Preparation method of UV-cured organic silicon modified non-isocyanate polyurethane antibacterial material as well as product and application of UV-cured organic silicon modified non-isocyanate polyurethane antibacterial material

Abstract

The invention discloses a preparation method of a UV-cured organosilicon modified non-isocyanate polyurethane antibacterial material as well as a product and application of the UV-cured organosilicon modified non-isocyanate polyurethane antibacterial material, and particularly relates to a preparation method of a non-isocyanate hyperbranched organosilicon sulfydryl prepolymer containing an antibacterial functional group by taking non-isocyanate polyurethane as a raw material; the preparation method comprises the following steps: uniformly mixing a non-isocyanate hyperbranched organic silicon sulfydryl prepolymer containing an antibacterial functional group and a hyperbranched secondary amine prepolymer containing an acrylate group, carrying out vacuum defoaming, and carrying out UV curing under the condition that a photoinitiator is not needed to obtain the bactericidal and bacteriostatic UV curing material. The antibacterial efficiency of the UV curing material on staphylococcus aureus, escherichia coli and pseudomonas aeruginosa within one hour can reach 99.9%, the hardness of the UV curing material is 3B-6B, the water contact angle is 32.0-45.6 degrees, and the UV curing material can be applied to the fields of antibacterial textiles, anti-corrosion and anti-mildew coatings, food packaging, medical equipment and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of silicone materials, and relates to a preparation method, a product and an application of a UV-curable silicone-modified non-isocyanate polyurethane antibacterial material. Background Art

[0002] Fungi and bacteria are microorganisms that people often come into contact with in daily life. Some bacteria are pathogens of human diseases, which can cause diseases such as tuberculosis, gonorrhea, anthrax, plague, trachoma, etc. Some fungi can cause skin itching, athlete's foot, tinea manus, tinea cruris, lymphatic infection, pulmonary fungal infection, etc. in humans; they may also adsorb and colonize on public health facilities, medical devices, biosensors, and medical equipment, posing a serious risk to people's lives; some of them can cause food spoilage, corruption, mildew... In recent years, materials with antibacterial activity have been developed to reduce the harm caused by fungi and bacteria. Therefore, developing efficient and low-toxic antibacterial materials, improving people's living environment, protecting human life and health, and promoting the development of the national economy are important tasks. For example, textile fabrics composed of fibers, due to their porous shape and the chemical structure of polymer, are conducive to the attachment of microorganisms and become good hosts for the survival and reproduction of microorganisms. In addition to the harm to the human body, these hosts will also contaminate the fibers. For this reason, fabrics with antibacterial functions have been developed, which can effectively inhibit the growth and reproduction of bacteria on the fabrics, eliminate odors, and keep the fabrics fresh and hygienic.

[0003] Small molecule organic antibacterial agents such as quaternary ammonium salts, alcohols, phenols, organometals, etc. have mature processing technologies and excellent bactericidal effects. However, they have relatively high toxicity, poor thermal stability, are prone to causing microbial drug resistance, and have a short service life. When small molecule organic antibacterial agents or metal antibacterial agents are added to polymer materials, the resulting additive-type polymer antibacterial materials also have disadvantages such as relatively high toxicity and being prone to causing microbial drug resistance because the small molecule organic antibacterial agents or metal antibacterial agents will migrate to the material surface [ACS Appl. Mater, 2016, 8, 21640 - 21647; J. Reinf. Plast. Comp., 2020, 39(3 - 4): 95 - 110.]. Structured polymer antibacterial materials are prepared by covalently bonding precursors with antibacterial groups to target polymers, which not only overcomes the disadvantage of high toxicity of small molecule antibacterial agents and additive-type polymer antibacterial materials, but also has advantages such as easy processing, stable performance, and good bactericidal effect [Macromol. Biosci., 2020, 20: 1900301; Progress in Organic Coatings, 2023, 174, 107313; Macromol. Rapid Commun. 2024, 2400300.].

[0004] Ultraviolet (UV) curing technology has the advantages of fast curing speed, simple processing technology, low energy consumption, and no pollution, and is widely used in the fields of paints, inks, and electronic packaging of furniture and industrial products. In recent years, with the enhancement of people's environmental awareness, the research and development of UV-curable antibacterial polymer materials have also attracted extensive attention. Hydrogen bonds can be formed between the imino group (N-H) and the carbonyl group (C=O) in polyurethane (PU) molecules, endowing it with excellent mechanical properties and making it one of the most widely used polymer materials. Chinese Patent Application for Invention CN201811359638.9 reported a highly wear-resistant waterborne UV floor paint and its preparation method, and the UV floor paint was prepared by adding in-can bactericides to a waterborne UV polyurethane dispersion. Chinese Patent Application for Invention CN201710716119.2 added flax cellulose to UV-curable waterborne polyurethane acrylate, and it was reported that a UV-curable waterborne polyurethane with antibacterial, breathable, and flame-retardant properties was obtained. However, the above UV-curable antibacterial materials are additive polymer materials. The inventors previously designed and synthesized a hyperbranched organosilicon polymer containing Schiff base and mercaptopropyl, and cured it with a castor oil-based polyurethane–acrylate via a UV-induced thiol–ene click reaction to prepare a hyperbranched organosilicon-modified antibacterial material. The initial thermal decomposition temperature of the obtained material was 219–251 °C, the pencil hardness could reach 4H, and it had good inhibitory effects on Staphylococcus aureus and fungi [Chinese Patent ZL202210512217.5; Progress in Organic Coatings, 2023, 174, 107313]. The synthesis of the above traditional polyurethane usually uses diisocyanate as a raw material, which is toxic and harmful. After people inhale it, it will cause bronchitis and pulmonary edema, and there is also a risk of cancer with long-term exposure. More seriously, phosgene used to produce diisocyanate is a colorless and highly toxic gas, posing a very high risk. Different from traditional polyurethane, non-isocyanate polyurethane (NIPU) can be prepared from CO2 as a raw material to prepare ethylene carbonate derivatives, and then reacted with amine compounds, avoiding toxic and harmful raw materials, and effectively utilizing CO2 to reduce greenhouse gas emissions [Eur. Polym. J. 2020, 137, 109915.]. Organosilicon polymer materials have the advantages of ultraviolet radiation resistance, temperature and weather resistance, and low shrinkage rate, and are also widely used in the national economy.

[0005] In order to overcome the above-mentioned disadvantages of the UV-curable antibacterial material and give full play to the advantages of the UV-curing technology, the present invention discloses a preparation method of a UV-curable antibacterial material. Specifically, without using diisocyanate as a raw material, a non-isocyanate polyurethane is used as a raw material to prepare a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group. Then, the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group and a hyperbranched secondary amine prepolymer containing an acrylate group are mixed evenly according to the molar ratio of mercapto to acrylate group of 1:1 to 1:3.0, and after vacuum degassing and without the need for a photoinitiator, a bactericidal and antibacterial UV-curable material is obtained after UV curing. The gelation rate of the UV-curable material is 67.5-73.4%, its hardness is 3B-6B, the water contact angle is 32.0-45.6°, and the antibacterial efficiency against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa can reach 99.9% within 4 hours. It can be used in fields such as antibacterial textiles, anti-corrosion and mildew-proof coatings, food packaging and medical equipment. Summary of the Invention

[0006] The object of the present invention is to provide a preparation method, product and application of a UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material in view of the deficiencies of the prior art.

[0007] In the first aspect, the present invention provides a preparation method of a UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material, including the following steps:

[0008] At 50-100 °C, a diamine is dropped into ethylene carbonate EC and reacted fully to obtain a non-isocyanate compound NIPU;

[0009] At 30-50 °C, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and potassium iodide are added to a reaction vessel containing a reaction solvent, and after reacting for a period of time under magnetic stirring, condensation reflux and nitrogen protection, vacuum filtration is carried out and the filter cake is washed, and then the reaction solvent is evaporated to obtain an alkoxysilane liquid containing an antibacterial functional group;

[0010] At 80-140 °C, the alkoxysilane liquid containing an antibacterial functional group is reacted with 3-mercaptopropylalkoxysilane and non-isocyanate compound NIPU for a period of time, then the temperature is raised to 120-160 °C and the reaction is continued for a period of time, and the temperature is lowered to 80-120 °C and the by-products and small molecules are removed by vacuum distillation to obtain a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group;

[0011] At 25 to 80 °C, a compound containing two acrylate groups and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) are reacted in a reaction solvent for a period of time, and the reaction solvent is removed by rotary evaporation to obtain a hyperbranched secondary amine prepolymer containing acrylate groups;

[0012] The non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups and the hyperbranched secondary amine prepolymer containing acrylate groups are mixed evenly, and after vacuum degassing and without the need for a photoinitiator, a UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material is obtained through UV curing.

[0013] Preferably, the diamine is one or a mixture of two or more of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, p-phenylenediamine, polyetheramine 230, and polyetheramine D400; the molar ratio of ethylene carbonate EC to diamine is 2.0:1 to 2.2:1, preferably 2.1:1.

[0014] Preferably, the 3-mercaptopropylalkoxysilane is one or a mixture of two or more of 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; the molar ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to potassium iodide is 1:1.1; the molar ratio of the alkoxysilane containing antibacterial functional groups to 3-mercaptopropylalkoxysilane is 5:95 to 30:70.

[0015] Preferably, in the preparation process of the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups, the temperature is raised from 80 to 140 °C at a rate of 5 to 15 °C per 10 to 40 min to 120 to 160 °C.

[0016] Preferably, the compound containing two acrylate groups is one or a mixture of two or more of polyethylene glycol diacrylate and neopentyl glycol polymethyloxirane diacrylate; among them, the molecular weight of polyethylene glycol in polyethylene glycol diacrylate is 200 to 1000, preferably 200 to 600;

[0017] The molar ratio of the compound containing two acrylate groups and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) is 3:1.

[0018] Preferably, the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups and the hyperbranched secondary amine prepolymer containing acrylate groups are in a molar ratio of mercapto to acrylate group of 1:1 to 1:3.0.

[0019] Preferably, the reaction time for preparing the non-isocyanate compound NIPU is 2 to 24 h; the reaction time for preparing the alkoxysilane liquid containing an antibacterial functional group is 1 to 5 h; the reaction time for preparing the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group is 2 to 8 h at 80 to 140 °C and 0.5 to 4 h at 120 to 160 °C; the reaction time for preparing the hyperbranched secondary amine prepolymer containing an acrylate group is 2 to 12 h.

[0020] Preferably, the UV curing time is 30 to 180 s.

[0021] Preferably, the reaction solvent is anhydrous methanol.

[0022] In a second aspect, the present invention provides a UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material, with a gelation rate of 67.5 to 73.4%, a hardness of 3B to 6B, a water contact angle of 32.0 to 45.6°, an antibacterial efficiency against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa reaching 99.9% within 4 h, and excellent thermal stability.

[0023] In a third aspect, the present invention provides the application of the UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material in the preparation of antibacterial textiles, anti-corrosion and anti-mildew coatings, food packaging, or medical devices.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] (1) In the present invention, the polyurethane segment is non-isocyanate polyurethane (NIPU), which is obtained by reacting a carbonate ethylene ester derivative prepared from CO2 as a raw material with an amine compound, avoiding toxic and harmful raw materials, and effectively utilizing CO2 to reduce greenhouse gas emissions. It avoids the traditional polyurethane synthesis relying on diisocyanates, whose production raw material phosgene is highly toxic and the diisocyanates themselves are harmful, and inhalation can cause health problems. The present invention adopts a brand-new synthesis route, starting from CO2 as the raw material, not only avoiding toxic substances but also realizing the resource utilization of CO2, in line with the concept of green chemistry.

[0026] (2) The UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material in the present invention contains an organosilicon polymer segment, having advantages such as resistance to ultraviolet radiation, temperature and weather resistance, and low shrinkage rate, improving the thermal stability of the material and overcoming the disadvantage of poor thermal stability of traditional small-molecule organic antibacterial agents.

[0027] (3) The present invention realizes crosslinking curing through thiol-acrylate click reaction, without adding photoinitiators, avoiding small-molecule residues and reducing the toxicity of the material. The curing system has no solvent and no photoinitiator residue, in line with the concept of green chemistry, and is suitable for sensitive fields such as food packaging and medical devices.

[0028] (4) In the present invention, the antibacterial quaternary ammonium salt group is connected to the macromolecular chain of the cured product through a chemical bond, avoiding the migration problem of small molecule antibacterial agents and reducing toxicity. At the same time, through the optimized synthesis process and raw material ratio, a suitable cross-linked structure is formed during the UV curing process of the material, ensuring properties such as gelation rate, hardness, and water contact angle. Therefore, the UV-curable silicone-modified non-isocyanate polyurethane antibacterial material is a solvent-free, structural UV-curable polymer antibacterial material with low toxicity. Its gelation rate is 67.5 - 73.4%, its hardness is 3B - 6B, and the water contact angle is 32.0 - 45.6°. Also, by optimizing the ratio of the prepolymer and the hyperbranched secondary amine prepolymer containing acrylate groups, reaction conditions, etc., the antibacterial performance is further enhanced. The antibacterial efficiency against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa can reach 99.9% within 4 hours, and it is easy to process and form.

[0029] (5) The UV-curable silicone-modified non-isocyanate polyurethane antibacterial material of the present invention can be used in fields such as antibacterial textiles, anti-corrosion and mold-proof coatings, food packaging, and medical equipment. Description of the Drawings

[0030] Figure 1 It is the FT-IR spectrum of SiNP-20.

[0031] Figure 2 It is of SiNP-20 1 1H-NMR spectrum.

[0032] Figure 3 It is of SiNP-20 13 13C-NMR spectrum.

[0033] Figure 4 It is the FT-IR spectrum of the hyperbranched secondary amine prepolymer containing acrylate groups prepared from neopentyl glycol poly(methyloxirane) diacrylate and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) at a molar ratio of 3:1 in Example 1.

[0034] Figure 5 It is the plate coating result of different molar ratios of alkoxysilane containing antibacterial functional groups and mercaptopropyltrimethoxysilane against Staphylococcus aureus in Example 1.

[0035] Figure 6 It is the plate coating result of different molar ratios of alkoxysilane containing antibacterial functional groups and mercaptopropyltrimethoxysilane against Escherichia coli in Example 1.

[0036] Figure 7 It is the plate coating result of different molar ratios of alkoxysilane containing antibacterial functional groups and mercaptopropyltrimethoxysilane against Pseudomonas aeruginosa in Example 1.

[0037] Figure 8 For Example 2, the results of plate coating of non-isocyanate hyperbranched organosilicon mercapto prepolymers containing antibacterial functional groups and hyperbranched secondary amine prepolymers containing acrylate groups with different molar ratios of mercapto groups and acrylate groups against Staphylococcus aureus.

[0038] Figure 9 For Example 2, the results of plate coating of non-isocyanate hyperbranched organosilicon mercapto prepolymers containing antibacterial functional groups and hyperbranched secondary amine prepolymers containing acrylate groups with different molar ratios of mercapto groups and acrylate groups against Escherichia coli. Detailed implementation manners

[0039] As described above, in view of the deficiencies of the prior art, the inventors of this case have proposed the technical solution of the present invention through long-term research and a large number of practices: in the UV-curable polymer antibacterial material of the present invention, a non-isocyanate polyurethane chain segment obtained by reacting a ethylene carbonate derivative prepared from CO2 as a raw material with an amine compound is introduced, avoiding toxic and harmful raw materials, and effectively utilizing CO2 to reduce greenhouse gas emissions; introducing an organosilicon polymer chain segment, which has advantages such as ultraviolet radiation resistance, temperature and weather resistance, and low shrinkage rate, improving the thermal stability of the material and overcoming the disadvantage of poor thermal stability of traditional small molecule organic antibacterial agents; the UV-curing system does not require an additional UV initiator, reducing the toxicity of the material and improving the storage stability of the material. The antibacterial quaternary ammonium salt groups are on the macromolecular chains of the cured product, so they cannot migrate, overcoming the disadvantage of relatively high toxicity of small molecule organic antibacterial agents and additive polymer antibacterial materials.

[0040] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0041] This embodiment provides a preparation method of a UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material, which includes the following steps:

[0042] Step (1), synthesize a non-isocyanate compound (NIPU): drop a diamine into ethylene carbonate (EC) at 50-100 °C, and then continue to react at 50-100 °C for 2-24 h, and remove unreacted raw materials under reduced pressure to obtain NIPU.

[0043] The present invention uses CO2 as a raw material to prepare ethylene carbonate (EC), which reacts with diamine to form a NIPU chain segment, completely abandoning the toxic diisocyanate and highly toxic phosgene in traditional polyurethanes, eliminating the use of isocyanate and phosgene from the source, and reducing the health risks in the production process.

[0044] Taking the reaction of ethylenediamine and EC as an example, the synthetic reaction technical route of NIPU is as follows:

[0045]

[0046] Step (2), non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups:

[0047] Dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride and potassium iodide were added to a three-necked flask using anhydrous methanol as the reaction solvent at a molar ratio of 1:1.1. The flask was reacted at 30-50 °C for 1-5 h under magnetic stirring, reflux condensation and nitrogen protection, preferably reacted at 35 °C for 3 h. After vacuum filtration and washing the filter cake with anhydrous methanol, methanol was removed at 50-80 °C using a rotary evaporator to obtain a pale yellow alkoxysilane liquid containing antibacterial functional groups.

[0048] Next, the obtained product was reacted with 3-mercaptopropylalkoxysilane and NIPU at 80-140 °C for 2-8 h, and then the temperature was increased by 5-15 °C every 10-40 min until 120-160 °C. Preferably, the temperature was increased by 10 °C every 0.5 h until 160 °C, and then the reaction was continued for 0.5-4 h. The temperature was lowered to 80-120 °C and by-products and small molecules were removed by vacuum distillation to obtain a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups.

[0049] In the present invention, 3-mercaptopropylalkoxysilane and antibacterial functional group silane are copolymerized to form a hyperbranched organosilicon prepolymer, endowing the material with organosilicon characteristics. The organosilicon chain segments significantly improve the ultraviolet radiation resistance (anti-yellowing), heat resistance and weather resistance of the material. At the same time, the antibacterial groups are stably fixed in the polymer network without migration risk. The toxicity of the material is significantly lower than that of additive antibacterial agents. The quaternary ammonium salt groups destroy the bacterial cell membrane by positive charge adsorption, and cooperate with the redox activity of the mercapto group to achieve multiple antibacterial mechanisms.

[0050] Taking the synthesis of a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups from NIPU, mercaptopropyltrimethoxysilane and alkoxysilane containing antibacterial functional groups obtained by the reaction of ethylenediamine and EC as an example, the preparation route of the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups is as follows:

[0051]

[0052]

[0053] Step (3), synthesize a hyperbranched secondary amine prepolymer containing acrylate groups: React a compound containing two acrylate groups and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(propane-2-amine) in a solvent at 25-80 °C for 2-12 h, and then remove the solvent by rotary evaporation to obtain a hyperbranched secondary amine prepolymer containing acrylate groups.

[0054] Taking the preparation of a hyperbranched secondary amine prepolymer containing acrylate groups by reacting neopentyl glycol polymethylethylene oxide diacrylate and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(propane-2-amine) in a molar ratio of 3:1 as an example, its preparation route is as follows:

[0055]

[0056] Step (4), prepare a UV-curable organosilicon-modified non-isocyanate polyurethane antibacterial material: Mix a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups and a hyperbranched secondary amine prepolymer containing acrylate groups evenly, and after vacuum degassing and without the need for a photoinitiator, obtain a bactericidal and antibacterial UV-curable material through UV curing.

[0057] In the present invention, the hyperbranched organosilicon mercapto prepolymer is mixed with the hyperbranched secondary amine acrylate prepolymer to form a high crosslink density network, enhance the intermolecular force, and endow the material with low shrinkage rate, high hardness and moderate flexibility.

[0058] In the present invention, the diamine is one or a mixture of several of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, p-phenylenediamine, polyetheramine 230 and polyetheramine D400. The molar ratio of EC to the diamine is 2.0:1 to 2.2:1; preferably, the molar ratio of EC to the diamine is 2.1:1.

[0059] In the present invention, the 3-mercaptopropylalkoxysilane is one or a mixture of two of 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; the molar ratio of the prepared alkoxysilane containing antibacterial functional groups to the 3-mercaptopropylalkoxysilane is 5:95 to 30:70.

[0060] In the present invention, the compound containing two acrylate groups is one or a mixture of several of polyethylene glycol diacrylate and neopentyl glycol polymethylethylene oxide diacrylate. Among them, the molecular weight of polyethylene glycol in polyethylene glycol diacrylate is 200-1000; preferably, the molecular weight of polyethylene glycol in polyethylene glycol diacrylate is 200-600.

[0061] In the present invention, the molar ratio of the compound containing two acrylate groups to 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(propane-2-amine) is 3:1.

[0062] In the present invention, the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group and the hyperbranched secondary amine prepolymer containing an acrylate group are in a molar ratio of mercapto group to acrylate group of 1:1 to 1:3.0, and the UV curing time is 30 to 180 s.

[0063] The curing time of the present invention only needs 30 to 180 seconds, with low energy consumption and high curing efficiency, suitable for industrial continuous production, high process reaction efficiency, and reduced by-products; no post-treatment is required to remove the photoinitiator, reducing production costs. In summary, through the synergistic effect of non-isocyanate polyurethane, organosilicon modification, structural antibacterial group fixation, and initiator-free UV curing technology, the present invention realizes a comprehensive improvement in the environmental protection, durability, and functionality of the material.

[0064] This embodiment also provides a UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material. The gelation rate of this antibacterial organosilicon material is 67.5 to 73.4%, its hardness is 3B to 6B, the water contact angle is 32.0 to 45.6°, and the antibacterial efficiency against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa can reach 99.9% within 4 h.

[0065] This embodiment also provides an application of the UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material in the fields of antibacterial textiles, anti-corrosion and mildew-proof coatings, food packaging, and medical equipment.

[0066] The following further explains the technical solutions of the present invention in conjunction with several preferred embodiments, but the experimental conditions and set parameters therein should not be regarded as a limitation to the basic technical solutions of the present invention. And the protection scope of the present invention is not limited to the following embodiments.

[0067] In the present invention, the analysis and testing methods are as follows:

[0068] Nuclear magnetic resonance: Measured at room temperature with a Brucker Advance-500 NMR nuclear magnetic resonance spectrometer from Brucker Company, Germany, using deuterated chloroform (CDCl3) as the solvent.

[0069] Fourier transform infrared spectroscopy: Tested with a Nicolet 700 Fourier transform infrared spectrometer (Nicolet Company, USA) in the range of 4000–650 cm -1 Infrared spectrum.

[0070] Gelation rate: Measured by the Soxhlet extraction method. The cured product is extracted with toluene at 150 °C for 4 h, and expressed as the percentage of the residue in the original mass of the cured product.

[0071] Pencil hardness: It is determined according to GB / T 6739—2006 "Determination of film hardness by pencil method for paints and varnishes".

[0072] Experiment on the antibacterial effect of UV-curing materials:

[0073] Tested Gram-positive bacteria: Staphylococcus aureus

[0074] Tested Gram-negative bacteria: Escherichia coli

[0075] Tested Gram-negative bacilli: Pseudomonas aeruginosa

[0076] Tested culture medium

[0077] PDA (Potato Dextrose Agar Medium): 200 g of potatoes, 15 g of agar, 20 g of dextrose, add pure water to make up to 1000 mL, and sterilize by high-pressure moist heat at 121 °C for 25 min. It is used for fungal culture, and agar is omitted for liquid culture.

[0078] LB (Luria-Bertani) medium: 10 g of tryptone, 5 g of yeast extract, 10 g of NaCl, 15 g of agar, add pure water to make up to 1000 mL, and sterilize by high-pressure moist heat at 121 °C for 25 min. It is used for bacterial culture, and agar is omitted for liquid culture.

[0079] Experimental method

[0080] Activation of bacterial strains: The preserved bacterial / fungal strains are streaked and cultured twice on the corresponding solid medium. The activated strains are added to 50 mL of the corresponding liquid medium, the shaker is set at 37 / 28 °C and 180 r / min, and they are continuously cultured on the shaker for 24 h to prepare a bacterial suspension.

[0081] Pipette 5 μL of the prepared bacterial suspension and drop it on the surface of the UV-cured coating. At the same time, set up a blank control group. After air-drying, seal the plate and place it in a constant temperature incubator at 37 / 28 °C in the dark for 1 - 5 d to observe the size and morphology of the bacterial plaque.

[0082] Example 1

[0083] (1) 60.100 g (1 mol) of ethylenediamine was added dropwise to 184.926 g (2.1 mol) of ethylene carbonate. After the addition was completed, the reaction was carried out at 100 °C for 8 h, and the by-products and small molecules were removed by vacuum distillation to obtain NIPU-1.

[0084] (2) 248.14 g (0.5 mol) of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and 91.3017 g (0.55 mol) of potassium iodide were added to a three-necked flask containing 340 g of anhydrous methanol. After reacting at 35 °C for 3 h under nitrogen protection, the mixture was filtered under reduced pressure. The filtrate was then rotary evaporated to remove methanol, obtaining a pale yellow viscous liquid N-Si (an alkoxysilane liquid containing antibacterial functional groups). React at 100 °C for 2 h according to the material ratio shown in Table 1, then raise the temperature by 10 °C every 0.5 h until the temperature reaches 160 °C and react for 1 h. Cool down to 80 °C and distill under reduced pressure to remove by-products and small molecules, obtaining a non-isocyanate hyperbranched organosilicon mercapto prepolymer SiNP containing antibacterial functional groups. The FT-IR of SiNP-20, 1 1H-NMR and 13 13C-NMR spectra are shown in Figures 1-3 .

[0085] Table 1 Material ratio for preparing non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups

[0086]

[0087] (3) 98.520 g (0.3 mol) of neopentyl glycol polymethylethylene oxide diacrylate and 44.400 g (0.1 mol) of 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) were added to a three-necked flask containing 166 g of anhydrous methanol. After reacting at 35 °C for 6 h, the methanol was removed by rotary evaporation, obtaining a hyperbranched secondary amine prepolymer containing acrylate groups. The FT-IR spectrum of the product is shown in Figure 4 .

[0088] (4) The non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups and the hyperbranched secondary amine prepolymer containing acrylate groups were mixed evenly according to a molar ratio of mercapto groups to acrylate groups of 1:2. After vacuum degassing for 0.5 h, UV curing was carried out for 50 s to obtain an antibacterial polymer material. Its basic properties and antibacterial effects are shown in Table 2 and Figures 5-7 .

[0089] Table 2 Influence of different non-isocyanate hyperbranched organosilicon mercapto prepolymers containing antibacterial functional groups

[0090]

[0091] Example 2

[0092] Take SiNP-20 and the hyperbranched secondary amine prepolymer containing acrylate groups in Example 1, mix them evenly according to different molar ratios of mercapto groups to acrylate groups, after vacuum degassing for 0.5 h, cure them by UV for 50 s to obtain the antibacterial polymer material. Its basic properties and antibacterial effects are shown in Table 3 and Figures 8-9 。

[0093] Table 3 Effects of different molar ratios of mercapto groups to acrylate groups

[0094]

[0095] Example 3

[0096] Take SiNP-20 and the hyperbranched secondary amine prepolymer containing acrylate groups in Example 1, mix them evenly according to the molar ratio of mercapto groups to acrylate groups of 1:2, after vacuum degassing for 0.5 h, cure them by UV for different times to obtain the antibacterial polymer material. Its basic properties and antibacterial effects are shown in Table 4.

[0097] Table 4 Effects of different UV curing times

[0098]

[0099]

[0100] Example 4

[0101] (1) According to the feeding ratios shown in Table 5, add polyethylene glycol diacrylate prepared from 0.3 mol of polyethylene glycol with different molecular weights and 44.400 g (0.1 mol) of 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(propane-2-amine) into a three-necked flask containing anhydrous methanol (the material ratios are shown in Table 5). After reacting at 35 °C for 6 h, remove methanol by rotary evaporation to obtain a liquid hyperbranched secondary amine prepolymer containing acrylate groups.

[0102] Table 5 Effects of polyethylene glycol with different molecular weights

[0103]

[0104] (2) Take the non-isocyanate hyperbranched organosilicon mercapto prepolymer SiNP-20 containing antibacterial functional groups in Example 1 and the hyperbranched secondary amine prepolymer containing acrylate groups in step (1) of this example, mix them evenly according to the molar ratio of mercapto groups to acrylate groups of 1:2, after vacuum degassing for 0.5 h, cure them by UV for 50 s to obtain the antibacterial polymer material. Its basic properties and antibacterial effects are shown in Table 6.

[0105] Table 6 Properties of cured products prepared from polyethylene glycol diacrylate with different molecular weights

[0106]

[0107] Example 5

[0108] (1) 74.130 g (1 mol) of propylenediamine was added dropwise to 184.926 g (2.1 mol) of ethylene carbonate. After the addition was complete, the reaction was carried out at 100 °C for 8 h, and by-products and small molecules were removed by vacuum distillation to obtain NIPU-2.

[0109] (2) 248.14 g (0.5 mol) of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and 91.3017 g (0.55 mol) of potassium iodide were added to a three-necked flask containing 340 g of anhydrous methanol. After reacting at 35 °C for 3 h under nitrogen protection, after vacuum filtration, the filtrate was rotary evaporated to remove methanol to obtain a pale yellow viscous liquid N-Si. 25.6050 g of NIPU-2, 11.7556 g of N-Si and 15.7072 g of mercaptopropyltrimethoxysilane were reacted at 100 °C for 2 h, and then the temperature was raised by 10 °C every 0.5 h until the temperature was raised to 160 °C and reacted for 1 h. The temperature was lowered to 80 °C and by-products and small molecules were removed by vacuum distillation to obtain a non-isocyanate hyperbranched organosilicon mercapto prepolymer SiNP-2 with antibacterial functional groups.

[0110] (3) SiNP-2 and the hyperbranched secondary amine prepolymer containing acrylate groups obtained in step (3) of Example 1 were mixed evenly according to the molar ratio of mercapto groups to acrylate groups of 1:2. After vacuum degassing for 0.5 h, it was UV-cured for 50 s to obtain an antibacterial polymer material with a gelation rate of 71.5 / %, a water contact angle of 45.7°, a pencil hardness of 4B, and antibacterial efficiencies of 95.6%, 99.5% and 99.9% against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa for 4 h, respectively.

[0111] Example 6

[0112] (1) 116.205 g (1 mol) of hexamethylenediamine was added dropwise to 184.926 g (2.1 mol) of ethylene carbonate. After the addition was complete, the reaction was carried out at 100 °C for 8 h, and by-products and small molecules were removed by vacuum distillation to obtain NIPU-3.

[0113] (2) 248.14 g (0.5 mol) of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and 91.3017 g (0.55 mol) of potassium iodide were added to a three-necked flask containing 340 g of anhydrous methanol. After reacting at 35 °C for 3 h under nitrogen protection, the mixture was filtered under reduced pressure. The filtrate was rotary-evaporated to remove methanol, and a pale yellow viscous liquid N-Si was obtained. 26.8150 g of NIPU-3, 11.7556 g of N-Si, and 15.7072 g of mercaptopropyltrimethoxysilane were reacted at 100 °C for 2 h, then the temperature was raised by 10 °C every 0.5 h until the temperature reached 160 °C and reacted for 1 h. The temperature was then lowered to 80 °C and the by-products and small molecules were removed by vacuum distillation to obtain a non-isocyanate hyperbranched organosilane mercapto-prepolymer SiNP-3 containing antibacterial functional groups.

[0114] (3) SiNP-3 and the hyperbranched secondary amine prepolymer containing acrylate groups obtained in step (3) of Example 1 were mixed evenly according to a molar ratio of mercapto groups to acrylate groups of 1:2. After vacuum degassing for 0.5 h, it was UV-cured for 50 s to obtain an antibacterial polymer material with a gelation rate of 71.8 / %, a water contact angle of 46.5°, a pencil hardness of 5B, and antibacterial efficiencies against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa of 90.2%, 98.0%, and 99.9% respectively after 4 h.

[0115] In the present invention, where a composition is described as having, comprising, or including a specific component, or where a process is described as having, comprising, or including a specific process step, it is contemplated that the composition taught by the present invention also consists essentially of the recited components or consists of the recited components, and the process taught by the present invention also consists essentially of the recited process steps or consists of the recited process step groups.

Claims

1. A preparation method of a UV-curable silicone-modified non-isocyanate polyurethane antibacterial material, characterized in that It includes the following steps: At 50 - 100 °C, the diamine is dropped into ethylene carbonate (EC) and fully reacted to obtain the non-isocyanate compound NIPU; At 30 - 50 °C, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and potassium iodide are added into a reaction vessel containing a reaction solvent. After reacting for a period of time under magnetic stirring, condensation reflux and nitrogen protection, vacuum filtration is carried out and the filter cake is washed, and then the reaction solvent is evaporated to obtain an alkoxysilane liquid containing antibacterial functional groups; At 80 - 140 °C, the alkoxysilane liquid containing antibacterial functional groups reacts with 3-mercaptopropylalkoxysilane and the non-isocyanate compound NIPU for a period of time. Then, the temperature is raised to 120 - 160 °C and the reaction continues for a period of time. After that, the temperature is lowered to 80 - 120 °C and by-product and small molecules are removed by vacuum distillation to obtain a non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups; At 25 - 80 °C, a compound containing two acrylate groups and 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) react in a reaction solvent for a period of time. After removing the reaction solvent by rotary evaporation, a hyperbranched secondary amine prepolymer containing acrylate groups is obtained; The non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups and the hyperbranched secondary amine prepolymer containing acrylate groups are mixed evenly, and after vacuum degassing and under the condition of not requiring a photoinitiator, a UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material is obtained through UV curing.

2. The method according to claim 1, characterized in that, The diamine is one or a mixture of several of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, p-phenylenediamine, polyetheramine 230 and polyetheramine D400; the molar ratio of ethylene carbonate (EC) to the diamine is 2.0:1 - 2.2:

1.

3. The method according to claim 1, wherein The 3-mercaptopropylalkoxysilane is one or a mixture of several of 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; the molar ratio of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride to potassium iodide is 1:1.1; the molar ratio of the alkoxysilane containing antibacterial functional groups to 3-mercaptopropylalkoxysilane is 5:95 - 30:

70.

4. The method according to claim 1, wherein During the preparation process of the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing antibacterial functional groups, the temperature is raised from 80 - 140 °C to 120 - 160 °C at a rate of 5 - 15 °C per 10 - 40 min.

5. The method according to claim 1, wherein The compound containing two acrylate groups is one or a mixture of several of polyethylene glycol diacrylate and neopentyl glycol polymethyloxirane diacrylate; among them, the molecular weight of polyethylene glycol in polyethylene glycol diacrylate is 200 - 1000; The molar ratio of the compound containing two acrylate groups to 1,1'-[(2-((2-aminopropoxy)methyl)-2-ethylpropane-1,3-diyl)dioxy]bis(prop-2-amine) is 3:

1.

6. The method according to claim 1, wherein The non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group and the hyperbranched secondary amine prepolymer containing an acrylate group are in a molar ratio of mercapto group to acrylate group of 1:1 to 1:3.

0.

7. The method according to claim 1, wherein The reaction time for preparing the non-isocyanate compound NIPU is 2 to 24 h; the reaction time for preparing the alkoxysilane liquid containing an antibacterial functional group is 1 to 5 h; the reaction time for preparing the non-isocyanate hyperbranched organosilicon mercapto prepolymer containing an antibacterial functional group is 2 to 8 h at 80 to 140 °C and 0.5 to 4 h at 120 to 160 °C; the reaction time for preparing the hyperbranched secondary amine prepolymer containing an acrylate group is 2 to 12 h.

8. The method according to claim 1, characterized in that, The UV curing time is 30 to 180 s.

9. A UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material prepared by the method according to any one of claims 1-8.

10. Use of the UV-cured organosilicon-modified non-isocyanate polyurethane antibacterial material according to claim 9 in the preparation of antibacterial textiles, anti-corrosion and anti-mildew coatings, food packaging or medical devices.

Images