CN114836043A - Preparation method of UV-cured transparent antibacterial organosilicon material and product thereof - Google Patents
Preparation method of UV-cured transparent antibacterial organosilicon material and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a UV-cured transparent antibacterial organosilicon material and a product thereof, and particularly relates to a preparation method of a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and a polyurethane-acrylate UV-cured prepolymer based on castor oil, which are uniformly mixed with a photoinitiator, and are subjected to vacuum defoaming and UV curing to obtain the UV-cured transparent organosilicon material with sterilization and bacteriostasis. The UV curing material has high light transmittance, good thermal stability, better mechanical property and bonding force to a base material, has good inhibiting effect on fungi and bacteria, can be used for anticorrosive and mildewproof coatings, protective layers of electronic components, medical equipment, food packages, textiles and marine ships, and is particularly suitable for packaging and protecting optical electronic devices needing antibiosis and mildewproof.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and relates to a preparation method of a UV-cured transparent antibacterial organic silicon material and a product thereof.
Background
Fungi and bacteria are microorganisms which people often contact in daily life, and the propagation of the fungi and the bacteria in normal life of people not only harms the health of people, but also seriously damages some medical materials. For example: the fields of medical equipment, food packaging, textiles, marine vessels, etc. are facing pollution by harmful fungi and bacteria. In recent years, materials having antibacterial activity have been developed to reduce the harm caused by fungi and bacteria. Compared with the conventional physical and chemical disinfection method, the method has the advantages of long time effect, economy, convenience and the like when the antibacterial material is used for antibiosis. The anti-bacterial material is used on the frequently touched parts of many public places, such as telephones, elevator buttons, computer keyboards and various electrical switches, so that the pollution source and the propagation source can be effectively isolated. The use of the antibacterial material on the household articles is beneficial to improving the living environment and improving the sanitary quality.
The small molecular organic antibacterial agents such as quaternary ammonium salt, alcohols, phenols, organic metal and the like have mature processing technology and excellent sterilization effect, but have higher toxicity and poorer thermal stability, are easy to cause the drug resistance of microorganisms and have shorter service life. The micromolecule organic antibacterial agent or the metal antibacterial agent is added into the high molecular material, and the prepared addition type high molecular antibacterial material has the defects of high toxicity, easy generation of drug resistance of microorganisms and the like because the micromolecule organic antibacterial agent or the metal antibacterial agent can migrate to the surface of the material [ ACS appl.Mater,2016,8, 21640-; J.Reinf.Plast.Comp.,2020,39(3-4):95-110 ]. The structural type high molecular antibacterial material is prepared by combining a precursor with antibacterial groups into a target polymer in a covalent bond mode, overcomes the defect of high toxicity of a small molecular antibacterial agent and an additive type high molecular antibacterial material, and has the advantages of easiness in processing, stable performance, good sterilization effect and the like [ Macromol.biosci.,2020,20:1900301 ].
The Ultraviolet (UV) curing technology has the advantages of high curing speed, simple processing technology, low energy consumption and no pollution, and is widely applied to the fields of paint, printing ink, electronic packaging and the like of furniture and industrial products. In recent years, with the enhancement of environmental protection awareness, research and development of UV curable antibacterial polymer materials have attracted much attention.
The Chinese patent application CN202110532968.9 reports a UV curing adhesive and a preparation method thereof, wherein oligomer and epoxy resin are added into a reaction vessel according to a ratio and stirred and heated, then polyol, a coupling agent and a dispersing agent are added, and then a bactericide and a photoinitiator are added to obtain the UV curing adhesive. Chinese patent application CN201811359638.9 discloses a high wear resistant aqueous UV floor paint and a method for preparing the same, wherein the UV floor paint is prepared by adding in-can bactericide to an aqueous UV polyurethane dispersion. Chinese patent application CN201710716119.2 adds flax cellulose to UV-curing aqueous polyurethane acrylate, and reports that UV-curing aqueous polyurethane with sterilization, ventilation and flame retardance is obtained. However, the UV curable antibacterial material is an additive type polymer material. Recently, the chinese patent application CN202011001135.1 discloses a method for synthesizing UV-cured bactericidal antistatic resin material and its application, specifically, tetranitro zinc phthalocyanine is synthesized by inert solvent method, and tetranitro zinc phthalocyanine is reduced to tetraamino zinc phthalocyanine by sodium sulfide nonahydrate, and unsaturated double bond is grafted on tetraamino zinc phthalocyanine at the same time, which is applied to UV light curing, but the preparation process is complicated, and the product of grafting unsaturated double bond on tetraamino zinc phthalocyanine has poor solubility. Chinese patent ZL202110800922.0 discloses a UV curable hardening resin with an antibacterial function and a synthesis method thereof, and specifically an antibacterial material is obtained by compounding terminal triacryloyloxy pentaerythritol metal phthalocyanine ester, urethane acrylate, a photoinitiator, MIBK, MEK, a leveling agent, a slipping agent and an AF surface oil stain prevention auxiliary agent and then carrying out UV curing. Although the patent reports that coatings made of the UV-cured sterilization, anti-static and anti-fingerprint resin material have fast and super-strong sterilization capability and anti-static capability, are permanent and have good wear resistance, the UV-cured material has a solvent which is not environment-friendly, and also has added slipping agent and AF surface anti-oil stain auxiliary agent, and the environment-friendly property of the UV-cured material needs to be improved.
In order to overcome the defects of the UV curing antibacterial material and exert the advantages of a UV curing technology, the invention discloses a preparation method of a UV curing transparent antibacterial organosilicon material, which comprises the steps of firstly preparing a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and a polyurethane-acrylate UV curing prepolymer based on castor oil, uniformly mixing the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl with a photoinitiator, defoaming in vacuum, and carrying out UV curing to obtain the UV curing transparent organosilicon material with sterilization and bacteriostasis, wherein the light transmittance of the UV curing transparent organosilicon material is 80-96% (the light wavelength range is 400-800 nm, the sample thickness is 10mm), the hardness is 6B-5H, the water absorption is 0.7-2.0%, the initial thermal decomposition temperature (thermal weight loss is 5%) is 162-184 ℃, the tensile strength is 0.6-12 MPa, the elongation at break is 45-130%, and the bonding force with a substrate is 4-1 grade. The UV curing material has high light transmittance, good thermal stability, better mechanical property and bonding force to a base material, has good inhibiting effect on fungi and bacteria, can be used for anticorrosive and mildewproof coatings, protective layers of electronic components, medical equipment, food packages, textiles and marine ships, and is particularly suitable for packaging and protecting optical electronic devices needing antibiosis and mildewproof.
Disclosure of Invention
The invention aims to provide a preparation method of a UV-cured transparent antibacterial organosilicon material aiming at the defects of the prior art.
In the invention, the preparation method of the UV-cured transparent antibacterial organosilicon material comprises the following steps:
step (1): reacting salicylaldehyde derivatives with aminopropyl alkoxy silane in absolute ethyl alcohol at the temperature of 60-78 ℃ for 1-6 h, and removing a solvent and unreacted raw materials under reduced pressure at the temperature of 78 ℃/130mmHg to obtain Schiff base modified alkoxy silane; reacting Schiff base modified alkoxy silane, mercaptopropyl alkoxy silane and a small molecular compound containing two hydroxyl groups for 2-12 h at 100-160 ℃ under the catalysis of p-toluenesulfonic acid, and removing unreacted raw materials under reduced pressure at 100 ℃/130mmHg to obtain a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
preferably, the p-toluenesulfonic acid is 0.5-2% of the total mass of the Schiff base modified alkoxysilane, the mercaptopropyl alkoxysilane and the small molecular compound containing two hydroxyl groups;
preferably, the amount of the absolute ethyl alcohol is 50-200% of the total mass of the salicylaldehyde derivative and the aminopropylalkoxysilane, and more preferably 100-150%.
Preferably, the salicylaldehyde derivative is one or a mixture of more of salicylaldehyde, 5-bromosalicylaldehyde, 3-nitro salicylaldehyde and 3, 5-di-tert-butyl salicylaldehyde.
Preferably, the aminopropyl alkoxysilane is one or a mixture of two of gamma-aminopropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the mercaptopropylalkoxysilane is one or a mixture of several of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
Preferably, the small molecular compound containing two hydroxyl groups is one or a mixture of more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and neopentyl glycol, and the amount of the small molecular compound is 1.1-2.0 times of the total mole number of the Schiff base modified alkoxy silane and the mercaptopropyl alkoxy silane.
Preferably, the salicylaldehyde derivative and the aminopropylalkoxysilane are used in a molar ratio of 1:1 of aldehyde group to amino group.
Preferably, the amount of the Schiff base modified alkoxysilane to the mercaptopropylalkoxysilane is 5:95 to 80:20 in molar ratio.
Step (2): reacting castor oil, trimethylolpropane and isophorone diisocyanate under the catalysis of dibutyltin dilaurate to obtain hyperbranched polyurethane based on castor oil; reacting castor oil-based hyperbranched polyurethane with hydroxypropyl methacrylate to obtain castor oil-based polyurethane-acrylate UV-cured prepolymer;
preferably, the mass ratio of castor oil, trimethylolpropane and isophorone diisocyanate is 62.2: 0.134: 44.4;
preferably, the mass ratio of dibutyltin dilaurate to castor oil is 0.4269: 62.2;
preferably, the mass ratio of hydroxypropyl methacrylate to castor oil is 26.0: 62.2;
preferably, the reaction temperature of the hyperbranched polyurethane reaction system based on the castor oil is 80 ℃, and the reaction time is 3 hours; the reaction temperature of a polyurethane-acrylate UV curing prepolymer reaction system based on castor oil is 80 ℃, and the reaction time is 3 hours;
and (3): and uniformly mixing the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl with the polyurethane-acrylate UV curing prepolymer based on castor oil and a photoinitiator, defoaming in vacuum for 10-30 min, and carrying out UV curing for 10-180 s to obtain the antibacterial UV curing transparent organosilicon material.
Preferably, the initiator is Irgacure-1173.
Preferably, the using amount of the initiator is 0.5-8% of the total mass of the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil; more preferably 1 to 5%.
Preferably, the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil are used according to the molar ratio of mercapto to acrylate of 1: 2-1: 3.
It is another object of the present invention to provide a UV-curable transparent antibacterial silicone material. The UV-cured transparent antibacterial organosilicon material has the light transmittance of 80-96% (the light wavelength range is 400-800 nm, the sample thickness is 10mm), the hardness is 6B-5H, the water absorption is 0.7-2.0%, the initial thermal decomposition temperature (the thermal weight loss is 5%) is 162-184 ℃, the tensile strength is 0.6-12 MPa, the elongation at break is 45-130%, and the bonding force with a base material is 4-1 grade.
The invention also aims to provide application of the UV-cured transparent antibacterial organic silicon material as an antiseptic and mildew-proof coating on protective layers of electronic components, medical equipment, food packaging, textiles and marine ships, and is particularly suitable for packaging and protecting optical electronic devices needing antibiosis and mildew prevention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the UV-cured transparent antibacterial organosilicon material is a solvent-free structural UV-cured macromolecular antibacterial material, has low toxicity, has the hardness of 6B-5H, the water absorption of 0.7-2.0 percent, the initial thermal decomposition temperature (thermal weight loss of 5 percent) of 162-184 ℃, the tensile strength of 0.6-12 MPa, the elongation at break of 45-130 percent and the bonding force with a base material of 4-1 grade, and is easy to process and mold.
(2) The UV-cured transparent antibacterial organosilicon material has the light transmittance of 80-96% (the light wavelength range is 400-800 nm, the sample thickness is 10mm), can be used for anticorrosive and mildew-proof coatings and protective layers of electronic components, medical equipment, food packages, textiles and marine ships, and is particularly suitable for packaging and protecting optical electronic devices needing antibiosis and mildew prevention.
Drawings
FIG. 1-1 and FIG. 1-2 are organic silicon compounds containing Schiff base and mercaptopropyl and obtained by reacting salicylaldehyde with gamma-aminopropyltrimethoxysilane and then reacting with neopentyl glycol 1 H-NMR and 13 a C-NMR spectrum;
FIG. 2 is a graph showing the comparison of the antibacterial effect of cured products with different molar ratios of mercapto groups to acrylate groups;
FIG. 3 is a graph showing the antibacterial effect of the cured products obtained by UV curing for 90s and 120 s;
FIG. 4 is a graph showing the antibacterial effect of the cured product of example 3;
FIG. 5 is a graph showing the antibacterial effect of the cured product of example 4.
Detailed Description
As described above, in view of the deficiencies of the prior art, the present inventors have made extensive studies and extensive practices, and propose a technical solution of the present invention, which is mainly based on at least:
(1) schiff base groups are introduced into the UV-cured organic silicon high polymer material to obtain the UV-cured transparent antibacterial organic silicon material, and the Schiff base groups cannot migrate due to the fact that the Schiff base groups are on a large molecular chain of a cured substance, so that the defect that small-molecular organic antibacterial agents and additive high-molecular antibacterial materials are high in toxicity is overcome.
(2) The organic silicon chain segment is introduced into the UV curing polymer material, so that the thermal stability of the material is improved, and the defect of poor thermal stability of the traditional micromolecule organic antibacterial agent is overcome.
(3) The castor oil is used as a raw material to prepare the UV-cured transparent antibacterial organosilicon material, the raw material is rich, and the mechanical property of the UV-cured material can be improved.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
According to the invention, the obtained UV-cured transparent antibacterial organosilicon material has the light transmittance of 80-96% (light wavelength range of 400-800 nm, sample thickness of 10mm), the hardness of 6B-5H, the water absorption of 0.7-2.0%, the initial thermal decomposition temperature (thermal weight loss of 5%) of 162-184 ℃, the tensile strength of 0.6-12 MPa, the elongation at break of 45-130% and the bonding force with a base material of 4-1 level. The UV curing material has high light transmittance and good thermal stabilityThe coating has good mechanical property and adhesive force to a base material, has good inhibiting effect on fungi and bacteria, can be used for anticorrosive and mildewproof coatings, and protective layers of electronic components, medical equipment, food packages, textiles and marine ships, and is particularly suitable for packaging and protecting optical electronic devices needing antibiosis and mildewproof. FIG. 1-1 and FIG. 1-2 are the Schiff base and mercaptopropyl-containing organosilicon compounds obtained by reacting salicylaldehyde with gamma-aminopropyltrimethoxysilane and then reacting with neopentyl glycol 1 H-NMR and 13 C-NMR spectrum.
The preparation method of the UV-cured transparent antibacterial organosilicon material comprises the following steps:
step (1): reacting salicylaldehyde derivatives with aminopropyl alkoxy silane in absolute ethyl alcohol at the temperature of 60-78 ℃ for 1-6 h, and removing a solvent and unreacted raw materials under reduced pressure at the temperature of 78 ℃/130mmHg to obtain Schiff base modified alkoxy silane; reacting Schiff base modified alkoxy silane, mercaptopropyl alkoxy silane and a small molecular compound containing two hydroxyl groups for 2-12 h at 100-160 ℃ under the catalysis of p-toluenesulfonic acid, and removing unreacted raw materials under reduced pressure at 100 ℃/130mmHg to obtain a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
preferably, the p-toluenesulfonic acid is 0.5-2% of the total mass of the Schiff base modified alkoxysilane, the mercaptopropyl alkoxysilane and the small molecular compound containing two hydroxyl groups;
preferably, the amount of the absolute ethyl alcohol is 50-200% of the total mass of the salicylaldehyde derivative and the aminopropylalkoxysilane, and more preferably 100-150%.
Preferably, the salicylaldehyde derivative is one or a mixture of more of salicylaldehyde, 5-bromosalicylaldehyde, 3-nitro salicylaldehyde and 3, 5-di-tert-butyl salicylaldehyde.
Preferably, the aminopropyl alkoxysilane is one or a mixture of two of gamma-aminopropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the mercaptopropylalkoxysilane is one or a mixture of several of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
Preferably, the small molecular compound containing two hydroxyl groups is one or a mixture of more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and neopentyl glycol, and the amount of the small molecular compound is 1.1-2.0 times of the total mole number of the Schiff base modified alkoxy silane and the mercaptopropyl alkoxy silane.
Preferably, the salicylaldehyde derivative and the aminopropylalkoxysilane are used in a molar ratio of 1:1 of aldehyde group to amino group.
Preferably, the amount of the Schiff base modified alkoxysilane to the mercaptopropylalkoxysilane is 5:95 to 80:20 in molar ratio.
Step (2): reacting castor oil, trimethylolpropane and isophorone diisocyanate under the catalysis of dibutyltin dilaurate to obtain hyperbranched polyurethane based on castor oil; reacting castor oil-based hyperbranched polyurethane with hydroxypropyl methacrylate to obtain castor oil-based polyurethane-acrylate UV-cured prepolymer;
preferably, the mass ratio of castor oil, trimethylolpropane and isophorone diisocyanate is 62.2: 0.134: 44.4;
preferably, the mass ratio of dibutyltin dilaurate to castor oil is 0.4269: 62.2;
preferably, the mass ratio of hydroxypropyl methacrylate to castor oil is 26.0: 62.2;
preferably, the reaction temperature of the hyperbranched polyurethane reaction system based on the castor oil is 80 ℃, and the reaction time is 3 hours; the reaction temperature of a polyurethane-acrylate UV curing prepolymer reaction system based on castor oil is 80 ℃, and the reaction time is 3 hours;
and (3): and uniformly mixing the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl with the polyurethane-acrylate UV curing prepolymer based on castor oil and a photoinitiator, defoaming in vacuum for 10-30 min, and carrying out UV curing for 10-180 s to obtain the antibacterial UV curing transparent organosilicon material.
Preferably, the initiator is Irgacure-1173.
Preferably, the using amount of the initiator is 0.5-8% of the total mass of the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil; more preferably 1 to 5%.
Preferably, the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil are used according to the molar ratio of mercapto to acrylate of 1: 2-1: 3.
The technical solutions of the present invention are further explained below with reference to some preferred embodiments, but the experimental conditions and the setting parameters should not be construed as limitations of the basic technical solutions of the present invention. And the scope of the present invention is not limited to the following examples.
In the present invention, the analytical test method is as follows:
nuclear magnetic resonance: deuterated chloroform (CDCl) 3 ) As solvent, hydrogen spectra were determined at room temperature using a Brucker Advance-400NMR Nuclear magnetic resonance apparatus (Brucker, Germany) ((R)) 1 H-NMR)。
Fourier transform infrared spectroscopy: 4000- -1 Infrared spectroscopy, liquid samples by coating method, solid samples by tabletting method.
Gelation rate: the cured product is extracted by a Soxhlet extraction method for 4 hours at 150 ℃ by toluene, and the residual quantity is expressed by the percentage of the original mass of the cured product.
Adhesion force: the BGD-502 paint film according to ISO2409-2007 standard is tested for adhesion by a cross-cut method.
And (3) testing light transmittance: an Evolution 300 type ultraviolet-visible spectrophotometer of Thermo Fisher corporation in America tests the light transmittance of the polymer, the test wavelength range is 300-800 nm, and the sample thickness is 10 mm.
Tensile strength test: the experimental equipment is a microcomputer-controlled electronic tension and compression cycle reciprocating tester UH6503D produced by Youhong measurement and control technology (Shanghai) Limited, the tensile speed is 2mm/min, each film is measured for 3 times, and the average value is obtained.
Pencil hardness: the measurement is carried out according to GB/T6739-2006 paint film hardness measurement by a colored paint and varnish pencil method.
Water absorption: cutting the coating into square blocks with certain shapes, soaking in deionized water for 24h at room temperature, sucking water on the surface of the coating by using filter paper, and calculating the water absorption of the coating according to the formula:
wherein B represents water absorption (%); m is 1 Represents the quality of the coating film before soaking; m is 2 The mass of the coating film after soaking was measured by blotting the liquid on the surface of the coating film with filter paper.
The experiment on the inhibition effect of the UV curing material on bacteria and fungi comprises the following steps:
test fungi: neurospora crassa (Neurospora crassa)
Test bacteria: escherichia coli (Escherichia coli)
Test medium
PDA (potato agar glucose medium): 200g of potato, 15g of agar and 20g of glucose, adding pure water to a constant volume of 1000mL, and carrying out high-pressure moist heat sterilization at 121 ℃ for 25 min. The culture medium is used for fungus culture, and agar is omitted in liquid culture.
LB (Luria-Bertani) medium: 10g of tryptone, 5g of yeast extract, 10g of NaCl and 15g of agar, adding pure water to a constant volume of 1000mL, and carrying out high-pressure moist heat sterilization at 121 ℃ for 25 min. For bacterial culture, agar is omitted in liquid culture.
Experimental methods
Bacterial/fungal strain activation: the bacteria/fungus strain is stored, streaked and cultured for 2 times on corresponding solid culture medium, the activated strain is added into 50mL corresponding liquid culture medium, a shaking table is set at 37/28 ℃ and 180r/min, and the strain is continuously cultured on the shaking table for 24h to prepare strain suspension.
Sucking 5 μ L of the prepared bacterial suspension, dripping on the surface of the UV cured coating, setting a blank control group, air drying, sealing, placing in a constant-temperature incubator at 37/28 deg.C, culturing in dark for 1-5d, and observing the size and shape of bacterial plaque.
Example 1
(1) 122.12g of salicylaldehyde and 179.29g of gamma-aminopropyltrimethoxysilane are reacted in 78 ℃ and 301g of absolute ethyl alcohol for 2 hours, the solvent and unreacted raw materials are removed under reduced pressure at 78 ℃/130mmHg to obtain 301.41g of Schiff base modified alkoxysilane, then the alkoxysilane, 458.127g of mercaptopropyl trimethoxysilane and 310.350g of ethylene glycol are reacted for 2 hours at 160 ℃ under the catalysis of 21.397g of p-toluenesulfonic acid, and unreacted raw materials are removed under reduced pressure at 100 ℃/130mmHg to obtain 589.887g of hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
(2) 62.2g of castor oil, 0.134g of trimethylolpropane and 44.4g of isophorone diisocyanate were reacted at 80 ℃ for 3h under the catalysis of 0.4269g of dibutyltin dilaurate, and the obtained product was reacted with 26.0g of hydroxypropyl methacrylate at 80 ℃ for 3h to obtain 132.734g of a castor oil-based urethane-acrylate UV-curable prepolymer;
(3) the obtained hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl, a polyurethane-acrylate UV curing prepolymer based on castor oil and a photoinitiator Irgacure-1173 are uniformly mixed, vacuum defoamed for 10-30 min, and subjected to UV curing for 90s to obtain the antibacterial UV cured transparent organosilicon material, wherein the comprehensive performance and the bactericidal performance of the antibacterial UV cured transparent organosilicon material are shown in Table 1 and figure 2, and the antibacterial UV cured material has high light transmittance, excellent mechanical properties, good thermal stability and good antibacterial effect.
TABLE 1 influence of molar ratio of different mercapto groups in hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl groups to acrylate groups in polyurethane-acrylate UV curing prepolymer based on castor oil on the properties of cured products
The addition amount of the Irgacure-1173 is 5 percent of the total mass of the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil, and the curing time is 90 s.
Example 2
(1) 20.1027g of 5-bromosalicylaldehyde and 22.137g of gamma-aminopropyltriethoxysilane are reacted in 21.12g of absolute ethanol at 78 ℃ for 2h, then the solvent and unreacted raw materials are removed under reduced pressure at 78 ℃/130mmHg to obtain 42.239g of Schiff base modified alkoxysilane, then the alkoxysilane, 420.603g of mercaptopropyltriethoxysilane and 228.30g of 1, 3-propylene glycol are reacted for 12h at 100 ℃ under the catalysis of 6.911g of p-toluenesulfonic acid, and the unreacted raw materials are removed under reduced pressure at 100 ℃/130mmHg to obtain 186.842g of hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
(2) the obtained hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl is uniformly mixed with the polyurethane-acrylate UV curing prepolymer based on castor oil and the photoinitiator Irgacure-1173 obtained in the embodiment 1, vacuum defoamation is carried out for 10-30 min, and then UV curing is carried out to obtain the antibacterial UV curing transparent organosilicon material, wherein the comprehensive performance and the sterilization performance of the antibacterial UV curing transparent organosilicon material are shown in the table 2 and the figure 3, which shows that when the UV curing time is 90-180 s, the obtained UV curing material has good mechanical property and thermal stability and has a good antibacterial effect.
TABLE 2 Effect of different UV curing times on the Properties of the cured products
The addition amount of the Irgacure-1173 is 1 percent of the total mass of the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on the castor oil, and the molar ratio of different sulfydryl in the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl to the acrylate group in the polyurethane-acrylate UV curing prepolymer based on the castor oil is 1: 2.5.
Example 3
(1) 167.119g of 3-nitro salicylaldehyde and 179.29g of gamma-aminopropyl trimethoxysilane are reacted in 692.8g of anhydrous ethanol at 78 ℃ for 2h, the solvent and unreacted raw materials are removed under reduced pressure at 78 ℃/130mmHg to obtain 346.409g of Schiff base modified alkoxysilane, then the alkoxysilane, 49.085g of mercaptopropyl trimethyl alkoxysilane and 168.975g of 1, 4-butanediol are reacted at 160 ℃ for 8h under the catalysis of 2.822g of p-toluenesulfonic acid, and the unreacted raw materials are removed under reduced pressure at 100 ℃/130mmHg to obtain 496.969g of hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
(2) the obtained hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil obtained in the embodiment 1 are uniformly mixed with 8 wt% of photoinitiator Irgacure-1173 according to the molar ratio of 1:2.5, and are subjected to vacuum defoaming for 10-30 min, and then the antibacterial UV curing transparent organosilicon material is obtained after UV curing for 90s, wherein the gelation rate of the antibacterial UV curing transparent organosilicon material is 92.5%, the water absorption rate of the antibacterial UV curing transparent organosilicon material is 1.2%, the pencil hardness is 5H, the light transmittance is 99.5%, the tensile strength is 15.0MPa, the elongation at break is 160%, the initial thermal decomposition temperature is 178.5 ℃, the adhesion force with a glass slide can reach level 1, and the antibacterial effect is shown in figure 4.
Example 4
(1) 234.33g of 3, 5-di-tert-butyl salicylaldehyde and 179.29g of gamma-aminopropyl trimethoxy silane are reacted in 620g of absolute ethyl alcohol at 78 ℃ for 6h, the solvent and unreacted raw materials are removed under reduced pressure at 78 ℃/130mmHg to obtain 413.62g of Schiff base modified alkoxy silane, then the alkoxy silane is reacted with 49.085g of mercaptopropyl trimethyl alkoxy silane and 195.281g of neopentyl glycol at 140 ℃ under the catalysis of 6.580g of p-toluenesulfonic acid for 5h, and the unreacted raw materials are removed under reduced pressure at 100 ℃/130mmHg to obtain 575.151g of hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
(2) the obtained hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil obtained in the embodiment 1 are uniformly mixed with 6 wt% of photoinitiator Irgacure-1173 according to the molar ratio of 1:2.5, and after vacuum deaeration is carried out for 10-30 min, the antibacterial UV curing transparent organosilicon material is obtained after UV curing for 90s, wherein the gelation rate is 92.0%, the water absorption rate is 0.8%, the pencil hardness is 5H, the light transmittance is 99.5%, the tensile strength is 16.5MPa, the elongation at break is 180%, the initial thermal decomposition temperature is 182.5 ℃, the adhesion force with a glass slide can reach level 1, and the antibacterial effect is shown in figure 5.
Claims (10)
1. A preparation method of a UV-cured transparent antibacterial organosilicon material is characterized by comprising the following steps:
reacting a salicylaldehyde derivative with aminopropyl alkoxy silane in absolute ethyl alcohol at the temperature of 60-78 ℃ for 1-6 h, and removing a solvent and unreacted raw materials under reduced pressure to obtain Schiff base modified alkoxy silane; reacting Schiff base modified alkoxy silane, mercaptopropyl alkoxy silane and a small molecular compound containing two hydroxyl groups for 2-12 h at 100-160 ℃ under the catalysis of p-toluenesulfonic acid, and removing unreacted raw materials under reduced pressure to obtain a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl;
reacting castor oil, trimethylolpropane and isophorone diisocyanate under the catalysis of dibutyltin dilaurate to obtain hyperbranched polyurethane based on castor oil; reacting castor oil-based hyperbranched polyurethane with hydroxypropyl methacrylate to obtain castor oil-based polyurethane-acrylate UV-cured prepolymer;
uniformly mixing a hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl with a polyurethane-acrylate UV curing prepolymer based on castor oil and a photoinitiator, defoaming for 10-30 min in vacuum, and curing for 10-180 s by UV to obtain an antibacterial UV curing transparent organosilicon material; the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV curing prepolymer based on castor oil are used according to the molar ratio of mercapto to acrylate of 1: 2-1: 3.
2. The method for preparing a UV-curable transparent antibacterial silicone material according to claim 1, wherein the salicylaldehyde derivative in the step (1) is one or a mixture of salicylaldehyde, 5-bromosalicylaldehyde, 3-nitrosalicylaldehyde, and 3, 5-di-tert-butylsalicylaldehyde.
3. The method for preparing a UV-curable transparent antibacterial silicone material according to claim 1, wherein the aminopropylalkoxysilane in step (1) is one or a mixture of two of γ -aminopropyltrimethoxysilane and γ -aminopropyltriethoxysilane.
4. The method for preparing a UV-curable transparent antibacterial silicone material according to claim 1, wherein the mercaptopropylalkoxysilane in step (1) is one or a mixture of mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
5. The method of claim 1, wherein the small molecular compound containing two hydroxyl groups in step (1) is one or more selected from ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, and neopentyl glycol, and the amount of the small molecular compound is 1.1-2.0 times of the total molar amount of the schiff base-modified alkoxysilane and the mercaptopropyl-alkoxysilane.
6. The method for preparing a UV-curable transparent antibacterial silicone material according to claim 1, wherein the salicylaldehyde derivative and aminopropylalkoxysilane in the step (1) are used in a molar ratio of aldehyde group to amino group of 1: 1.
7. The method for preparing a UV-curable transparent antibacterial organosilicon material according to claim 1, wherein the amount of the Schiff base modified alkoxysilane and the mercaptopropyl alkoxysilane in the step (1) is 5:95 to 80:20 by mole ratio.
8. The method for preparing a UV-curable transparent antibacterial silicone material according to claim 1, wherein the amount of the initiator used in the step (3) is 0.5-8% of the total mass of the hyperbranched silicon-containing polymer containing Schiff base and mercaptopropyl and the polyurethane-acrylate UV-curable prepolymer based on castor oil.
9. A UV-cured transparent antimicrobial silicone material prepared by the method of any one of claims 1 to 8; the UV-cured transparent antibacterial organosilicon material is characterized by having the light transmittance of 80-96%, the hardness of 6B-5H, the water absorption of 0.7-2.0%, the initial thermal decomposition temperature of 162-184 ℃, the tensile strength of 0.6-12 MPa, the elongation at break of 45-130% and the bonding force with a base material of 4-1 level.
10. The use of a UV-curable transparent antibacterial organosilicon material prepared by the method of any one of claims 1 to 8 as an anticorrosive and mildewproof coating for electronic components, medical equipment, food packaging, textiles and protective coatings of marine vessels.
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