS-1 (f).

[0032] Figure 7 The antibacterial properties of FPUF and FPUF / QAS-1.

[0033] Figure 8 HRR (a) and THR (b) curves of FPUF and FPUF / QAS-1. DETAILED DESCRIPTION

[0034] In order to further illustrate the technical solution of the present invention, the preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention. Based on the examples in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention. Embodiment 1:

[0035] 1. Add 2.16 g DOPO to 300 mL chloroform and stir, and heat to 40°C. After DOPO is completely dissolved, add 1.16 g hydroxyethyl acrylate and 2.02 g triethylamine, and stir at this temperature for 1 h. Then add 2.31 g carbon tetrachloride dropwise and react for 6 h. After the reaction, cool to room temperature, wash with 1 mol / L hydrochloric acid, saturated salt water and 1 mol / L sodium bicarbonate solution, and remove water with anhydrous magnesium sulfate. Recover the solvent by rotary evaporation to obtain the product (DOPO grafted hydroxyethyl acrylate, DHA).

[0036] 2. Add 1.28 g of hydroxyethyl methacrylate and 2.02 g of triethylamine to 300 mL of dichloromethane, stir, and heat to 50°C. After the mixture is evenly dispersed, add 3.56 g of diphenylphosphinyl chloride dropwise to the solution and react for 5 hours. After the reaction is completed, cool to room temperature, wash with 1 mol / L hydrochloric acid, saturated saline, and 1 mol / L sodium bicarbonate solution, and remove water with anhydrous magnesium sulfate. Recover the solvent by rotary evaporation to obtain the product (diphenylphosphinyl chloride grafted hydroxyethyl methacrylate, DCHA).

[0037] 3. Add 1.16 g of hydroxyethyl acrylate and 2.02 g of triethylamine to 300 mL of tetrahydrofuran, stir, and heat to 50°C. After the mixture is evenly dispersed, add 2.69 g of diphenylphosphinyl chloride dropwise to the solution and react for 7 hours. After the reaction is completed, cool to room temperature, wash with 1 mol / L hydrochloric acid, saturated brine, and 1 mol / L sodium bicarbonate solution, and remove water with anhydrous magnesium sulfate. Recover the solvent by rotary evaporation to obtain the product (diphenyl phosphate grafted hydroxyethyl acrylate, HDPP). Embodiment 2:

[0038] 2.48g KH570, 2.08g DMC, 3.3g DCHA and 100mL anhydrous ethanol were added to a 250mL three-necked flask, heated to 80°C, stirred continuously and added with a condensation reflux device. Then 0.1g azobisisobutyronitrile (AIBN) initiator was added and reacted for 6 hours. After the reaction, extraction, separation and washing were performed, and then the solvent was removed by rotary evaporation to obtain QAS. Finally, QAS was dissolved in ethanol to obtain a QAS-1 coating solution with a concentration of 0.03g / mL.

[0039] First, 5×4×2cm 3 The FPUF was immersed in a QAS-1 coating solution with a concentration of 0.03 g / mL. After 1 min, the FPUF was taken out and placed in a 60°C oven for drying to obtain FPUF / QAS-1. The antibacterial properties of the coating were tested by the following tests: Disinfect with ultraviolet sterilization lamp in the clean bench for 5 min. Take 0.5 mL of bacterial solution and drop it on the prepared sample, place it in a culture dish, and then cover it with sterilized film, and culture it in a constant temperature and humidity incubator at 37°C and 90% relative humidity for 24 h; take out the sample cultured for 24 h, add 20 mL of washing solution, wash the sample and cover it with film repeatedly, dilute it, take the washing solution and inoculate it in nutrient agar medium, culture it in a constant temperature and humidity incubator at 37°C and 90% relative humidity for 48 h, count the live bacteria, and take pictures to observe the survival of bacteria.

[0040] Embodiment 3:

[0041] 1.48g A171, 2.08g DMC, 6.8g DHA and 100mL anhydrous methanol were added to a 250mL three-necked flask, heated to 80°C, stirred continuously and added with a condensation reflux device. Then 0.1g azobisisobutyronitrile (AIBN) initiator was added and reacted for 6 hours. After the reaction, extraction, separation and washing were performed, and then the solvent was removed by rotary evaporation to obtain QAS. Finally, QAS was dissolved in methanol to obtain a QAS-2 coating solution with a concentration of 0.04g / mL.

[0042] First, 0.04 g / mL of QAS-2 coating solution was sprayed on a 6×4 cm 2 The surface of cotton fabric (CF) was coated with QAS-2 and the CF was dried in an oven at 55 °C for 1 min to obtain CF / QAS-2. Embodiment 4:

[0043] 5.6g A172, 2.08g DMC, 3.5g HDPP and 100mL tetrahydrofuran were added to a 250mL three-necked flask, heated to 80°C, stirred continuously and a condensation reflux device was added. Then 0.1g azobisisobutyronitrile (AIBN) initiator was added and the reaction was continued for 6 hours. After the reaction was completed, extraction, separation and washing were performed, and then the solvent was removed by rotary evaporation to obtain QAS. Finally, QAS was dissolved in tetrahydrofuran to obtain a QAS-3 coating solution with a concentration of 0.05g / mL.

[0044] First, 0.5 g / mL QAS-3 coating solution was spin-coated on a 13×1×1 cm 3 The surface of the wood was dried in an oven at 50°C for 1 minute to obtain W / QAS-3. Embodiment 5:

[0045] 1.9g A151, 4.16g DMC, 3.5g HDPP and 100mL dichloromethane were added to a 250mL three-necked flask, heated to 80°C, stirred continuously and added with a condensation reflux device. Then 0.1g azobisisobutyronitrile (AIBN) initiator was added and reacted for 6 hours. After the reaction, extraction, separation and washing were performed, and then the solvent was removed by rotary evaporation to obtain QAS. Finally, QAS was dissolved in dichloromethane to obtain a QAS-4 coating solution with a concentration of 0.05g / mL.

[0046] QAS-4 multifunctional silicone antibacterial coating was applied on 8×4cm 2 After 1 min, the SP was placed in an oven at 65 °C to dry to obtain SP / QAS-4.

[0047] The weight, density, PHRR, THR value, water contact angle, and antibacterial efficiency of the samples in Examples 3, 4, and 5 were tested to evaluate the hydrophobic, fire-retardant, and long-lasting antibacterial properties of the multifunctional antibacterial silicone coating.

[0048]

[0049] The QAS-1, QAS-2, QAS-3 and QAS-4 coatings in Examples 2, 3, 4 and 5 were coated on glass sheets and steel sheets respectively to carry out bonding strength tests to evaluate their adhesion properties.

[0050]

[0051] Based on the above experimental results, the following conclusions are drawn: (1) The synthesized multifunctional antibacterial silicone coating has high adhesion, can be firmly fixed on the surface of the substrate, and can improve the hydrophobicity of the substrate material.

[0052] (2) The synthetic multifunctional antibacterial silicone coating, when applied on the surface of natural materials, polymer materials and metal materials, has an antibacterial efficiency of more than 98% against Gram-negative Escherichia coli and Staphylococcus aureus, and has excellent antibacterial properties.

[0053] (3) The synthesized multifunctional antibacterial silicone coating can improve the fire safety of the substrate material and significantly reduce the thermal hazards of the substrate material.

Claims

1. A method for preparing a multifunctional antibacterial organosilicon coating, characterized in that The steps include: Dissolve a double-bond flame retardant monomer, methacryloyloxyethyl trimethylammonium chloride, a double-bond silane coupling agent and a free radical initiator in a solvent, and stir at 60-80° C. for 6-10 hours; after the reaction is completed, add a solvent for dilution to obtain a multifunctional antibacterial organic silicon coating solution; The double-bond-containing flame-retardant monomer is prepared by reacting hydroxyethyl acrylate or hydroxyethyl methacrylate with a phosphorus-containing flame-retardant small molecule.

2. The preparation method according to claim 1, characterized in that: The raw materials are composed of 5-50 parts of double-bond flame retardant monomer, 5-50 parts of methacryloyloxyethyl trimethyl ammonium chloride, 5-50 parts of double-bond silane coupling agent, 0.5-1.5 parts of free radical initiator and 100-300 parts of solvent in parts by mass.

3. The preparation method according to claim 1, characterized in that: The double bond-containing silane coupling agent is selected from one or more of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltri(b-methoxyethoxy)silane and vinyltriethoxysilane.

4. The preparation method according to claim 1, characterized in that: The phosphorus-containing flame retardant small molecule is selected from one of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinyl chloride, and diphenyl chlorophosphate, and the corresponding structural formula is as follows: 。 5. The preparation method according to claim 4, characterized in that The flame retardant monomer containing double bonds is selected from one or more of the following structural compounds: 。 6. The preparation method according to claim 1, characterized in that: The free radical initiator is selected from one or more of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile and azobisisoheptanenitrile.

7. The preparation method according to claim 1, characterized in that: The solid content of the multifunctional antibacterial organic silicon coating solution is 0.02-0.08 g / mL.

8. Use of the multifunctional antibacterial organosilicon coating prepared by the preparation method according to any one of claims 1 to 7 in preparing a multifunctional coating having hydrophobic, flame retardant and antibacterial properties.

9. The use according to claim 8, characterized in that: The multifunctional antibacterial organic silicon coating solution is applied to the surface of the substrate and dried.

10. The use according to claim 9, characterized in that: The substrate comprises one of natural materials, polymer materials and metal materials.

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