CN113913046B - Bio-based antibacterial ultraviolet fluorescent paint and preparation method thereof - Google Patents

Abstract

The invention relates to an ultraviolet fluorescent paint, in particular to a bio-based antibacterial ultraviolet fluorescent paint and a preparation method thereof, belonging to the technical field of biomaterial synthesis. The bio-based antibacterial ultraviolet fluorescent paint is prepared by performing a cross-linking reaction on a prepolymer and a polythiol compound under the action of a catalyst 1,1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] (Irgacure 127). Wherein the prepolymer is a linear polymer obtained by polymerizing 5', 5-diallyl-2, 2' -biphenol and 1, 6-hexanedithiol under the action of an Azodiisobutyronitrile (AIBN) catalyst. The 5', 5-diallyl-2, 2' -biphenol in the invention is derived from bio-based compounds of arbors of Magnoliaceae deciduous, and the bio-based ultraviolet fluorescent paint has the characteristics of antibiosis, environmental protection, renewable and biodegradable raw materials, simple process, wide raw material source and the like; and the risk of generating toxicity to human bodies is avoided, and the application of the ultraviolet fluorescent paint is greatly widened.

Description

Bio-based antibacterial ultraviolet fluorescent paint and preparation method thereof

Technical Field

The invention relates to an ultraviolet fluorescent paint, in particular to a bio-based antibacterial ultraviolet fluorescent paint and a preparation method thereof, belonging to the biomaterial synthesis technology.

Background

With the improvement of living standard and the endless emergence of new materials, the demands of people and working environment have new requirements on printing. The fluorescent printing plays an increasingly important role in military police identification, anti-counterfeiting technology and stage performance clothes. At present, fluorescent printing is mostly composed of multiple additives such as fluorescent paint, adhesive, cross-linking agent, thickening agent and the like; among them, fluorescent paint is used to exhibit a fluorescent function, and fluorescent paint is paint that can emit light when irradiated with ultraviolet rays.

Most of fluorescent coatings on the market are inorganic fluorescent coatings, which are various and comprise crystals such as metal oxides and sulfides, and activators such as rare earths or metals; it has good durability and wide application range. However, the inorganic fluorescent pigment has higher density and is easy to precipitate, so a large amount of diluent is needed during use, and the product quality is greatly influenced by dilution and dispersion degree; in addition, the inorganic fluorescent paint must use organic resin as the film-forming binder of paint particles, and the organic resin uses a large amount of organic solvent in the production and construction processes, which brings great harm to human body.

Chinese patent publication No.: CN201510310149.4, published: 2015-09-23, the invention discloses an antibacterial fluorescent ultraviolet curing water-based paint, wherein the adhesive comprises acrylate, fluorescent powder, a nano-silver antibacterial agent, nano-titanium dioxide, graphene and the like. Although the antibacterial agent has a good antibacterial effect, the raw material composition and the preparation process are complex, the production cost is high, and the nano silver ions have certain hidden danger to human health.

Disclosure of Invention

Aiming at the existing problems, the invention aims to provide a bio-based antibacterial ultraviolet fluorescent paint, so as to overcome the defect that the traditional inorganic fluorescent material causes harm to human health, and prepare the bio-based ultraviolet fluorescent paint with characteristics of antibacterium, greenness, environmental friendliness and renewable raw materials.

In order to realize the aim, the invention provides a bio-based antibacterial ultraviolet fluorescent paint and a preparation method thereof.

The bio-based antibacterial ultraviolet fluorescent paint comprises, by mass, 80-90 parts of a prepolymer, 10-20 parts of a polythiol compound and 1-5 parts of a catalyst a.

The molecular chain of the prepolymer contains biphenyl diphenol and thioether structures, and both ends of the molecular chain have alkylene functional groups, wherein the prepolymer is a linear polymer obtained by polymerizing 5', 5-diallyl-2, 2' -biphenyl diphenol and 1, 6-hexanedithiol under the action of a catalyst b, and the catalyst b is Azobisisobutyronitrile (AIBN).

The multi-mercapto compound is trimethylolpropane tri (3-mercaptopropionic acid) ester.

The catalyst a is 1,1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] (Irgacure 127).

A preparation method of a bio-based antibacterial ultraviolet fluorescent paint comprises the following steps:

s1, dissolving 5', 5-diallyl-2, 2' -biphenol and 1, 6-hexanedithiol in an organic solvent at the stirring speed of 200-400r/min at room temperature to obtain a mixed solution.

Wherein the mass part ratio of the 5', 5-diallyl-2, 2' -biphenol to the 1, 6-hexanedithiol is 65-80: 20-35, wherein the mass part ratio of the solute to the solvent is 10-20: 80-90.

The organic solvent is one of toluene, acetone, DMSO and DMF.

S2, adding a catalyst b into the mixed solution obtained in the step S1, wherein the mass part ratio of the catalyst b to the solute in the step S1 is 1-5: 100, respectively; and the temperature is raised to 60-100 ℃ to react for 4-6 at the stirring speed of 600-800 r/min.

S3, adding the product solution obtained after the reaction in the step S2 into a cyclohexane solution, stirring at the speed of 500-1000 r/min for 20min, and then standing, wherein the mass part ratio of the product solution to the cyclohexane solution is 5-10: 90-95.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and trimethylolpropane tri (3-mercaptopropionic acid) ester at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionic acid) ester to obtain a mixed substance, wherein the mass part ratio of the prepolymer to the trimethylolpropane tri (3-mercaptopropionic acid) ester is 80-90: 10-20.

S6, adding the catalyst a into the mixed substance obtained in the step S5, and stirring until the catalyst a is completely dissolved to obtain a mixed solution, wherein the ratio of the catalyst a to the mixed substance is (1-5): 100.

s7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Due to the adoption of the technical scheme, the technical scheme of the invention has the following technical effects:

1. the synthesis of the prepolymer utilizes the mercaptan-alkene addition reaction, and has the characteristics of high efficiency, rapidness and insensitivity to water and oxygen; the coating is prepared by directly mixing prepolymer, trimethylolpropane tri (3-mercaptopropionic acid) ester and catalyst a, and the preparation method is simple and has short process flow.

2. The 5', 5-diallyl-2, 2' -biphenol used in the bio-based ultraviolet fluorescent paint prepolymer is a bio-based compound of a magnolia deciduous tree plant, has two allyl groups, and is subjected to click addition with a sulfydryl group. The 5', 5-diallyl-2, 2' -biphenol and dimercaptoalcohol compounds are polymerized to generate a linear polymer, and under the condition that the 5', 5-diallyl-2, 2' -biphenol is excessive, two ends of a linear molecular chain are still allyl functional groups, so that the linear molecular chain has the capability of further click-polymerizing with the mercapto functional groups to form the cross-linked network coating. The bio-based ultraviolet fluorescent coating prepolymer is then crosslinked with micromolecules with trithiol or tetramercapto functional groups to form a reticular polymer.

3. Because the conjugated double bonds are ultraviolet-visible light intensity absorption groups, the molecular chain of the linear prepolymer of the bio-based antibacterial ultraviolet fluorescent coating has more conjugated aromatic rings with a biphenyl structure, the biphenyl aromatic ring structure provides a larger conjugated system, and the stronger the delocalization of pi electrons, the stronger the fluorescence generated by excitation; and the groups capable of generating ultraviolet fluorescence are combined together, so that the effect of the ultraviolet fluorescence is enhanced.

4.5', 5-diallyl-2, 2' -biphenol, and has antiinflammatory, antibacterial, and pathogenic microorganism resisting effects. The phenolic hydroxyl structure of the 5', 5-diallyl-2, 2' -biphenol does not participate in the reaction, and the phenolic hydroxyl structure is remained after the polymerization reaction is carried out to form a film, so that the antibacterial capability is remained, and the service life of the material is prolonged due to the antibacterial capability. In addition, phenolic hydroxyl groups on the 5', 5-diallyl-2, 2' -biphenol can form hydrogen bond action with hydroxyl groups on cotton fabrics, carbon fibers, wood, inorganic matters and the like, so that the bonding fastness of the fluorescent paint and a base material is greatly improved.

5, 5', 5-diallyl-2, 2' -biphenol is derived from bio-based compounds of arbors of Magnoliaceae, and fluorescent paint prepared by using the 5', 5-diallyl-2, 2' -biphenol or derivatives thereof has excellent biocompatibility, does not generate toxicity risk of staying a human body for a long time, and greatly widens the application of the bio-based ultraviolet fluorescent paint.

6. The bio-based ultraviolet fluorescent paint prepared from the bio-based ultraviolet fluorescent paint prepolymer has the characteristics of greenness, environmental friendliness, renewable raw materials, biodegradability and the like which are not possessed by the traditional high polymer material, and does not cause damage to human health; in addition, the preparation methods of the bio-based ultraviolet fluorescent paint prepolymer and the fluorescent paint are simple and quick, are easy to operate, have easily available raw materials, and have low cost and the like.

Drawings

FIG. 1 is the NMR spectrum of the prepolymer of bio-based UV fluorescent paint prepared in example 1 of the present invention.

FIG. 2 is a nuclear magnetic resonance spectrum of the prepolymer of bio-based UV fluorescent paint prepared in example 2 of the present invention.

FIG. 3 is a graph of the UV absorption spectrum of the bio-based fluorescent paint prepared in example 1 and example 2 of the present invention after curing.

FIG. 4 is a graph showing the results of measuring the absorbance of the co-cultured bacterial suspension by UV-visible spectrophotometry in examples 1 and 2 of the present invention and in comparative example.

Detailed Description

The invention is further illustrated with reference to the figures and the specific embodiments.

The bio-based antibacterial ultraviolet fluorescent paint comprises, by mass, 80-90 parts of a prepolymer, 10-20 parts of a polythiol compound and 1-5 parts of a catalyst a.

The molecular chain of the prepolymer contains biphenyl diphenol and thioether structures, and both ends of the molecular chain have alkylene functional groups, wherein the prepolymer is a linear polymer obtained by polymerizing 5', 5-diallyl-2, 2' -biphenyl diphenol and 1, 6-hexanedithiol under the action of a catalyst b, and the catalyst b is Azobisisobutyronitrile (AIBN).

The multi-mercapto compound is trimethylolpropane tri (3-mercaptopropionic acid) ester.

The catalyst a is 1,1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] (Irgacure 127).

The prepolymer contains biphenol and thioether structures in molecular chains, and a linear compound with olefin functional groups at two ends of the molecular chains can be obtained under the condition that 5', 5-diallyl-2, 2' -biphenol is excessive during synthesis, and the structural formula is as follows:

wherein n is 10 to 20, and the number average molecular weight of the prepolymer is 4000 to 8000.

The preparation method of the bio-based antibacterial ultraviolet fluorescent paint comprises the following steps:

s1, dissolving 5', 5-diallyl-2, 2' -biphenol and 1, 6-hexanedithiol in an organic solvent at the stirring speed of 200-400r/min at room temperature to obtain a mixed solution.

Wherein the mass part ratio of the 5', 5-diallyl-2, 2' -biphenol to the 1, 6-hexanedithiol is 65-80: 20-35, wherein the mass part ratio of the solute to the solvent is 10-20: 80-90.

The organic solvent is one of toluene, acetone, DMSO and DMF.

S2, adding a catalyst b into the mixed solution obtained in the step S1, wherein the mass part ratio of the catalyst b to the solute in the step S1 is 1-5: 100, respectively; and the temperature is raised to 60-100 ℃ and the reaction is carried out for 4-6h at the stirring speed of 600-800 r/min.

S3, adding the product solution obtained after the reaction in the step S2 into a cyclohexane solution, stirring at the speed of 500-1000 r/min for 20min, and then standing, wherein the mass part ratio of the product solution to the cyclohexane solution is 5-10: 90-95.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

Specifically, the reaction equation for preparing the prepolymer is:

s5, uniformly stirring the prepolymer obtained in the step S4 and trimethylolpropane tri (3-mercaptopropionic acid) ester at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionic acid) ester to obtain a mixed substance, wherein the mass part ratio of the prepolymer to the trimethylolpropane tri (3-mercaptopropionic acid) ester is 80-90: 10-20.

S6, adding the catalyst a into the mixed substance obtained in the step S5, and stirring until the catalyst a is completely dissolved to obtain a mixed solution, wherein the ratio of the catalyst a to the mixed substance is 1-5: 100.

s7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

When the paint is used, a photocuring method is adopted, namely the obtained paint is printed with a preset pattern on a base material through a printing machine or other coating modes, and the ultraviolet fluorescent pattern is obtained by irradiating and curing under a light source with the wavelength of 365 nm.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, 6.5g of 5', 5-diallyl-2, 2' -biphenol and 3.5g of 1, 6-hexanedithiol are dissolved in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 100mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 900g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 1.1g of trimethylolpropane tri (3-mercaptopropionate) at the temperature of 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 100mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

FIG. 1 shows the NMR spectra of the prepolymer of bio-based UV fluorescent paint prepared in example 1: 1H NMR (400MHz, DMSO-d6) δ 9.01(s,5H),6.97(s,9H),6.81(d, J ═ 7.9Hz,6H),2.91(s,2H),2.75(s,2H),2.55(d, J ═ 8.0Hz,26H),2.47(s,10H), 2.31(s,1H),1.76(s,15H),1.25(s,1H),1.09(t, J ═ 7.0Hz, 2H). Wherein the chemical shifts are 2.47 and 2.32

Structure of which is

And

the result after addition reaction.

The bio-based ultraviolet fluorescent paint in the example 1 and a staphylococcus aureus liquid are cultured for 24 hours at the culture temperature of 37 ℃, the absorbance and the bacteriostasis rate of the bio-based ultraviolet fluorescent paint are tested by an ultraviolet-visible spectrophotometry method, wherein the comparative example 1 is a blank control group.

FIG. 3 shows the UV absorption spectra of the bio-based fluorescent coatings obtained in examples 1 and 2 after curing. The test result shows that the absorption of the fluorescent paint prepared in example 1 reaches the peak value when the ultraviolet wavelength is 308nm, and the absorbance is 1.10a.u. Therefore, when the pattern is irradiated by ultraviolet after the biological fluorescent paint is cured, the fluorescent pattern can be displayed, and the pattern can be used in the fields of anti-counterfeiting and the like.

FIG. 4 shows the absorbance of the co-cultured bacterial liquid measured by UV-visible spectrophotometry in examples 1 and 2 and comparative example. Comparative example 1 is that the OD value of ultraviolet absorbance after the pure bacterial solution is cultured for 24 hours at 37 ℃ is 0.725; the OD value of the ultraviolet absorbance of the sample 1 is 0.068, and the bacteriostasis rate is 90.62% compared with the blank control group of the comparative example. The ultraviolet absorbance, OD value, of example 2 is 0.074, and the bacteriostatic rate thereof is 89.79%, which indicates that the bio-based ultraviolet fluorescent paint of the invention has a certain bacteriostatic effect.

Example 2

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 8.0g of 5', 5-diallyl-2, 2' -biphenol and 2.0g of 1, 6-hexanedithiol in 100g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 500mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 100 ℃, and reacting for 4 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1900g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 2.5g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 500mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

FIG. 2 shows the NMR spectra of the prepolymer of bio-based UV fluorescent paint prepared in example 2:

1H NMR (400MHz, DMSO-d6) δ 9.01(s,5H),6.97(s,9H),6.81(d, J ═ 7.9Hz,6H),2.91(s,2H),2.75(s,2H),2.55(d, J ═ 8.0Hz,26H),2.47(s,10H),2.32 (s,1H),1.77(s,15H),1.25(s,1H),1.11(t, J ═ 7.0Hz, 2H). Wherein the chemical shifts are 2.47 and 2.32

Structure of which is

And

the result after addition reaction.

FIG. 3 shows the UV absorption spectra of the bio-based fluorescent coatings obtained in examples 1 and 2 after curing. The test result shows that the absorption of the fluorescent paint prepared in example 2 reaches the peak value when the ultraviolet wavelength is 314nm, and the absorbance is 1.119 a.u.. Therefore, when the pattern is irradiated by ultraviolet after the biological fluorescent paint is cured, the fluorescent pattern can be displayed, and the pattern can be used in the fields of anti-counterfeiting and the like.

The bio-based ultraviolet fluorescent paint in the example 2 and the golden yellow staphylococcus liquid are cultured for 24 hours at the culture temperature of 37 ℃, the absorbance and the bacteriostasis rate of the bio-based ultraviolet fluorescent paint are tested by an ultraviolet-visible spectrophotometry method, wherein the comparative example 1 is a blank control group.

FIG. 4 shows the absorbance of the co-cultured bacteria solution measured by UV-Vis spectrophotometry in examples 1-2 and comparative example 1. Comparative example 1 is that the OD value of ultraviolet absorbance after the pure bacterial solution is cultured for 24 hours at 37 ℃ is 0.725; the ultraviolet absorbance, OD value, of example 2 is 0.074, and the bacteriostatic rate thereof is 89.79%, which indicates that the bio-based ultraviolet fluorescent paint of the invention has a certain bacteriostatic effect.

Example 3

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 7.0g of 5', 5-diallyl-2, 2' -biphenol and 3.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 100mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1200g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 1.1g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 100mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Example 4

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 7.0g of 5', 5-diallyl-2, 2' -biphenol and 3.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 200mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1500g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 1.5g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 300mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Example 5

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 7.0g of 5', 5-diallyl-2, 2' -biphenol and 3.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 500mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1900g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 2.5g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 500mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Example 6

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 8.0g of 5', 5-diallyl-2, 2' -biphenol and 2.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 100mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1200g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 1.5g of trimethylolpropane tri (3-mercaptopropionate) at the temperature of 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 100mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Example 7

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 8.0g of 5', 5-diallyl-2, 2' -biphenol and 2.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 300mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1500g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 1.5g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 300mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Example 8

A method for preparing bio-based antibacterial ultraviolet fluorescent paint.

The preparation method comprises the following steps:

s1, dissolving 8.0g of 5', 5-diallyl-2, 2' -biphenol and 2.0g of 1, 6-hexanedithiol in 90g of toluene at room temperature at a stirring speed of 200r/min to obtain a mixed solution.

S2, adding 500mg of azobisisobutyronitrile into the mixed solvent obtained in the step S1, raising the temperature to 60 ℃, and reacting for 6 hours at a stirring speed of 600 r/min.

S3, adding the product solution obtained in the step S2 into 1900g of cyclohexane solution, stirring at the speed of 500r/min for 20min, and then standing.

S4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain the prepolymer.

S5, uniformly stirring the prepolymer obtained in the step S4 and 2.5g of trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance.

S6, adding 500mg of catalyst 1,1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] into the mixed substance obtained in the step S5, and stirring until the catalyst is completely dissolved.

S7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

Claims (2)

1. The bio-based antibacterial ultraviolet fluorescent paint is characterized by comprising 80-90 parts by mass, 10-20 parts by mass and 1-5 parts by mass of a prepolymer, a multi-mercapto compound and a catalyst a;

the molecular chain of the prepolymer contains biphenyl diphenol and thioether structures, and both ends of the molecular chain have alkylene functional groups, wherein the prepolymer is a linear polymer obtained by polymerizing 5', 5-diallyl-2, 2' -biphenyl diphenol and 1, 6-hexanedithiol under the action of a catalyst b, and the catalyst b is azobisisobutyronitrile;

the multi-mercapto compound is trimethylolpropane tri (3-mercaptopropionic acid) ester;

the catalyst a is 1,1' - (methylene di-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ].

2. A preparation method of a bio-based antibacterial ultraviolet fluorescent paint is characterized by comprising the following steps:

s1, dissolving 5', 5-diallyl-2, 2' -biphenol and 1, 6-hexanedithiol in an organic solvent at the stirring speed of 200-;

wherein the mass part ratio of the solutes of 5', 5-diallyl-2, 2' -biphenol and 1, 6-hexanedithiol is 65-80: 20-35, wherein the mass part ratio of the solute to the solvent is 10-20: 80-90;

the solvent is one of toluene, acetone, dimethyl sulfoxide or N, N-dimethylformamide;

s2, adding a catalyst b into the mixed solution obtained in the step S1, wherein the mass part ratio of the catalyst b to a solute in the step S1 is (1-5): 100; and the temperature is raised to 60-100 ℃, and the reaction is carried out for 4-6h at the stirring speed of 600-800 r/min;

s3, adding the product solution obtained after the reaction in the step S2 into a cyclohexane solution, stirring at the speed of 500-1000 r/min for 20min, and then standing, wherein the mass part ratio of the product solution to the cyclohexane solution is 5-10: 90-95;

s4, removing the supernatant of the solution obtained in the step S3, collecting lower-layer colloidal precipitate, and drying at 30 ℃ and 0.09Mpa for 30min to obtain a prepolymer;

s5, uniformly stirring the prepolymer obtained in the step S4 and trimethylolpropane tri (3-mercaptopropionate) at 80 ℃ to fully mix the prepolymer and the trimethylolpropane tri (3-mercaptopropionate) to obtain a mixed substance, wherein the mass part ratio of the prepolymer to the trimethylolpropane tri (3-mercaptopropionate) is 80-90: 10-20 parts of;

s6, adding the catalyst a into the mixed substance obtained in the step S5, and stirring until the catalyst a is completely dissolved to obtain a mixed solution, wherein the ratio of the catalyst a to the mixed substance is 1-5: 100, respectively;

s7, standing the mixed solution obtained in the step S6 and cooling to room temperature to obtain viscous transparent slurry, namely the bio-based antibacterial ultraviolet fluorescent paint.

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