Antibacterial filler for water-based paint and method for preparing the same

Abstract

The present application belongs to the technical field of fillers, and relates to a novel bacteriostatic filler for water-based paint and a preparation method thereof.The novel bacteriostatic filler for water-based paint comprises the following components: 8-10 parts of chitosan, 8-12 parts of methacrylic anhydride, 3-5 parts of polyaminopropyl biguanide, 2-3 parts of a catalyst, and 2-3 parts of a photoinitiator.The filler prepared by the present application is hydrophilic, and is convenient to use;it can be used by mixing with water-based paint in proportion.The filler greatly improves the stability and toughness of the paint after water absorption and swelling in the water-based paint, and has a relatively broad application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fillers, and relates to a novel bacteriostatic filler for water-based paint and a preparation method thereof, in particular to a novel bacteriostatic filler for water-based paint which is durable and has high antibacterial efficiency and a preparation method thereof. BACKGROUND

[0002] With the continuous development of the construction industry, the construction capacity in China has developed rapidly, and the amount of paint required for construction has been increasing. Under the influence of various factors, paint is prone to mold, affecting the appearance and even endangering people's health. As people's demand for living quality improves and national environmental protection standards improve, the development and production of an environmentally friendly, non-toxic, bacteriostatic and anticorrosive filler are particularly urgent.

[0003] The bacteriostatic agents commonly used in paint on the market are mainly divided into three types: inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents. The inorganic antibacterial agent has the longest development and use time, and the technology is relatively mature. However, the introduction of metal atoms (or ions) obtained by modifying means into some porous materials will cause damage to the environment and even humans. The organic antibacterial agent has fast bactericidal efficiency, but it is prone to hydrolysis, temperature change resistance and relatively poor durability. The natural antibacterial agent is mainly derived from various plant tissues and is environmentally friendly, non-toxic and harmless, but has low bactericidal efficiency and needs to be modified to improve its performance.

[0004] Therefore, it is necessary to develop an antibacterial agent that synergistically acts with natural antibacterial agents and organic antibacterial agents. SUMMARY

[0005] In order to solve the above problems, the present application provides a novel bacteriostatic filler for water-based paint and a preparation method thereof, which can not only improve the antibacterial property and durable antibacterial property of the paint, but also improve the stability of the paint.

[0006] A novel bacteriostatic filler for water-based paint comprises the following components: chitosan, methacrylic anhydride, polyaminopropyl biguanide, a catalyst and a photoinitiator. The mass fraction of each component is as follows: chitosan 8-10 parts, methacrylic anhydride 8-12 parts, polyaminopropyl biguanide 3-5 parts, catalyst 2-3 parts and photoinitiator 2-3 parts.

[0007] Further, the catalyst is any one of triethylamine, N,N-dimethylbenzylamine and N,N-dimethylcyclohexylamine.

[0008] Further, the photoinitiator is any one of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone (I2959), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) and 1-hydroxycyclohexyl phenyl ketone.

[0009] The application relates to a preparation method of a novel bacteriostatic filler for water-based paint, which comprises the following steps:

[0010] Step 1,

[0011] (1) dissolving chitosan in a buffer solution at room temperature, stirring uniformly, filtering off insoluble substances, and preparing a chitosan solution;

[0012] (2) adding methyl methacrylate into the chitosan solution to perform a substitution reaction under constant-temperature oscillation, terminating the reaction after 3 hours; after the reaction is completed, precipitating with 90% ethanol, centrifugally collecting the precipitate, washing the precipitate with 90% ethanol for three times, and vacuum drying to obtain a chitosan derivative.

[0013] Step 2, weighing polyaminopropyl biguanide and methyl acrylate, adding the two into a dimethyl sulfoxide solvent, mixing uniformly and completely dissolving, then weighing a catalyst and adding the catalyst into the dimethyl sulfoxide solvent, waiting for the reaction to be completed, extracting with dichloromethane, filtering, and drying to obtain modified polyaminopropyl biguanide.

[0014]

[0015] Step 3, weighing the chitosan derivative and the modified polyaminopropyl biguanide, dissolving a photoinitiator in deionized water, stirring uniformly on a magnetic stirrer, then irradiating with an ultraviolet lamp, generating a three-dimensional netted porous material through free radical copolymerization and crosslinking, filtering, drying, grinding into powder and long-term preservation as the bacteriostatic filler.

[0016] Further, in the step 1 (1), the buffer solution is a 1% acetic acid-water compound solution, and the pH value is 5.5.

[0017] Further, in the step 1 (2), the mass ratio of the chitosan solution to the methyl methacrylate is 1:1.

[0018] Further, in the step 1 (2), the chitosan solution and the methyl methacrylate are reacted under the conditions that the temperature is 50-70 DEG C, the rotating speed is 150-200 r / min. -1

[0019] Further, in the step 3, the mass ratio of the chitosan derivative to the modified polyaminopropyl biguanide is 20:2-3.

[0020] Further, in the step 3, the irradiation time of the ultraviolet lamp is 8-15 min.

[0021] Compared with the prior art, the application has the beneficial effects that.

[0022] ​1. Chitosan and polyaminopropyl biguanide are commonly used antibacterial substances. After modification, they are copolymerized by free radicals to form a three-dimensional network porous material. The antibacterial mechanisms of chitosan derivatives and modified polyaminopropyl biguanide are complementary. Both are positively charged and readily adsorb onto the negatively charged bacterial cell membranes. Chitosan derivatives adsorb onto the cell membrane, causing the loss of internal nutrients, while modified polyaminopropyl biguanide can form a film and adsorb onto the cell membrane, blocking bacterial respiration. The synergistic effect of the copolymer products greatly improves the antibacterial efficiency, making the antibacterial performance of the filler exceed that of a single component, and also improving the antibacterial durability. The addition of modified polyaminopropyl biguanide also has a certain deodorizing effect on the coating.

[0023] 2. The filler prepared by this invention is hydrophilic and easy to use. It can be used by mixing it with water-based coatings in a certain proportion. After the filler absorbs water and swells in the water-based coatings, its three-dimensional network porous structure greatly improves the stability and toughness of the coatings and has a broad application prospect. Detailed Implementation

[0024] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] A novel antibacterial filler for water-based coatings comprises the following components: chitosan, methacrylic anhydride, polyaminopropyl biguanide, catalyst, and photoinitiator; the mass fractions of each component are: 8-10 parts chitosan, 12-15 parts methacrylic anhydride, 3-5 parts polyaminopropyl biguanide, 2-3 parts catalyst, and 2-3 parts photoinitiator.

[0026] Furthermore, the catalyst is any one of triethylamine, N,N-dimethylbenzylamine, and N,N-dimethylcyclohexylamine.

[0027] Further, the photoinitiator is any one of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone (I2959), 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP), and 1-hydroxycyclohexylphenyl ketone.

[0028] A method for preparing a novel antibacterial filler for water-based coatings includes the following steps:

[0029] Step 1

[0030] (1) Dissolve chitosan in buffer solution at room temperature, stir well, filter out insoluble matter, and prepare chitosan solution;

[0031] (2) in the chitosan solution is added methyl methacrylate under constant temperature oscillation conditions to carry out substitution reaction, and the reaction is terminated after 3h; after the reaction is completed, the chitosan derivative is obtained by precipitating with 90% ethanol, centrifugally collecting the precipitate, washing with 90% ethanol for 3 times, and vacuum drying.

[0032]

[0033] Step 2, the polyaminopropyl biguanide and methacrylic anhydride are weighed and added to a dimethyl sulfoxide solvent, mixed uniformly and completely dissolved, and then the catalyst is weighed and added, after the reaction is completed, extraction is carried out with dichloromethane, filtration and drying to obtain modified polyaminopropyl biguanide.

[0034]

[0035] Step 3, the chitosan derivative and the modified polyaminopropyl biguanide are weighed and dissolved in deionized water, and then stirred uniformly on a magnetic stirrer, and then irradiated with an ultraviolet lamp, to generate a three-dimensional network porous material through free radical copolymerization and crosslinking, and then filtered, dried and ground into powder for long-term storage as the antibacterial filler.

[0036] Further, in the step 1 (1), the buffer solution is a 1% acetic acid-water compound solution, and the pH is 5.5.

[0037] Further, in the step 1 (2), the mass ratio of the chitosan solution to methyl methacrylate is 1:1.

[0038] Further, in the step 1 (2), the chitosan solution and methyl methacrylate are reacted at a temperature of 50-70℃ and a rotation speed of 150-200r·min -1 .

[0039] Further, in the step 3, the mass ratio of the chitosan derivative to the modified polyaminopropyl biguanide is 20:2-3.

[0040] Further, in the step 3, the ultraviolet lamp irradiation time is 8-15min.

[0041] The application provides a novel antibacterial filler for water-based paint, which is synthesized from chitosan, methacrylic anhydride, polyaminopropyl biguanide, a catalyst and a photoinitiator.

[0042] Example 1.

[0043] A preparation method of a novel antibacterial filler for water-based paint, comprising the following steps:

[0044] Step 1,

[0045] (1) Chitosan is dissolved in 1% acetic acid-water buffer solution (pH=5.5) at room temperature, stirred uniformly, and filtered to remove insoluble substances to prepare a 3% chitosan solution;

[0046] (2) 8 parts of the chitosan solution are taken, 8 parts of methyl methacrylate are added, and a substitution reaction is carried out at 60°C and 180 r·min -1 for 3 hours under constant temperature oscillation. After 3 hours, the reaction is terminated. After the reaction is completed, 90% ethanol is used for precipitation, the precipitate is collected by centrifugation, and the precipitate is washed with 90% ethanol for 3 times. Vacuum drying is performed to obtain a chitosan derivative.

[0047] Step 2, 3 parts of polyaminopropyl biguanide and 1 part of methacrylic anhydride are added to a dimethyl sulfoxide good solvent, mixed uniformly, and 2 parts of triethylamine catalyst are added. After the reaction is completed, dichloromethane is used for extraction, filtration, and drying to obtain modified polyaminopropyl biguanide.

[0048] Step 3, 20 parts of the chitosan derivative and 3 parts of the modified polyaminopropyl biguanide are dissolved in deionized water, and a photoinitiator I2959 is added. The mixture is stirred uniformly on a magnetic stirrer, irradiated with a ultraviolet lamp for 10 minutes, and subjected to free radical copolymerization and crosslinking to generate a three-dimensional network porous material. The material is filtered, dried, and ground into a powder.

[0049] The performance is tested, and the results are shown in Table 1.

[0050] Example 2.

[0051] A preparation method of a novel antibacterial filler for a water-based paint includes the following steps:

[0052] Step 1,

[0053] (1) Chitosan is dissolved in 1% acetic acid-water buffer solution (pH=5.5) at room temperature, stirred uniformly, and filtered to remove insoluble substances to prepare a 3% chitosan solution;

[0054] (2) 8 parts of the chitosan solution are taken, 8 parts of methyl methacrylate are added, and a substitution reaction is carried out at 60°C and 180 r·min -1 for 3 hours under constant temperature oscillation. After 3 hours, the reaction is terminated. After the reaction is completed, 90% ethanol is used for precipitation, the precipitate is collected by centrifugation, and the precipitate is washed with 90% ethanol for 3 times. Vacuum drying is performed to obtain a chitosan derivative.

[0055] Step 2, 3 parts of polyaminopropyl biguanide and 1 part of methacrylic anhydride are added to a dimethyl sulfoxide good solvent, mixed uniformly, and 2 parts of triethylamine catalyst are added. After the reaction is completed, dichloromethane is used for extraction, filtration, and drying to obtain modified polyaminopropyl biguanide.

[0056] Step 3, 20 parts of chitosan derivatives, 2 parts of modified polyamine propyl biguanide, 1 part of photoinitiator I2959 are dissolved in deionized water, stirred uniformly on a magnetic stirrer, and then irradiated with an ultraviolet lamp for 10 min. A three-dimensional network porous material is generated by free radical copolymerization and crosslinking. After filtration, drying treatment and grinding into powder.

[0057] The performance is tested, and the results are shown in Table 1.

[0058] Comparative Example 1.

[0059] A preparation method of a novel antibacterial filler for water-based paint comprises the following steps:

[0060] Step 1,

[0061] (1) Chitosan is dissolved in 1% acetic acid-water buffer solution (pH=5.5) at room temperature, stirred uniformly, and filtered to remove insoluble substances to prepare a 3% chitosan solution.

[0062] (2) 8 parts of chitosan solution are taken, and 8 parts of methyl methacrylate are added. Substitution reaction is carried out at 60°C and 180 r·min -1 for 3 h. After the reaction is completed, 90% ethanol is used for precipitation, and the precipitate is collected by centrifugation, washed with 90% ethanol for 3 times, and vacuum dried to obtain chitosan derivatives.

[0063] Step 2, 20 parts of chitosan derivatives and 2 parts of photoinitiator I2959 are dissolved in deionized water, stirred uniformly on a magnetic stirrer, and then irradiated with an ultraviolet lamp for 10 min. After crosslinking, filtration, drying treatment and grinding into powder.

[0064] The performance is tested, and the results are shown in Table 1.

[0065] Comparative Example 2.

[0066] A preparation method of a novel antibacterial filler for water-based paint comprises the following steps:

[0067] Step 1,

[0068] (1) Chitosan is dissolved in 1% acetic acid-water buffer solution (pH=5.5) at room temperature, stirred uniformly, and filtered to remove insoluble substances to prepare a 3% chitosan solution.

[0069] (2) 8 parts of chitosan solution are taken, and 8 parts of methyl methacrylate are added. Substitution reaction is carried out at 60°C and 180 r·min -1 for 3 h. After the reaction is completed, 90% ethanol is used for precipitation, and the precipitate is collected by centrifugation, washed with 90% ethanol for 3 times, and vacuum dried to obtain chitosan derivatives.

[0070] Step 2, 20 parts of the chitosan derivative, 3 parts of polyaminopropyl biguanide, 2 parts of the photoinitiator I2959 are dissolved in deionized water, stirred uniformly on a magnetic stirrer, and then irradiated with a UV lamp for 10 min to crosslink. After filtration, drying treatment, and grinding into powder, the three-dimensional network porous material is obtained.

[0071] The performance is tested, and the results are shown in Table 1.

[0072] Comparative Example 3.

[0073] A preparation method of a new antibacterial filler for water-based paint comprises the following steps:

[0074] Step 1,

[0075] (1) Chitosan is dissolved in 1% acetic acid-water buffer solution (pH=5.5) at room temperature, stirred uniformly, and filtered to remove insoluble substances to prepare a 3% chitosan solution.

[0076] (2) 8 parts of the chitosan solution are taken, 8 parts of methyl methacrylate are added, and a substitution reaction is performed at 60°C and 180 r·min -1 for 3 h. After the reaction is completed, the reaction product is precipitated with 90% ethanol, centrifuged to collect the precipitate, washed with 90% ethanol for 3 times, and dried in vacuum to obtain the chitosan derivative.

[0077] Step 2, 3 parts of polyaminopropyl biguanide and 1 part of methacrylic anhydride are added to a dimethyl sulfoxide solvent, mixed uniformly, and then 2 parts of triethylamine catalyst are added. After the reaction is completed, extraction is performed with dichloromethane, filtration, and drying to obtain the modified polyaminopropyl biguanide.

[0078] Step 3. 20 parts of the chitosan derivative, 4 parts of the modified polyaminopropyl biguanide, and 2 parts of the photoinitiator I2959 are dissolved in deionized water, stirred uniformly on a magnetic stirrer, and then irradiated with a UV lamp for 10 min to crosslink. Through free radical copolymerization and crosslinking, the three-dimensional network porous material is obtained, which is filtered, dried, and ground into powder.

[0079] The performance is tested, and the results are shown in Table 1.

[0080] Table 1. Test results of examples and comparative examples.

[0081]

Claims

1. A method for preparing an antibacterial filler for a water-based coating, characterized in that, Includes the following steps: Step 1 (1) Dissolve chitosan in buffer solution at room temperature, stir well, filter out insoluble matter, and prepare chitosan solution; (2) Methyl methacrylate was added to the chitosan solution and a substitution reaction was carried out under constant temperature shaking conditions. The reaction was terminated after 3 hours. After the reaction was completed, the chitosan was precipitated with 90% ethanol, centrifuged to collect the precipitate, washed 3 times with 90% ethanol, and dried under vacuum to obtain the chitosan derivative. Step 2: Weigh out polyurethane biguanide and methacrylic anhydride and add them to a solvent containing dimethyl sulfoxide. Mix well and dissolve completely. Then weigh out the catalyst and add it to the solvent. After the reaction is complete, extract with dichloromethane, filter, and dry to obtain modified polyurethane biguanide. Step 3: Weigh out the chitosan derivative, modified polyaminopropyl biguanide, and photoinitiator, dissolve them in deionized water, stir evenly on a magnetic stirrer, and then irradiate with an ultraviolet lamp to generate a three-dimensional network porous material through free radical copolymerization and cross-linking. After filtration, drying, and grinding into powder, it can be used as an antibacterial filler for long-term preservation.

2. The method for preparing the antibacterial filler for water-based coatings according to claim 1, characterized in that, In step 1 (1), the buffer solution is a 1% acetic acid-water compound solution with pH=5.

5.

3. The method for preparing the antibacterial filler for water-based coatings according to claim 1, characterized in that, In step 1 (2), the mass ratio of chitosan solution to methyl methacrylate is 1:

1.

4. The method for preparing the antibacterial filler for water-based coatings according to claim 1, characterized in that, In step 1(2), the chitosan solution and methyl methacrylate are reacted at a temperature of 50-70℃ and a rotation speed of 150-200 r·min. -1 The reaction takes place under specific conditions.

5. The method for preparing the antibacterial filler for water-based coatings according to claim 1, characterized in that, In step 3, the chitosan derivative and the modified polyaminopropyl biguanide are mixed in a mass ratio of 20:2~3.

6. The method for preparing the antibacterial filler for water-based coatings according to claim 1, characterized in that, In step 3, the ultraviolet lamp irradiation time is 8-15 minutes.

7. An antibacterial filler for a water-based coating prepared by a method for preparing an antibacterial filler for a water-based coating as described in any one of claims 1-6.

8. The antibacterial filler for water-based coatings as described in claim 7, characterized in that, The catalyst is any one of triethylamine, N,N-dimethylbenzylamine, or N,N-dimethylcyclohexylamine.

9. The antibacterial filler for water-based coatings as described in claim 7, characterized in that, The photoinitiator is any one of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 1-hydroxycyclohexylphenyl ketone.

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