A choline derivative modified organosilicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material and its preparation method and application

Abstract

The present invention discloses a choline derivative-modified organosilicon UV-curable transparent hydrophilic antibacterial, flame-retardant, and antistatic material, as well as its preparation method and application. Specifically, a hyperbranched silicon-containing polymer and a phosphine-containing acrylate containing a choline derivative and a mercaptopropyl group are prepared, uniformly mixed with a photoinitiator, and subjected to vacuum degassing and UV curing to obtain the antibacterial, flame-retardant, and antistatic UV-curable transparent organosilicon material. In addition to excellent antibacterial, flame-retardant, and antistatic properties, this UV-curable material also has high light transmittance, excellent mechanical properties, and strong adhesion to substrates. It can be used in antibacterial, flame-retardant, and antistatic coatings, optical and electronic devices, food packaging, medical equipment, textiles, and other fields.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic silicon materials, and relates to a choline derivative modified organic silicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material, and a preparation method and application thereof. Background Art

[0002] Pathogenic microorganisms such as bacteria, fungi, and viruses can cause pathological changes in body tissues, posing a serious threat to human physical and mental health. Bacteria growing on the surfaces of medical devices after insertion into the body is the primary cause of infection, resulting in significant financial losses and even life-threatening consequences for patients. Consequently, antimicrobial materials have been developed to mitigate the harmful effects of bacterial transmission. Compared to conventional physical and chemical disinfection methods, the use of antimicrobial materials offers advantages such as long-term efficacy, cost-effectiveness, and convenience. For example, the use of antimicrobial materials on frequently touched surfaces in public places, such as telephones, elevator buttons, computer keyboards, and various electrical switches, effectively eliminates both contamination and transmission sources. The use of antimicrobial materials on household items also improves the living environment and enhances hygiene.

[0003] Small-molecule organic antimicrobial agents, such as quaternary ammonium salts, alcohols, phenols, and organometallics, have mature processing technologies and excellent bactericidal effects. However, they are highly toxic, have poor thermal stability, are prone to drug resistance in microorganisms, and have a short service life. Additive-based polymer antimicrobial materials prepared by adding small-molecule organic or metallic antimicrobial agents to polymer materials also have disadvantages such as high toxicity and the tendency for microorganisms to develop drug resistance, as the small-molecule organic or metallic antimicrobial agents migrate to the material surface [ACS Appl. Mater, 2016, 8, 21640-21647; J. Reinf. Plast. Comp., 2020, 39(3-4):95-110.]. Structural polymer antimicrobial materials are prepared by covalently bonding precursors with antimicrobial groups to target polymers. They not only overcome the shortcomings of high toxicity of small molecule antimicrobial agents and additive polymer antimicrobial materials, but also have the advantages of easy processing, stable performance, and good bactericidal effect [Macromol.Biosci., 2020, 20:1900301.].

[0004] Ultraviolet (UV) curing technology has the advantages of fast curing speed, simple processing, low energy consumption, and no pollution. It is widely used in paints, inks, electronic packaging, and other fields for furniture and industrial products. In recent years, with the increasing awareness of environmental protection, the research and development of UV-curable antibacterial polymer materials has also attracted widespread attention. Chinese invention patent application CN202110532968.9 reports a UV-curable adhesive and preparation method. Oligomers and epoxy resins are added to a reaction vessel according to a certain ratio and stirred and heated. Then, polyols, coupling agents, and dispersants are added. Then, a fungicide and photoinitiator are added to obtain the UV-curable adhesive. Chinese invention patent application CN201811359638.9 reports a highly wear-resistant water-based UV floor paint and its preparation method. The UV floor paint is prepared by adding an in-can fungicide to a water-based UV polyurethane dispersion. Chinese invention patent application CN201710716119.2 adds flax cellulose to a UV-curable water-based polyurethane acrylate, reportedly obtaining a UV-curable water-based polyurethane with bactericidal, breathable, and flame-retardant properties. However, the above-mentioned UV-curable antibacterial material is an additive polymer material. Not long ago, Chinese invention patent application CN202011001135.1 disclosed a method for synthesizing a UV-curable bactericidal and antistatic resin material and its application. Specifically, tetranitrophthalocyanine zinc is synthesized by an inert solvent method, and tetranitrophthalocyanine zinc is reduced to tetraaminophthalocyanine zinc with sodium sulfide nonahydrate. At the same time, unsaturated double bonds are grafted on the tetraaminophthalocyanine zinc, and applied to UV light curing, but the preparation process is complicated, and the product of the unsaturated double bonds grafted on the tetraaminophthalocyanine zinc has poor solubility. Chinese invention patent CN202110800922.0 discloses a UV-curable hardened resin with antibacterial function and a synthesis method. Specifically, terminal triacryloxy pentaerythritol metal phthalocyanine ester, polyurethane acrylate, photoinitiator, MIBK, MEK, leveling agent, lubricant, and AF surface anti-oil additive are compounded and then UV-cured to obtain an antibacterial material. Although according to the patent report, the coating made of the UV-cured bactericidal, antistatic and anti-fingerprint resin material has rapid and super-strong bactericidal and anti-static capabilities, and is permanent and has good wear resistance, the UV-curing material contains both environmentally unfriendly solvents and added lubricants and AF surface anti-oil additives, and its environmental friendliness needs to be improved.

[0005] In order to overcome the shortcomings of the above-mentioned UV-curable antibacterial materials and give full play to the advantages of UV curing technology, the inventors previously proposed Chinese invention patent CN202210512217, which discloses a method for preparing a UV-curable transparent antibacterial silicone material. Specifically, a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and a castor oil-based polyurethane-acrylate UV-curable prepolymer are first prepared, mixed evenly with a photoinitiator and vacuum degassed, and then UV-cured to obtain a bactericidal and antibacterial UV-curable transparent silicone material with a light transmittance of 80-96% (light wavelength range 400-800nm, sample thickness 10mm), hardness 6B-5H, water absorption 0.7-2.0%, initial thermal decomposition temperature (thermal weight loss 5%) 162-184°C, tensile strength 0.6-12MPa, elongation at break 45-130%, and adhesion to the substrate level 4 to 1. This UV-curable material has high light transmittance, good thermal stability, excellent mechanical properties, and strong adhesion to substrates, and has a strong inhibitory effect on both fungi and bacteria. However, the material's surface is hydrophobic, and the antimicrobial activity of its Schiff base groups is relatively low, leaving room for further improvement in the antimicrobial properties of UV-curable materials.

[0006] Choline is a positively charged tetravalent base, a component of all biological membranes and a precursor of acetylcholine in cholinergic neurons. Its chemical formula is C5H 14 ON +This type of compound is mainly a cation that adsorbs negatively charged bacteria through electrostatic forces, hydrogen bonds, and hydrophobic binding between surfactant molecules and protein molecules, resulting in a cell wall resistance effect, which inhibits bacterial growth and causes death. Chinese invention application 202111101725.6 first prepares phosphorylcholine polyvinylamine, which is mixed with a silica sol prepared from ethyl orthosilicate and KH-560 to form a compound solution. Then, a plasma-treated medical catheter is placed in the compound solution, removed after a suitable period of time, and cross-linked and cured to obtain a medical catheter that is hydrophilic, low-friction, and resists bacterial adhesion. Chinese invention patent application 202080088237.3 (priority patent 2019239653JP) discloses a polysiloxane monomer containing a phosphorylcholine group. This monomer is a macromolecular monomer containing a phosphorylcholine group in the side chain, a polysiloxane segment in the main chain, and acrylate groups at both ends. It can undergo free radical polymerization with hydrophilic acrylates, etc. to obtain a polymer that can be hydrophilic and stable on the surface of ophthalmic devices. Not long ago, Chinese invention patent application 202210877447.1 disclosed a photocurable antibacterial oligomer and its preparation method. Specifically, a diisocyanate is reacted with a hydroxy acrylate, and then reacted with choline chloride to obtain an oligomer, which is then added to a photocurable system and used as an active diluent, thereby giving the photocurable system a good antibacterial effect. However, this prepolymer has a low molecular weight and only one active group participates in UV curing. When added in large amounts, the mechanical strength of the material is often unsatisfactory, and when added in small amounts, the antibacterial effect of the material is poor. In addition, this photocurable material is opaque and has a hydrophobic surface.

[0007] In order to overcome the shortcomings of existing polymer materials, the present invention discloses a preparation method and product of a choline derivative modified organic silicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material. Specifically, a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group, a phosphorus-containing trifunctional acrylate, and a photoinitiator are first prepared and uniformly mixed, and the mixture is vacuum degassed for 10 to 30 minutes, and then UV cured for 30 to 180 seconds to obtain a UV curing transparent organic silicon material. The material has a bactericidal efficiency of 85 to 95.6% against Staphylococcus aureus and 90 to 99.5% against Candida albicans, a water contact angle of 20 to 30 degrees, a light transmittance of 85 to 98%, a horizontal and vertical combustion oxygen index of 24 to 35, a flame retardancy of V1 to V0, and a surface impedance of 10 5 ~10 12 ohm, hardness 4B ~ 3H, tensile strength 0.6 ~ 7.5MPa, adhesion to substrate 4 to 1, can be used in antibacterial, flame retardant and antistatic coatings, optical electronic devices, food packaging, medical equipment and textiles and other fields. Summary of the Invention

[0008] The purpose of the present invention is to provide a method for preparing a choline derivative modified organic silicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material in view of the deficiencies in the prior art.

[0009] A method for preparing a choline derivative-modified organosilicon UV-curable transparent hydrophilic antibacterial, flame-retardant and antistatic material adopts the following technical scheme:

[0010] Step (1), preparation of a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group

[0011] (1-1) An isocyanate alkoxysilane, a choline derivative, and dibutyltin dilaurate are reacted in a solvent at 30 to 80° C. for 1 to 12 hours, and then the solvent and unreacted raw materials are removed under reduced pressure to obtain an alkoxysilane containing a choline derivative;

[0012] (1-2) reacting an alkoxysilane containing a choline derivative, a mercaptopropyl alkoxysilane, and a small molecule compound containing two hydroxyl groups at 100-160° C. for 2-12 hours under the catalysis of p-toluenesulfonic acid, and removing the unreacted raw materials under reduced pressure to obtain a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group;

[0013] Preferably, the molar ratio of the isocyanate alkoxysilane to the choline derivative is 1:1;

[0014] Preferably, the isocyanate alkoxysilane is a mixture of one or both of 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane;

[0015] Preferably, the choline derivative is one or a mixture of choline, N-oleoyl-D-erythro-sphingylphosphocholine and N-palmitoyl-D-erythro-sphingylphosphocholine;

[0016] Preferably, the amount of dibutyltin dilaurate is 0.05-1% of the total mass of the isocyanate alkoxysilane and the choline derivative;

[0017] Preferably, the solvent is one or a mixture of DMF, DMAc, tetrahydrofuran, acetonitrile, and DMSO; more preferably, the solvent is one or a mixture of DMF, DMAc, and acetonitrile;

[0018] Preferably, the reaction temperature of the isocyanate alkoxysilane and the choline derivative is 50 to 80° C., and the reaction time is 3 to 8 hours;

[0019] Preferably, the amount of solvent is 0.5 to 4 times, more preferably 1 to 3 times;

[0020] Preferably, the mercaptopropyl alkoxysilane is a mixture of one or both of mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane;

[0021] Preferably, the amount of p-toluenesulfonic acid used is 0.5-2% of the total mass of the alkoxysilane containing choline derivatives, mercaptopropyl alkoxysilane and the small molecule compound containing two hydroxyl groups;

[0022] Preferably, the molar ratio of the alkoxysilane containing a choline derivative to the mercaptopropylalkoxysilane is 5:95 to 40:60, more preferably 15:85 to 40:60.

[0023] Preferably, the small molecule compound containing two hydroxyl groups is one or a mixture of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and neopentyl glycol, and its amount is 1.1 to 2.0 times the total molar number of the alkoxysilane containing the choline derivative and the mercaptopropyl alkoxysilane.

[0024] Step (2), preparation of phosphorus-containing trifunctional acrylate

[0025] Under nitrogen protection, tetrahydrofuran and phosphorus oxychloride are added to a reaction vessel, and then a mixture of triethylamine, hydroxyethyl acrylate, and tetrahydrofuran is added dropwise at 0-5°C. After the addition is complete, the mixture is reacted at room temperature. After the reaction is complete, the triethylamine is filtered out, and the solvent and residual reactants are removed under reduced pressure to obtain a primary product. The primary product is dissolved in dichloromethane, washed with 10% hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution until neutral, respectively, dried, and then the dichloromethane is removed by rotation to obtain a phosphorus-containing trifunctional acrylate.

[0026] Preferably, the mass ratio of tetrahydrofuran to phosphorus oxychloride in the reaction vessel is 2:1;

[0027] Preferably, the reaction time at room temperature is 12 h;

[0028] Preferably, the molar ratio of phosphorus oxychloride, triethylamine and hydroxyethyl acrylate is 1:3:3; in the mixture, the mass of tetrahydrofuran is 3 times the total mass of triethylamine and hydroxyethyl acrylate.

[0029] Step (3): Preparation of UV-curable transparent silicone material

[0030] A hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group is mixed with a phosphorus-containing trifunctional acrylate and a photoinitiator, and the mixture is vacuum degassed for 10 to 30 minutes, and then UV-cured for 30 to 180 seconds to obtain a UV-curable transparent silicone material; wherein the hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group and the phosphorus-containing trifunctional acrylate are mixed at a molar ratio of mercapto group to acrylate group of 1:(1 to 3.5);

[0031] Preferably, the photoinitiator is Irgacure-1173, 2959, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenyl acetophenone, α,α-dimethoxy-α-phenylacetophenone, α,α-diethoxyacetophenone, α-hydroxyalkyl phenone, α-aminoalkyl phenone, aromatic phosphine oxide, bisbenzoylphenyl phosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, Michler's ketone; thiopropoxythioxanthone, isopropyl thioxanthone or a mixture thereof; more preferably, the photoinitiator is Irgacure-1173, 2959, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenyl acetophenone or a mixture thereof;

[0032] Preferably, the amount of the photoinitiator is 1 to 12% of the mass of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer, more preferably 3 to 8%;

[0033] Preferably, the hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group and the phosphorus-containing trifunctional acrylate are reacted in a molar ratio of mercapto group to acrylate group of 1:(1.5-3.5).

[0034] Another object of the present invention is to provide a UV-curable transparent antibacterial silicone material. The UV-curable transparent antibacterial silicone material has a sterilization efficiency of 85-95.6% against Staphylococcus aureus and 90-99.5% against Candida albicans, a water contact angle of 20-30°, a light transmittance of 85-98%, a horizontal and vertical combustion oxygen index of 24-35, a flame retardancy of V1-V0, and a surface impedance of 10 5 ~10 12 ohm, hardness 4B ~ 3H, tensile strength 0.6 ~ 7.5MPa, adhesion to the substrate 4 to 1 level.

[0035] Another object of the present invention is to provide a UV-curable transparent antibacterial silicone material for use as antibacterial, flame-retardant and antistatic coatings, optical electronic devices, food packaging, medical equipment and textiles, and is particularly suitable for the packaging and protection of optical electronic devices that require antibacterial properties.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The choline derivative modified organic silicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material of the present invention is a solvent-free, structural UV curing polymer antibacterial, flame retardant and antistatic material with excellent antibacterial, flame retardant and antistatic properties and low toxicity. The bactericidal efficiency of Staphylococcus aureus can reach 85-95.6%, and the bactericidal efficiency of Candida albicans can reach 90-99.5%. The water contact angle is 20-30°, the transmittance is 85-98%, the horizontal and vertical combustion oxygen index is 24-35, the horizontal and vertical combustion flame retardancy can reach V1-V0 level, and the surface impedance value is 10 5 ~10 11 ohm, hardness 4B ~ 3H, tensile strength 0.6 ~ 7.5MPa, adhesion to substrate 4 to 1, easy to process and shape, can be used in antibacterial, flame retardant and antistatic coatings, as well as optical electronic devices, food packaging, medical equipment and textiles, etc., especially suitable for the packaging and protection of optical electronic devices that require antibacterial, flame retardant and antistatic.

[0038] (2) The present invention introduces a choline derivative group with excellent bactericidal effect into the UV-curable silicone modified material, so that the prepared material has good antistatic effect, antibacterial effect and hydrophilicity.

[0039] The choline derivative modified organic silicon UV curing transparent hydrophilic antibacterial, flame retardant and antistatic material of the present invention introduces a choline derivative group containing a quaternary ammonium salt group, which has a good hydrophilic effect, thereby causing the static electricity accumulated on its surface to be conducted by the adsorbed water molecules, thereby showing a good antistatic effect, and the surface impedance value can reach 10 5 ~10 11 The presence of quaternary ammonium groups also reduces bacterial adhesion to surfaces, creating a self-cleaning antimicrobial surface for effective sterilization. Because the choline derivative groups are located on the macromolecular chains of the solidified material, they cannot migrate, overcoming the toxicity of small-molecule organic antimicrobial agents and additive-based polymer antimicrobial materials.

[0040] (3) The choline derivative modified organic silicone UV-curable transparent hydrophilic antibacterial, flame retardant and antistatic material of the present invention contains silicon and phosphorus in the obtained UV-curable material molecules. When it burns, silicon and phosphorus have a synergistic flame retardant effect, making the material have a good flame retardant effect, the horizontal and vertical combustion oxygen index is 24 to 35, and the flame retardancy can reach V1 to V0 level. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The alkoxysilane containing the choline derivative group obtained by the reaction of choline with 3-isocyanate propyltrimethoxysilane in Example 1 is 1 H-NMR spectrum;

[0042] Figure 2This is a comparison of the water contact angles on the surfaces of the cured products with different molar ratios of mercapto groups to acrylate groups in Example 1;

[0043] Figure 3 The antibacterial effects of the cured products with different molar ratios of thiol groups to acrylate groups in Example 1 on Staphylococcus aureus are compared, where a is a blank sample, b is a molar ratio of 1:1, c is a molar ratio of 1:1.5, d is a molar ratio of 1:2, e is a molar ratio of 1:2.5, and f is a molar ratio of 1:3.5. DETAILED DESCRIPTION

[0044] As mentioned above, in view of the shortcomings of the existing technology, the inventors of this case proposed the technical solution of the present invention after long-term research and extensive practice, which is mainly based on at least:

[0045] (1) The present invention introduces a choline derivative group with excellent bactericidal effect into a UV-curable organosilicon modified material, resulting in a choline derivative-modified organosilicon UV-curable transparent hydrophilic antibacterial, flame-retardant, and antistatic material having excellent biocompatibility and antibacterial effect. Because the choline derivative group is located on the macromolecular chain of the cured material and is unable to migrate, this overcomes the disadvantage of the high toxicity of small-molecule organic antibacterial agents and additive-type polymer antibacterial materials.

[0046] (2) Due to the presence of quaternary ammonium groups in choline derivatives, the antibacterial material has excellent hydrophilic properties, which can reduce the adhesion of bacteria on the surface and create an antibacterial surface with self-cleaning function to achieve effective sterilization. The quaternary ammonium groups can also cause the static electricity accumulated on the surface to be conducted to the adsorbed water molecules, thereby showing a good antistatic effect.

[0047] The choline derivative modified organosilicon UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material of the present invention is prepared by the following scheme:

[0048] Step (1), mixing an isocyanate alkoxysilane and a choline derivative in a molar ratio of 1:1 at 30-80° C., adding a dibutyltin dilaurate catalyst in an amount of 0.05-1% of the total mass of the isocyanate alkoxysilane and the choline derivative, reacting in 0.5-4 times the solvent for 1-12 hours, and then removing the solvent and unreacted raw materials under reduced pressure to obtain an alkoxysilane containing a choline derivative;

[0049] A choline derivative-containing alkoxysilane, mercaptopropyl alkoxysilane, and a small molecule compound containing two hydroxyl groups are reacted at 100-160° C. for 2-12 hours under the catalysis of p-toluenesulfonic acid, and the unreacted raw materials are removed under reduced pressure to obtain a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group; wherein the molar ratio of the choline derivative-containing alkoxysilane to the mercaptopropyl alkoxysilane is 5:95-40:60; the amount of the small molecule compound containing two hydroxyl groups is 1.1-2.0 times the total molar number of the choline derivative-containing alkoxysilane and the mercaptopropyl alkoxysilane; and the amount of the p-toluenesulfonic acid is 0.5-2% of the total mass of the choline derivative-containing alkoxysilane, mercaptopropyl alkoxysilane, and the small molecule compound containing two hydroxyl groups;

[0050] The isocyanate alkoxysilane is one or a mixture of two of 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane;

[0051] The choline derivative is one or a mixture of choline, N-oleoyl-D-erythro-sphingylphosphocholine and N-palmitoyl-D-erythro-sphingylphosphocholine;

[0052] The chemical structural formula of the choline is as follows:

[0053]

[0054] The chemical structural formula of the N-oleoyl-D-erythro-sphingylphosphorylcholine is as follows:

[0055]

[0056] The chemical structural formula of the N-palmitoyl-D-erythro-sphingosylphosphocholine is as follows:

[0057]

[0058] The solvent is one or a mixture of DMF, DMAc, tetrahydrofuran, acetonitrile, and DMSO;

[0059] The mercaptopropyl alkoxysilane is one or a mixture of two of mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane;

[0060] The small molecule compound containing two hydroxyl groups is one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and neopentyl glycol, or a mixture of several of them.

[0061] Step (2), under nitrogen protection, tetrahydrofuran and phosphorus oxychloride are added to a reaction vessel in a mass ratio of 2:1, and then a mixture of triethylamine, hydroxyethyl acrylate and tetrahydrofuran is added dropwise at 0-5°C, and the mixture is reacted at room temperature for 12 hours after the addition is complete; after the reaction is complete, the triethylamine is filtered out, and the solvent and residual reactants are removed under reduced pressure to obtain a primary product; the primary product is dissolved in dichloromethane, and washed with 10% hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution until neutral, dried with anhydrous sodium sulfate, and then the dichloromethane is removed by rotation to obtain a phosphorus-containing trifunctional acrylate;

[0062] The molar ratio of phosphorus oxychloride, triethylamine and hydroxyethyl acrylate is 1:3:3; in the mixture, the mass of tetrahydrofuran is 3 times the total mass of triethylamine and hydroxyethyl acrylate.

[0063]

[0064] Step (3), mixing the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups with phosphorus-containing trifunctional acrylate and a photoinitiator, degassing the mixture in vacuum for 10 to 30 minutes, and then UV curing the mixture for 30 to 180 seconds to obtain an antibacterial UV-curable transparent silicone material; the amount of the photoinitiator is 1 to 12% of the mass of the acrylate-terminated hyperbranched silicone-modified polyurethane-acrylate fluorescent polymer; the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups and the phosphorus-containing trifunctional acrylate are in a molar ratio of mercapto groups to acrylate groups of 1:(1 to 3.5);

[0065] The photoinitiator is Irgacure-1173, 2959, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenyl acetophenone, α,α-dimethoxy-α-phenylacetophenone, α,α-diethoxyacetophenone, α-hydroxyalkyl phenone, α-aminoalkyl phenone, aromatic phosphine oxide, bisbenzoylphenyl phosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, Michler's ketone; thiopropoxythioxanthone, isopropyl thioxanthone or a mixture thereof; more preferably, the photoinitiator is Irgacure-1173, 2959, benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and a mixture thereof or several thereof.

[0066] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely for the purpose of explaining the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

[0067] In the present invention, the analysis and testing method is as follows:

[0068] Nuclear magnetic resonance: Deuterated chloroform (CDCl3) was used as solvent and the hydrogen spectrum was measured at room temperature using a Brucker Advance-400 NMR nuclear magnetic resonance instrument from Brucker, Germany ( 1 H-NMR).

[0069] Gelation rate: The solidified material was extracted with toluene at 150°C for 4 h using the Soxhlet extraction method, and the residual amount was expressed as a percentage of the original mass of the solidified material.

[0070] Adhesion: Adhesion is tested using the cross-hatch method on BGD-502 paint films according to ISO 2409-2007.

[0071] Transmittance test: The transmittance of the polymer was tested using an Evolution 300 UV-visible spectrophotometer from Thermo Fisher Scientific, USA. The test wavelength range was 300–800 nm and the sample thickness was 10 mm.

[0072] Flame retardant properties: Horizontal and vertical combustion were measured using a KS-50C horizontal and vertical combustion tester (Shanghai Jinsen Testing Equipment Co., Ltd.).

[0073] Antistatic performance: measured using a PRS-801 surface resistance tester (Prostat, USA).

[0074] Tensile strength test: The experimental equipment is UH6503D microcomputer-controlled electronic tension-compression cyclic reciprocating testing machine produced by Youhong Measurement and Control Technology (Shanghai) Co., Ltd. The tensile speed is 2 mm / min. Each film is measured 3 times and the average value is taken.

[0075] Pencil hardness: Determined according to GB / T 6739-2006 “Paints and varnishes - Determination of film hardness by pencil method”.

[0076] Water absorption rate: Cut the coating into squares of a certain shape, soak them in deionized water at room temperature for 24 hours, use filter paper to absorb the water on the surface of the coating, and calculate the water absorption rate of the coating according to the formula:

[0077]

[0078] Where B represents the water absorption rate (%); m1 represents the mass of the coating before immersion; m2 represents the mass of the coating after immersion after the liquid on the surface of the coating is absorbed with filter paper.

[0079] Experiment on the inhibitory effect of UV curing materials on bacteria and fungi:

[0080] Test fungus: Neurospora crassa

[0081] Test bacteria: Staphylococcus aureus

[0082] Test culture medium

[0083] PDA (potato agar-dextrose medium): 200g potatoes, 15g agar, 20g glucose, dilute to 1000mL with purified water, and autoclave at 121°C for 25min. For fungal culture, omit the agar for liquid culture.

[0084] LB (Luria-Bertani) medium: 10 g tryptone, 5 g yeast extract, 10 g NaCl, 15 g agar. Add purified water to 1000 mL. Autoclave at 121°C for 25 min. Use for bacterial culture; omit the agar for liquid culture.

[0085] Experimental methods

[0086] Activation of bacterial / fungal strains: Streak the preserved bacterial / fungal strains twice on the corresponding solid culture medium. Add the activated strains to 50 mL of the corresponding liquid culture medium and culture them on a shaker set at 37 / 28°C and 180 rpm for 24 hours to prepare a bacterial suspension.

[0087] 5 μL of the prepared bacterial suspension was aspirated and dropped onto the surface of the UV-cured coating. A blank control group was set up at the same time. After air drying, the plate was sealed and placed in a 37 / 28°C constant temperature incubator in the dark for 1-5 days to observe the size and morphology of the bacterial plaques.

[0088] Example 1

[0089] (1) 225 g of 3-isocyanatepropyltrimethoxysilane, 121.18 g of choline and 700 g of acetonitrile were heated to 80° C., 0.346 g of dibutyltin dilaurate was added, and the mixture was reacted for 8 h. The solvent and unreacted raw materials were removed under reduced pressure at 80° C. / 130 mmHg to obtain 346.18 g of alkoxysilane containing a choline derivative. The alkoxysilane was then reacted with 458.127 g of mercaptopropyltrimethoxysilane and 310.350 g of ethylene glycol at 160° C. for 2 h under the catalysis of 21.293 g of p-toluenesulfonic acid. The unreacted raw materials were removed under reduced pressure at 100° C. / 130 mmHg to obtain 1021.657 g of a hyperbranched silicon-containing polymer containing a choline derivative and mercaptopropyl. 1 H-NMR see attached Figure 1 ;

[0090] (2) Under N2 protection, 306.664g of tetrahydrofuran and 153.332g of phosphorus oxychloride were maintained at 0-5°C in an ice bath, and a mixture of 303.57g of triethylamine, 348.345g of hydroxyethyl acrylate, and 1955.745g of tetrahydrofuran was added dropwise over 4 hours. After the addition was complete, the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the triethylamine salt was filtered out, and the solvent and residual reactants were removed under reduced pressure to obtain the primary product. The primary product was dissolved in dichloromethane and washed with 10% hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution until neutral. Drying was performed over anhydrous magnesium sulfate, and the dichloromethane was removed by vortexing to obtain 294.132g of a yellow phosphorus-containing trifunctional acrylate oily liquid with a yield of 75%.

[0091] (3) The obtained hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups was mixed with phosphorus-containing trifunctional acrylate in different molar ratios, and photoinitiator Irgacure-1173 was added and vacuum degassed for 10 to 30 minutes, and then UV cured for 120 seconds to obtain antibacterial UV-curable transparent silicone materials. The comprehensive properties and bactericidal properties of the materials are shown in Table 1. Figure 2 and Figure 3 , indicating that the obtained UV-curable material has excellent antibacterial effect, high light transmittance, excellent hydrophilicity and good adhesion.

[0092] Table 1 Effect of the molar ratio of mercapto groups to acrylate groups of hyperbranched silicon-containing polymers containing choline derivatives and mercaptopropyl groups and phosphorus-containing trifunctional acrylates on the properties of the cured products

[0093]

[0094] The amount of Irgacure-1173 added is 5% of the total mass of the hyperbranched silicon-containing polymer containing a choline derivative and mercaptopropyl and the phosphorus-containing trifunctional acrylate, and the curing time is 120 seconds.

[0095] Example 2

[0096] The hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group obtained in Example 1 was mixed evenly with a phosphorus-containing trifunctional acrylate and a photoinitiator Irgacure-1173, and subjected to vacuum degassing for 10 to 30 minutes. After different UV curing times, an antibacterial UV-curable transparent silicone material was obtained. The comprehensive properties and bactericidal properties of the obtained UV-curable material are shown in Table 2, indicating that the obtained UV-curable material has excellent antibacterial effect, high light transmittance, excellent hydrophilicity and good adhesion.

[0097] Table 2 Effect of different UV curing time on the properties of cured products

[0098]

[0099]

[0100] The amount of Irgacure-1173 added is 5% of the total mass of the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups and the phosphorus-containing trifunctional acrylate, and the molar ratio of mercapto groups to acrylate groups is 1:2.5.

[0101] Example 3

[0102] (1) 250 g of 3-isocyanatepropyltriethoxysilane, 729.065 g of N-oleoyl-D-erythrosphingylphosphorylcholine and 489.533 g of DMF were heated to 60° C., 0.979 g of dibutyltin dilaurate was added, and the mixture was reacted for 12 h. The solvent and unreacted raw materials were removed under reduced pressure at 120° C. / 130 mmHg to obtain 979.065 g of alkoxysilane containing a choline derivative. The alkoxysilane was then reacted with 420.603 g of mercaptopropyltrimethoxysilane and 228.30 g of 1,3-propylene glycol at 160° C. for 2 h under the catalysis of 16.280 g of p-toluenesulfonic acid. The unreacted raw materials were removed under reduced pressure at 100° C. / 130 mmHg to obtain 1021.657 g of a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group.

[0103] (2) The obtained hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups was taken, the phosphorus-containing trifunctional acrylate obtained in Example 1, and the photoinitiator 2959 were mixed evenly and vacuum degassed for 10 to 30 minutes, and then UV cured for 120 seconds to obtain an antibacterial UV-curable transparent silicone material. Its comprehensive properties and bactericidal properties are shown in Table 3, indicating that the obtained UV-curable material has excellent antibacterial effect, high light transmittance, excellent hydrophilicity and good adhesion.

[0104] Table 3 Effect of the molar ratio of mercapto groups to acrylate groups of hyperbranched silicon-containing polymers containing choline derivatives and mercaptopropyl groups and phosphorus-containing trifunctional acrylates on the properties of the cured products

[0105]

[0106]

[0107] The addition amount of the above 2959 is 7% of the total mass of the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups and the phosphorus-containing trifunctional acrylate, and the curing time is 120 seconds.

[0108] Example 4

[0109] (1) 250 g of 3-isocyanatepropyltriethoxysilane, 703.028 g of N-palmitoyl-D-erythrosphingylphosphocholine, 476.514 g of DMF, and 476.514 g of tetrahydrofuran were heated to 40° C., 7.624 g of dibutyltin dilaurate was added, and the mixture was reacted for 6 h. The solvent and unreacted raw materials were removed under reduced pressure at 120° C. / 130 mmHg to obtain 953.028 g of alkoxysilane containing a choline derivative. The mixture was then reacted with 49.085 g of mercaptopropyltrimethoxysilane and 168.975 g of 1,4-butanediol under the catalysis of 9.368 g of p-toluenesulfonic acid at 160° C. for 2 h. The unreacted raw materials were removed under reduced pressure at 100° C. / 130 mmHg to obtain 1036.088 g of a hyperbranched silicon-containing polymer containing a choline derivative and a mercaptopropyl group.

[0110] (2) 20 g of the obtained hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups, 2.2 l of the phosphorus-containing trifunctional acrylate obtained in Example 1, and a photoinitiator were mixed uniformly and subjected to vacuum degassing for 10 to 30 minutes, followed by UV curing for 120 seconds to obtain an antibacterial UV-curable transparent silicone material. Its comprehensive properties and bactericidal properties are shown in Table 4, indicating that the obtained UV-curable material has excellent antibacterial effect, high light transmittance, excellent hydrophilicity and good adhesion.

[0111] Table 4 Effect of UV curing initiator

[0112]

[0113]

[0114] The molar ratio of mercapto groups to acrylate groups was 1:3.5, and the curing time was 120 s.

Claims

1. A method for preparing a choline derivative modified silicone UV-curable transparent hydrophilic antibacterial, flame retardant and antistatic material, characterized in that: The preparation method comprises the following steps: Step (1): isocyanate alkoxysilane, choline derivative and dibutyltin dilaurate are placed in a solvent for reaction at 30-80°C for 1-12 hours, and then the solvent and unreacted raw materials are removed under reduced pressure to obtain an alkoxysilane containing a choline derivative; the alkoxysilane containing a choline derivative, mercaptopropyl alkoxysilane and a small molecule compound containing two hydroxyl groups are reacted at 100-160°C for 2-12 hours under the catalysis of p-toluenesulfonic acid, and the unreacted raw materials are removed under reduced pressure to obtain a hyperbranched silicon-containing polymer containing a choline derivative and mercaptopropyl; the choline derivative is one or a mixture of choline, N-oleoyl-D-erythro-sphingylphosphocholine and N-palmitoyl-D-erythro-sphingylphosphocholine; Step (2), under nitrogen protection, tetrahydrofuran and phosphorus oxychloride are added to a reaction vessel, and then a mixture of triethylamine, hydroxyethyl acrylate and tetrahydrofuran is added dropwise at 0-5°C, and the mixture is reacted at room temperature after the addition is complete; after the reaction is complete, the triethylamine is filtered out, and the solvent and residual reactants are removed under reduced pressure to obtain a primary product; the primary product is dissolved in dichloromethane, washed to neutrality, dried, and then the dichloromethane is removed by rotation to obtain a phosphorus-containing trifunctional acrylate; Step (3): uniformly mixing the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups, phosphorus-containing trifunctional acrylate, and a photoinitiator, and subjecting the mixture to vacuum degassing for 10 to 30 minutes, and then subjecting the mixture to UV curing for 30 to 180 seconds to obtain the desired UV-curable transparent organic silicone material; wherein the hyperbranched silicon-containing polymer containing choline derivatives and mercaptopropyl groups and the phosphorus-containing trifunctional acrylate are in a molar ratio of mercapto groups to acrylate groups of 1:(1 to 3.5).

2. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The isocyanate alkoxysilane in step (1) is a mixture of one or both of 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane; the molar ratio of the isocyanate alkoxysilane to the choline derivative is 1:

1.

3. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The solvent in step (1) is one or a mixture of DMF, DMAc, tetrahydrofuran, acetonitrile, and DMSO.

4. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The mercaptopropyl alkoxysilane in step (1) is one or a mixture of two of mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane.

5. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The molar ratio of the alkoxysilane containing the choline derivative to the mercaptopropyl alkoxysilane in step (1) is 5:95 to 40:

60.

6. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The small molecule compound containing two hydroxyl groups in step (1) is one or a mixture of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and neopentyl glycol, and its amount is 1.1 to 2.0 times the total molar number of the alkoxysilane containing the choline derivative and the mercaptopropyl alkoxysilane.

7. The method for preparing a choline derivative modified silicone UV curable transparent hydrophilic antibacterial, flame retardant and antistatic material according to claim 1, characterized in that: The molar ratio of phosphorus oxychloride, triethylamine and hydroxyethyl acrylate in step (2) is 1:3:3; in the mixture, the mass of tetrahydrofuran is 3 times the total mass of triethylamine and hydroxyethyl acrylate.

8. A UV-curable transparent antibacterial, flame-retardant and antistatic silicone material, prepared by the method according to any one of claims 1 to 7.

9. Use of the UV-curable transparent antibacterial, flame-retardant and antistatic silicone material according to claim 8 as antibacterial coatings, optical electronic devices, food packaging, medical equipment and textiles.

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