CN111978443A - Antibacterial acrylic material and preparation method thereof - Google Patents
Antibacterial acrylic material and preparation method thereof Download PDFInfo
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- CN111978443A CN111978443A CN202010806001.0A CN202010806001A CN111978443A CN 111978443 A CN111978443 A CN 111978443A CN 202010806001 A CN202010806001 A CN 202010806001A CN 111978443 A CN111978443 A CN 111978443A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application relates to the technical field of polymer modification, in particular to an antibacterial acrylic material and a preparation method thereof. The method comprises the steps of carrying out surface modification on inorganic antibacterial agent powder to obtain modified inorganic antibacterial agent powder, and then mixing and grinding the modified inorganic antibacterial agent powder, methyl methacrylate and a medium-temperature initiator in proportion to obtain nano oily antibacterial slurry. In the grinding process, the particle size of the modified inorganic antibacterial agent powder is reduced, and the dispersion performance of the modified inorganic antibacterial agent powder in a system is improved; at the same time, methyl methacrylate is prepolymerized under the action of a medium-temperature initiator and is tightly combined with the modified inorganic antibacterial agent powder. The compatibility of the antibacterial acrylic material can be remarkably improved through the mode, the basic performance and the antibacterial performance of the antibacterial acrylic material are improved, and the antibacterial acrylic material can be stably used for a long time. The preparation method is simple in process and controllable in cost, and the prepared antibacterial acrylic material is excellent in performance and stable in quality, so that the antibacterial acrylic material has a good economic value.
Description
Technical Field
The application relates to the technical field of polymer modification, in particular to an antibacterial acrylic material and a preparation method thereof.
Background
The acrylic material is polymerized from methyl methacrylate monomer, has a chemical name of polymethyl methacrylate (PMMA), and is also called organic glass due to its good transmittance. The acrylic sheet has the characteristics of light transmittance, difficult cracking, good toughness, easy cleaning, soft texture and the like, and is mainly applied to living scenes such as lighting bodies, roofs, shed roofs, stairs, indoor wall guard plates and the like. Meanwhile, with the construction of commercial houses and the popularization of environmental awareness of consumers, the market demand for novel environment-friendly, healthy, nontoxic and radiationless building materials is rapidly increasing; since the acrylic material has the advantages of good chemical stability, easy dyeing, easy processing, electric insulation, chemical reagent corrosion resistance and the like, the acrylic material is widely used in building materials and furniture materials.
A common application scenario of the acrylic material is used as a toilet and a bathroom product, and since the toilet and the bathroom product are in a humid and relatively closed application environment, harmful bacteria are easily grown on the surface of the acrylic toilet and the bathroom product in the using process, and the health of a human body is affected, the acrylic toilet and the bathroom product are endowed with an antibacterial function, which is particularly necessary. Nowadays, some patents related to the preparation of antibacterial acrylic sheet materials have appeared, and most of the antibacterial acrylic patents are acrylic modified materials obtained by simply blending inorganic antibacterial agents as fillers into polymethyl methacrylate matrices, although the acrylic modified materials can combine the advantages of the antibacterial materials and the properties of polymethyl methacrylate to some extent, so that the optical, thermal and mechanical properties of the sheet materials using the acrylic modified materials meet the use requirements and have certain antibacterial properties. However, the inorganic antibacterial agent powder and the polymethyl methacrylate have large polarity difference and poor compatibility and are easy to generate phase separation, and the factors cause that the inorganic antibacterial agent powder is not uniformly distributed in the polymethyl methacrylate matrix and is easy to precipitate, so that the appearance of the product is influenced, the optical, thermal and mechanical properties of the product are reduced, and the quality of the product is seriously influenced. In addition, these patents have the disadvantages of complicated preparation process, high cost and unstable antibacterial effect. At present, no mature and stable antibacterial acrylic material and product exist in the market, so that the research on the antibacterial acrylic material with good compatibility and excellent performance has good application prospect and can bring good economic benefit.
Disclosure of Invention
The application provides the technical content of the first aspect, in particular to an antibacterial acrylic material, which comprises the following raw materials in parts by weight:
85-90 parts of methyl methacrylate
5-15 parts of nano oily antibacterial slurry
0.01-0.05 part of medium-temperature initiator
The nano oily antibacterial slurry comprises raw materials of inorganic antibacterial agent powder, a powder surface modifier, methyl methacrylate and a moderate temperature initiator; in the raw material composition of the nano oily antibacterial slurry, the mass ratio of the inorganic antibacterial agent powder, the powder surface modifier, the methyl methacrylate and the medium-temperature initiator is 5-15: 0.05-0.3: 85-90: 0.001-0.005; the preparation method of the nano oily antibacterial slurry comprises the following steps: coating the powder surface modifier on inorganic antibacterial agent powder in advance to obtain modified inorganic antibacterial agent powder, then mixing the modified inorganic antibacterial agent powder, methyl methacrylate and a moderate temperature initiator, grinding to obtain the nano oily antibacterial slurry, and in the grinding process, raising the temperature of the slurry to between 40 and 100 ℃ and keeping the temperature for at least 20 min.
Optionally, the preparation method of the nano oily antibacterial slurry comprises the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and powder surface modifier according to a mass ratio, then adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 60-85 ℃ and the linear velocity is 50-100 m/s to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a ceramic sand mill according to a mass ratio for grinding and dispersing, wherein zirconium beads with the volume fraction of 40-60% and the particle size of 0.3-0.5 mm are filled in a cavity of the sand mill; and grinding the mixture for 30-90 minutes by a sand mill at a rotation linear speed of 10-25 m/s to obtain the nano oily antibacterial slurry.
Optionally, the medium-temperature initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azodiisopropylate and a peroxyacyl initiator.
Optionally, the inorganic antibacterial agent powder is one or more of zinc oxide, silver oxide, copper oxide, silver-loaded zirconium phosphate powder and zinc-loaded zirconium phosphate powder with an average primary particle size of less than 100 nm.
Optionally, the nano oily antibacterial slurry has an average particle size of 15.0-60.0 nm and an absolute viscosity of 0.165-0.275Pa · S.
Optionally, the powder surface modifier is one or more of silane coupling agents KH-540, KH-550, KH-560, KH-570, KH-792, Si-602, Si-563, A-151, A-171 and A-172.
The application also provides technical contents of a second aspect, and particularly relates to a preparation method of any one of the antibacterial acrylic material in the technical contents of the first aspect, wherein the preparation method comprises the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and a powder surface modifier according to a mass ratio, and coating the powder surface modifier on the surface of the inorganic antibacterial agent powder at a temperature of between 60 and 85 ℃ for coating modification to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a grinding machine according to the mass ratio, and grinding to obtain nano oily antibacterial slurry, wherein in the grinding process, the temperature of the slurry is increased to 40-100 ℃ and is kept for at least 20 min;
3) mixing: mixing and stirring methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio to obtain a mixture;
4) polymerization: the mixture is prepolymerized for 1.5 to 3 hours at the temperature of 60 to 70 ℃ to obtain an antibacterial acrylic prepolymer, then the prepolymer is polymerized for 2 to 4 hours at the temperature of 110 to 120 ℃, and the antibacterial acrylic material is obtained after cooling.
Optionally, the preparation method comprises the following steps
1) Preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and powder surface modifier according to a mass ratio, then adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 60-85 ℃ and the linear velocity is 50-100 m/s to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a ceramic sand mill according to a mass ratio for grinding and dispersing, wherein zirconium beads with the volume fraction of 40-60% and the particle size of 0.3-0.5 mm are filled in a cavity of the sand mill; grinding the mixture for 30-90 minutes by a sand mill at a rotation linear speed of 10-25 m/s to obtain the nano oily antibacterial slurry;
3) mixing: mixing methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio, and mixing and stirring for 5-10 minutes at a linear speed of 1-5 m/s to obtain a mixture;
4) polymerization: the mixture is prepolymerized for 1.5 to 3 hours at the temperature of 60 to 70 ℃ to obtain an antibacterial acrylic prepolymer, then the prepolymer is polymerized for 2 to 4 hours at the temperature of 110 to 120 ℃, and the antibacterial acrylic material is obtained after cooling.
Optionally, in the step 4), the mixture is subjected to prepolymerization by heating in a water bath; and heating the antibacterial acrylic prepolymer by adopting an air bath, and cooling to obtain the antibacterial acrylic material.
Optionally, in step 4), the pre-polymerization and polymerization processes of the mixture are performed in a mold, and after step 4) is completed, the mold with the acrylic material is placed in water at 10-20 ℃ for cooling and demolding.
The antibacterial acrylic material is used for specially treating conventional inorganic antibacterial agent powder, and specifically comprises the following steps: the modified inorganic antibacterial agent powder is coated with a powder surface modifier in advance to obtain lipophilic modified inorganic antibacterial agent powder, and then the modified inorganic antibacterial agent powder, methyl methacrylate and a medium-temperature initiator are mixed in proportion and ground to obtain the nano oily antibacterial slurry. In the grinding process, the modified inorganic antibacterial agent powder is crushed into smaller particle size, which is beneficial to the dispersion performance of the modified inorganic antibacterial agent powder in a system, thereby improving the compatibility of the material; in addition, due to the friction heating, methyl methacrylate in the slurry is prepolymerized under the action of a medium-temperature initiator and is tightly combined with the modified inorganic antibacterial agent powder. The compatibility of the antibacterial acrylic material can be remarkably improved in the mode, the basic performance and the antibacterial performance of the antibacterial acrylic material are improved, and the antibacterial acrylic material can be stably used for a long time. The preparation method is simple in process and controllable in cost, and the prepared antibacterial acrylic material is excellent in performance and stable in quality, so that the antibacterial acrylic material has a good economic value.
Detailed Description
The application provides an antibacterial acrylic material, the antibacterial acrylic material adopts special oily antibacterial slurry of nanometer as antibiotic component, and this component has good compatibility with methyl methacrylate to can exert antibacterial action well. The antibacterial acrylic material can keep good antibacterial property for a long time under the condition that the overall mechanical and optical properties meet the use requirements.
The antibacterial acrylic material comprises the following raw materials in parts by weight:
85-90 parts of methyl methacrylate
5-15 parts of nano oily antibacterial slurry
0.01-0.05 part of medium-temperature initiator
The nano oily antibacterial slurry is characterized by comprising raw materials of inorganic antibacterial agent powder, powder surface modifier, methyl methacrylate and medium-temperature initiator, wherein the mass ratio of the inorganic antibacterial agent powder to the powder surface modifier to the methyl methacrylate to the medium-temperature initiator is 5-15: 0.05-0.3: 85-90: 0.001-0.005; the preparation method of the nano oily antibacterial slurry comprises the following steps: coating a powder surface modifier on inorganic antibacterial agent powder to obtain modified inorganic antibacterial agent powder, mixing the modified inorganic antibacterial agent powder, methyl methacrylate and a moderate temperature initiator, and grinding to obtain the nano oily antibacterial slurry, wherein the temperature of the slurry is increased to 40-100 ℃ and kept for at least 20min in the grinding process, and the arrangement is to perform proper prepolymerization on the methyl methacrylate in the grinding process.
The powder surface modifier is coated on the surface of the inorganic antibacterial agent powder, wherein the hydrophilic end of the powder surface modifier is adsorbed on the surface of the inorganic antibacterial agent powder, and the lipophilic end of the powder surface modifier is exposed outside.
While specific types of powder surface modifying agents will be readily apparent to those of ordinary skill in the art in view of the foregoing, as an alternative embodiment, the present application provides a specific combination of powder surface modifying agents, specifically one or more of the silane coupling agents KH-540, KH-550, KH-560, KH-570, KH-792, Si-602, Si-563, A-151, A-171, and A-172. The silane coupling agent has the hydrophilic group and the lipophilic group of the conventional surface modifier, and can improve the bonding strength of the inorganic antibacterial agent powder and the polymethyl methacrylate, thereby improving the problem that the inorganic antibacterial agent powder is easy to separate out to a certain extent.
In the grinding process, the modified inorganic antibacterial agent powder is crushed into smaller fine particles, and generates a large amount of heat under the friction of mechanical force, so that the temperature of the mixed slurry rises, at the moment, the methyl methacrylate monomer is polymerized into polymethyl methacrylate with a certain degree of polymerization under the action of the medium-temperature initiator, and in the process, the fine modified inorganic antibacterial agent powder with good lipophilicity can be well dispersed in a system and combined with the polymethyl methacrylate, so that a very stable and uniform phase structure is formed, and the interface firmness is very high. Through the mode, the nano oily antibacterial slurry is prepared into a mixture of inorganic antibacterial agent powder with good dispersibility and bonding performance in polymethyl methacrylate.
As a preferred embodiment, the average primary particle diameter of the obtained nano oily antibacterial slurry is controlled to be 16-60nm by grinding the mixture of the modified inorganic antibacterial agent powder, the methyl methacrylate and the medium-temperature initiator, and the absolute viscosity of the nano oily antibacterial slurry is 0.165-0.275 Pa.S. The average primary particle size of the nano oily antibacterial slurry is mainly controlled in consideration of dispersibility and bactericidal performance of the modified inorganic antibacterial agent powder in the polymethyl methacrylate, and the finer the particle size of the modified inorganic antibacterial agent powder is, the better the dispersibility is, the larger the specific surface area is, the better the bonding with the polymethyl methacrylate can be realized, and the firmness of an interface is improved; in addition, the larger specific surface area means that the inorganic antibacterial agent powder can release more sterilizing substances, thereby improving the sterilizing effect. In addition, the absolute viscosity of the nano oily antibacterial slurry is mainly controlled in consideration of controlling the prepolymerization degree of the methyl methacrylate in the grinding process, the polymerization degree and the molecular weight of the methyl methacrylate are controlled in a proper range in the integral preparation process, and the stable operation of the polymerization process is ensured. The dispersion performance, the sterilization performance and the polymerization degree of the polymethyl methacrylate of the modified inorganic antibacterial agent powder can be controlled by controlling the average primary particle size and the absolute viscosity of the nano oily antibacterial slurry in the process, and the technical control means for achieving the technical effect is easy to implement, namely the grinding effect is easy to achieve, and the influence on the whole preparation difficulty and the preparation cost is small.
And then, the nano oily antibacterial slurry, the methyl methacrylate and the medium-temperature initiator are used for further polymerization, and the polymerization process adopts a common means that the methyl methacrylate is initiated to polymerize at the medium-temperature initiator, so that a person skilled in the art can correctly and completely implement the nano oily antibacterial slurry, the methyl methacrylate and the medium-temperature initiator in combination with common general knowledge in the field, and therefore, the above means can constitute a clear and complete technical scheme, and the person skilled in the art can completely implement the nano oily antibacterial slurry, the methyl methacrylate and the medium-temperature initiator.
The intermediate temperature initiator is an auxiliary chemical substance used for chain initiation reaction at 40-100 ℃ in the prior art, and similarly, a person skilled in the art can easily think of a specific variety of the intermediate temperature initiator used in combination with methyl methacrylate at the temperature. Similarly, a person skilled in the art can select other chemical substances with the same technical effect as the medium-temperature initiator described in the present application in combination with the above-mentioned matters, and such technical means also fall within the scope of the present application.
In combination with the above, it is easy to think that the inorganic antimicrobial powder should be selected from inorganic antimicrobial powders with small particle size. As an optional scheme, the inorganic antibacterial agent powder is one or more of zinc oxide, silver oxide, copper oxide, zirconium phosphate-loaded silver, and zirconium phosphate-loaded zinc powder with an average primary particle size of less than 100nm, the inorganic antibacterial agent powder can free metal particles such as metal copper, silver, and zinc ions, and the heavy metal ions have high chemical activity, are combined with cell membranes of bacteria, and can react with functional groups such as sulfydryl and amino groups in proteins, so that the protein activity is destroyed, and the bactericidal effect is realized. The particle size of the inorganic antibacterial agent powder has a large influence on the sterilization performance of the inorganic antibacterial agent powder, and the smaller the particle size, the larger the surface area of the antibacterial agent is, the metal ions are relatively more easily dissociated, so that the sterilization effect is improved; further, the inorganic antibacterial agent powder having a smaller particle size is more easily dispersed in polymethyl methacrylate, and is also advantageous for improving compatibility.
The application also provides a preparation method of the antibacterial acrylic material, which adopts the raw materials and mainly comprises the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and a powder surface modifier according to a mass ratio, and coating the powder surface modifier on the surface of the inorganic antibacterial agent powder at a temperature of between 60 and 85 ℃ for coating modification to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a grinding machine according to the mass ratio, and grinding to obtain nano oily antibacterial slurry, wherein in the grinding process, the temperature of the slurry is increased to 40-100 ℃ and is kept for at least 20 min;
3) mixing: mixing and stirring methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio to obtain a mixture;
4) polymerization: the mixture is prepolymerized for 1.5 to 3 hours at the temperature of 60 to 70 ℃ to obtain an antibacterial acrylic prepolymer, then the prepolymer is polymerized for 2 to 4 hours at the temperature of 110 to 120 ℃, and the antibacterial acrylic material is obtained after cooling.
In view of the foregoing, it will be apparent to those skilled in the art that the powder surface modifier can be coated on the inorganic antimicrobial powder by a specific technique, such as a specific method of coating the inorganic antimicrobial powder with a powder surface modifier, a specific grinding apparatus, a specific process setting, a specific material mixing method, a specific polymerization method, and the like.
As a preferred embodiment, in the preparation process of the antibacterial acrylic material, in the step 4), the pre-polymerization and polymerization processes of the mixture are performed in a mold, after the step 4) is completed, the mold with the acrylic material is placed in water at 10-20 ℃ for cooling and demolding to obtain a molded acrylic plate, and the molded acrylic plate can be directly polymerized by the method without secondary molding, so that the production efficiency can be greatly improved by the method.
The preparation method is simple in process and low in cost, and the antibacterial acrylic material prepared by the preparation method has good compatibility, can improve basic performances such as mechanical performance and optical performance, and meanwhile improves the antibacterial performance. The antibacterial acrylic material has excellent performance and good sterilization effect, can meet the long-time use requirement, has lower production cost, has good economic benefit and is worthy of industrial popularization.
In order to further explain the preparation method and technical effects of the antibacterial acrylic material, the technical solution of the present application is explained by the following specific examples.
Example 1
The embodiment provides an antibacterial acrylic material and a preparation method thereof.
Specifically, the antibacterial acrylic material of the embodiment comprises the following raw materials in parts by weight
85-90 parts of methyl methacrylate
5-15 parts of nano oily antibacterial slurry
0.01-0.05 part of medium-temperature initiator
The nanometer oily antibacterial slurry comprises the following raw materials: inorganic antibacterial agent powder, powder surface modifier, methyl methacrylate and moderate temperature initiator, the mass ratio of which is 10: 0.15: 88: 0.003.
In this embodiment, the inorganic antimicrobial powder is zinc oxide with an average primary particle size of less than 100 nm; the powder surface modifier is a silane coupling agent KH 560; the medium-temperature initiator is azobisisobutyronitrile; the methyl methacrylate is produced in the chemical industry of Jilin, and other materials which are not shown are common commercial materials in the market.
The preparation method of the antibacterial acrylic material comprises the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and a powder surface modifier according to a mass ratio, adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 70 ℃ and the linear velocity is 75m/s to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a ceramic sand mill according to a mass ratio for grinding and dispersing, wherein zirconium beads with the volume fraction of 50% and the particle size of 0.3-0.5 mm are filled in a cavity of the sand mill; grinding the mixture for 60 minutes at a rotation linear speed of 20m/s by a sand mill to obtain the nano oily antibacterial slurry, wherein the mixed slurry can be raised to 40 ℃ when the grinding time is less than 10 minutes by testing at room temperature, so that the grinding conditions meet the requirement that the slurry is kept at 40-100 ℃ for at least 20 minutes;
3) mixing: mixing methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio, and mixing and stirring for 8 minutes at a linear speed of 3m/s to obtain a mixture;
4) polymerization: and pre-polymerizing the mixture at 65 ℃ for 2 hours to obtain an antibacterial acrylic prepolymer, then polymerizing the prepolymer at 115 ℃ for 3 hours, and cooling to obtain the antibacterial acrylic material.
The following antibacterial acrylic material is prepared according to the preparation method:
the preparation method of the comparative group 1 is as follows:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and a powder surface modifier according to a mass ratio, adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 70 ℃ and the linear velocity is 75m/s to obtain modified inorganic antibacterial agent powder;
2) mixing: mixing methyl methacrylate, modified inorganic antibacterial agent powder and a medium-temperature initiator according to a mass ratio, and mixing and stirring for 8 minutes at a linear speed of 3m/s to obtain a mixture;
3) polymerization: and pre-polymerizing the mixture at 65 ℃ for 2 hours to obtain an antibacterial acrylic prepolymer, then polymerizing the prepolymer at 115 ℃ for 3 hours, and cooling to obtain the antibacterial acrylic material.
The comparative group 1 and other implementation groups adopt the same materials, and the main difference is that the modified inorganic antibacterial agent powder is not prepared into nano oily antibacterial slurry and is directly used in a blending system.
For each of the above examples and comparative examples, the following properties were obtained as shown in the table:
in the present example, each of the examples and comparative example 1 was tested for antibacterial performance using QB/T2591-2003 standard.
According to the data, the antibacterial acrylic material prepared by the preparation method has better compatibility, and the impact performance of the acrylic material obtained from each implementation group is higher than that of the acrylic material obtained from the comparison group 1. In addition, the antibacterial performance of each implementation group reaches more than 99 percent, and the plastic belongs to class I antibacterial plastics. The comparison between the comparison group 1 and the implementation group shows that the compatibility and the antibacterial performance of the material can be obviously improved by preparing the nano oily antibacterial slurry.
Example 2
The embodiment provides an antibacterial acrylic material and a preparation method thereof.
Specifically, the antibacterial acrylic material of the embodiment comprises the following raw materials in parts by weight
88 parts of methyl methacrylate
10 parts of nano oily antibacterial slurry
0.03 part of medium-temperature initiator
The nanometer oily antibacterial slurry comprises the following raw materials: inorganic antibacterial agent powder, powder surface modifier, methyl methacrylate and moderate temperature initiator, the mass ratio of which is 5-15: 0.05-0.3: 85-90: 0.001-0.005.
In this embodiment, the inorganic antibacterial agent powder is silver-loaded zirconium phosphate with an average primary particle size of less than 100 nm; the powder surface modifier is a silane coupling agent A-171; the medium-temperature initiator is benzoyl peroxide; the methyl methacrylate is produced in the chemical industry of Jilin, and other materials which are not shown are common commercial materials in the market.
The preparation method of the antibacterial acrylic material in this embodiment is the same as that in embodiment 1, and the difference is only in the variety and ratio of the materials used, and in this embodiment, the difference of each embodiment is that the raw material composition ratio of the prepared nano oily antibacterial slurry is different, and the rest are the same.
The following antibacterial acrylic material is prepared according to the preparation method:
for each of the above examples and comparative examples, the following properties were obtained as shown in the table:
in the present example, each of the implemented groups was tested for antibacterial performance using QB/T2591-2003 standard.
According to the data, the antibacterial acrylic material prepared by the preparation method has the antibacterial performance of more than 99%, meets the I-type antibacterial plastic standard, and is not affected in mechanical and optical properties.
The same and similar parts among the various embodiments in the specification of the present application may be referred to each other. In particular, for the system and terminal embodiments, since the method therein is substantially similar to the method embodiments, the description is relatively simple, and the relevant points can be referred to the description in the method embodiments.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Of course, the above description is not limited to the above examples, and technical features that are not described in this application may be implemented by or using the prior art, and are not described herein again; the above examples are only for illustrating the technical solutions of the present application and not for limiting the present application, and the present application is only described in detail with reference to the preferred embodiments, and those skilled in the art should understand that those skilled in the art should make changes, modifications, additions or substitutions within the spirit and scope of the present application without departing from the spirit of the present application and also fall within the scope of the claims of the present application.
Claims (10)
1. The antibacterial acrylic material is characterized by comprising the following raw materials in parts by weight:
85-90 parts of methyl methacrylate
5-15 parts of nano oily antibacterial slurry
0.01-0.05 part of medium-temperature initiator
The nano oily antibacterial slurry comprises raw materials of inorganic antibacterial agent powder, a powder surface modifier, methyl methacrylate and a moderate temperature initiator; in the raw material composition of the nano oily antibacterial slurry, the mass ratio of the inorganic antibacterial agent powder, the powder surface modifier, the methyl methacrylate and the medium-temperature initiator is 5-15: 0.05-0.3: 85-90: 0.001-0.005; the preparation method of the nano oily antibacterial slurry comprises the following steps: coating the powder surface modifier on inorganic antibacterial agent powder in advance to obtain modified inorganic antibacterial agent powder, then mixing the modified inorganic antibacterial agent powder, methyl methacrylate and a moderate temperature initiator, grinding to obtain the nano oily antibacterial slurry, and in the grinding process, raising the temperature of the slurry to between 40 and 100 ℃ and keeping the temperature for at least 20 min.
2. The antibacterial acrylic material according to claim 1, wherein the preparation method of the nano oily antibacterial slurry comprises the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and powder surface modifier according to a mass ratio, then adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 60-85 ℃ and the linear velocity is 50-100 m/s to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a ceramic sand mill according to a mass ratio for grinding and dispersing, wherein zirconium beads with the volume fraction of 40-60% and the particle size of 0.3-0.5 mm are filled in a cavity of the sand mill; and grinding the mixture for 30-90 minutes by a sand mill at a rotation linear speed of 10-25 m/s to obtain the nano oily antibacterial slurry.
3. The antibacterial acrylic material according to claim 1, wherein the medium-temperature initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azodiisopropylate and peroxyacyl initiator.
4. The antibacterial acrylic material according to claim 1, wherein the inorganic antibacterial agent powder is one or more of zinc oxide, silver oxide, copper oxide, silver-loaded zirconium phosphate powder and zinc-loaded zirconium phosphate powder with an average primary particle size of less than 100 nm.
5. The antibacterial acrylic material as claimed in claim 1, wherein the nano oily antibacterial slurry has an average particle size of 15.0-60.0 nm and an absolute viscosity of 0.165-0.275 Pa-S.
6. The antibacterial acrylic material according to claim 1, wherein the powder surface modifier is one or more of silane coupling agents KH-540, KH-550, KH-560, KH-570, KH-792, Si-602, Si-563, A-151, A-171 and A-172.
7. The method for preparing the antibacterial acrylic material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
1) preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and a powder surface modifier according to a mass ratio, and coating the powder surface modifier on the surface of the inorganic antibacterial agent powder at a temperature of between 60 and 85 ℃ for coating modification to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a grinding machine according to the mass ratio, and grinding to obtain nano oily antibacterial slurry, wherein in the grinding process, the temperature of the slurry is increased to 40-100 ℃ and is kept for at least 20 min;
3) mixing: mixing and stirring methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio to obtain a mixture;
4) polymerization: the mixture is prepolymerized for 1.5 to 3 hours at the temperature of 60 to 70 ℃ to obtain an antibacterial acrylic prepolymer, then the prepolymer is polymerized for 2 to 4 hours at the temperature of 110 to 120 ℃, and the antibacterial acrylic material is obtained after cooling.
8. The method for preparing the antibacterial acrylic material as claimed in claim 7, which comprises the following steps
1) Preparing inorganic antibacterial agent powder by dry modification: mixing inorganic antibacterial agent powder and powder surface modifier according to a mass ratio, then adding the mixture into a powder surfactant, and coating and modifying the surface of the inorganic antibacterial agent powder under the conditions that the temperature is 60-85 ℃ and the linear velocity is 50-100 m/s to obtain modified inorganic antibacterial agent powder;
2) preparing nano oily antibacterial slurry: putting the modified inorganic antibacterial agent powder prepared in the step 1), methyl methacrylate and a medium-temperature initiator into a ceramic sand mill according to a mass ratio for grinding and dispersing, wherein zirconium beads with the volume fraction of 40-60% and the particle size of 0.3-0.5 mm are filled in a cavity of the sand mill; grinding the mixture for 30-90 minutes by a sand mill at a rotation linear speed of 10-25 m/s to obtain the nano oily antibacterial slurry;
3) mixing: mixing methyl methacrylate, nano oily antibacterial slurry and a medium-temperature initiator according to a mass ratio, and mixing and stirring for 5-10 minutes at a linear speed of 1-5 m/s to obtain a mixture;
4) polymerization: the mixture is prepolymerized for 1.5 to 3 hours at the temperature of 60 to 70 ℃ to obtain an antibacterial acrylic prepolymer, then the prepolymer is polymerized for 2 to 4 hours at the temperature of 110 to 120 ℃, and the antibacterial acrylic material is obtained after cooling.
9. The method for preparing the antibacterial acrylic material according to claim 8, wherein in the step 4), the mixture is subjected to prepolymerization by heating in a water bath; and heating the antibacterial acrylic prepolymer by adopting an air bath, and cooling to obtain the antibacterial acrylic material.
10. The method for preparing an antibacterial acrylic material according to claim 8, wherein in step 4), the pre-polymerization and polymerization processes of the mixture are performed in a mold, and after the step 4) is completed, the mold with the acrylic material is placed in water at 10-20 ℃ for cooling and demolding.
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