CN113817198B - Use of non-releasing antimicrobial adhesive coating in antimicrobial feeding bottles - Google Patents
Use of non-releasing antimicrobial adhesive coating in antimicrobial feeding bottles Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/02—Characterised by the use of homopolymers or copolymers of esters
Abstract
The invention relates to an application of a non-release antimicrobial adhesion coating in an antimicrobial feeding bottle, wherein the main component of the coating is composed of a copolymer of two monomers, namely Borneol Acrylate (BA) and polyethylene glycol diacrylate (PEGDA), so as to construct an amphiphilic stereochemical antimicrobial high-molecular coating, and the coating has good antimicrobial adhesion. The preparation method of the coating mainly comprises the following steps: the first step is to fix the photoinitiator on the surface of the feeding bottle, and the second step is to graft and copolymerize the monomer through surface free radical initiation polymerization. The preparation method of the coating is simple, and the obtained grafted coating is safe and stable; the advantages of the borneol polyacrylate and the polyethylene glycol diacrylate can be fully exerted, and the adhesion of microorganisms is synergistically prevented; the coating can be applied to the modification of the surface of the feeding bottle, and the structural flatness of the grafted coating can be ensured.
Description
Technical Field
The invention belongs to the field of biological materials, and relates to application of a non-release antimicrobial adhesion coating in an antimicrobial feeding bottle.
Background
The polymer base material is widely applied to the life and industrial production of people, such as agriculture, food, medical treatment, chemical industry and the like. However, these polymers generally do not have the function of resisting microbial adhesion, which provides a medium for adhesion and transmission of microorganisms, seriously affects the production efficiency and threatens the health of human beings. These problems of microbial contamination have been attracting attention from many researchers in recent years, and therefore it is important to modify the surface of a polymer to impart antimicrobial adhesion properties thereto without damaging the internal structure of the polymer.
The existing preparation methods of the high-molecular antibacterial material are mainly divided into two types: one is to add antibacterial components in the preparation process, such as filling nano particles, adding antibacterial agents and the like, and the method has high film forming stability, but at the same time, the difficulty of the production process is often increased, and the problem of low utilization rate of the antibacterial components exists; the other method is to load the antibacterial component on the surface after the polymer is processed and formed, and the method can improve the utilization rate of the antibacterial component, but has the problem that the durability of the antibacterial effect is poor due to exposure along with the release of the antibacterial component.
For example, china patent No. 201020104663 discloses an anti-adsorption and antibacterial feeding bottle, and the invention is provided with a PEO film layer on the inner surface of the feeding bottle, so that bacteria can be effectively prevented from adhering and propagating. The Chinese patent of application number 201510334709 provides a production method of a composite nano silver antibacterial feeding bottle, and the invention fills silver antibacterial particles in the feeding bottle and has excellent antibacterial effect. The antibacterial milk bottles have the problems of insufficient antibacterial effect durability, even release of antibacterial components and the like. In addition, it is difficult to have both fungal and bacterial resistance in the existing antibacterial materials. Thus, the production of baby bottles with highly effective and stable non-releasing antimicrobial adherent coatings has been an important goal of research and development in the industry.
In recent years, the method of introducing functional groups by ultraviolet light assisted surface modification has attracted the interest of researchers. In 1996, poplar and Ranby invented a method for "two-step" active photo grafting of polymers, under the condition of ultraviolet irradiation, a photoinitiator Benzophenone (BP) can abstract H atoms of C-H bonds on the surface of a substrate, so that surface free radicals are generated to initiate polymerization, growth of grafted chains is realized, and terminal free radicals can be coupled with semipinacol free radicals generated by reduction of BP, so that controllable active surface grafting polymerization is realized (Macromolecules, 1996, 29, 3308). Subsequently, studies of poplar and Yi, etc., found that Isopropyl Thioxanthone (ITX) which is similar to the benzophenone structure also has similar properties and realizes grafting to a polymer substrate in the visible light range. The general description of uv-initiated surface technology is given in the university of beijing chemistry Yang Motai in "photoinitiation and surface modification" (polymer chemistry, 2001, chemical industry press), indicating that all vinyl monomers suitable for use in the process, such as acrylic acid, acrylic esters, acrylamides, etc., and photosensitizers suitable for use in the process, such as benzophenone, anthrone, etc. The invention of application numbers 200310100364 and 200710146564 optimizes the method and achieves the aim of modifying the surfaces of various polymer materials.
The invention of application number 201410081985 discloses an antibacterial material of cellulose composite borneol, which uses borneol molecules to esterify and modify the high molecular structure of cellulose so as to realize the aim of resisting microbial adhesion. The method is simple and easy to implement, and has good antibacterial performance. The invention of application number 201910411303 discloses the use of borneol as a surface modifying component for textiles which are first surface modified with aminosilicones and then the aldehyde benzoic acid borneol is bonded to the surface of the textile. The invention can obtain stable and safe antimicrobial adhesion textile, and has good adhesion resistance to fungi and bacteria.
At present, the research on the antimicrobial property of borneol only stays on the modification of a substrate by using borneol alone and has remarkable antimicrobial effect, but the antimicrobial property of the surface of a modified material cannot be realized by photoinitiated polymerization of an acrylic monomer of borneol (see a comparative example).
In addition, the modification method of the aforementioned patent is limited to a group having high reactivity, and the operation steps are relatively complicated, resulting in unnecessary waste of resources during the production process. The active light grafting method can reduce the dosage of functional monomers, and realize the application of most polymers in the field of antimicrobial adhesion, which has important significance for production and life.
Disclosure of Invention
The invention aims to provide an application of a non-release type antimicrobial adhesion coating in an antibacterial milk bottle, by which the non-release type antimicrobial adhesion coating mainly composed of a copolymer of borneol acrylate and polyethylene glycol diacrylate is modified on the surface of the milk bottle, and the milk bottle with the non-release type antimicrobial adhesion coating is obtained, and has excellent and durable antibacterial performance.
The invention provides an application of a non-release type antimicrobial adhesion coating in an antibacterial milk bottle, which comprises grafting borneol acrylate and polyethylene glycol diacrylate on the surface of the milk bottle through photoinitiated polymerization to obtain the non-release type antimicrobial adhesion coating, thus obtaining the milk bottle with the non-release type antimicrobial adhesion coating; wherein, the polymer forming the non-release type antimicrobial adhesion coating is formed by copolymerizing two monomers of borneol acrylate and polyethylene glycol diacrylate, and the molecular structure is shown in a formula (I):
in the formula (I), n is the number of repeated units of the polymer, and the value is a positive integer;
the feeding bottle comprises a feeding bottle made of PP (polypropylene) or PET (Polyethylene terephthalate, polyester).
In the invention, the borneol acrylate is one or more of L-borneol acrylate, D-borneol acrylate and Iso-borneol acrylate.
In the invention, the molecular weight of the polyethylene glycol diacrylate is 200-1000.
According to the present invention, the non-releasing antimicrobial adhesion coating is capable of preventing fungi and bacteria from adhering; preferably, the molar ratio of borneol acrylate to polyethylene glycol diacrylate in the non-release antimicrobial adhesive coating is (0.3-3) to 1; further preferably, the mole fraction of the borneol acrylate in the non-releasing antimicrobial adhesion coating is 0.25 to 0.75.
In the present invention, the photoinitiator for photoinitiated polymerization includes benzophenone and/or isopropylthioxanthone.
According to some embodiments of the invention, the application includes,
step C, dispersing the photoinitiator solution on the surface of the feeding bottle, and carrying out illumination, washing and drying in a nitrogen atmosphere to obtain the feeding bottle with the surface modified by the photoinitiator;
step D, dispersing a mixed solution of a borneol acrylate monomer and a polyethylene glycol diacrylate monomer on the surface of the feeding bottle with the surface modified by the photoinitiator, and carrying out illumination, washing and drying in a nitrogen atmosphere to obtain the feeding bottle with the surface provided with the non-release type antimicrobial adhesion coating;
And, the surface of the feeding bottle includes an inner surface of the feeding bottle and an outer surface of the feeding bottle.
According to some embodiments of the invention, the photoinitiator solution is obtained by dissolving a photoinitiator in ethanol, performing vortex and ultrasonic treatment, and then introducing nitrogen to remove oxygen; preferably, the concentration of the photoinitiator solution is between 0.1 and 0.5g/mL; further preferably, the photoinitiator comprises benzophenone and/or isopropylthioxanthone.
According to other embodiments of the present invention, the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer is obtained by dissolving the borneol acrylate monomer and the polyethylene glycol diacrylate monomer in ethanol, performing vortex and ultrasonic treatment, and then introducing nitrogen to remove oxygen; preferably, in the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer, the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate is (0.3-3) to 1; further preferably, the concentration of the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer is 50% -80% (v/v).
In the invention, the light source is a high-pressure mercury lamp with the weight of 200-1000W, and the illumination time is 5-10min.
In some embodiments of the invention, in step C, the washing comprises soaking with an ethanol solution at room temperature for 5-10 hours;
in other embodiments of the present invention, in step D, the washing comprises soaking sequentially with dichloromethane and ethanol solution at room temperature for 5-10 hours, followed by sonication for 20-30min after each soak.
According to the invention, in step C, the feeding bottle is a pretreated feeding bottle; further preferably, the pretreatment method of the feeding bottle comprises soaking in ethanol for 10 hours, performing ultrasonic treatment for 30 minutes, washing with ethanol, and drying in vacuum.
The invention also provides a feeding bottle with a non-releasing antimicrobial adhesion coating on the surface, which is obtained in the application.
The invention provides an application of a non-release type antimicrobial adhesion coating in an antimicrobial feeding bottle, wherein the main component of the non-release type antimicrobial adhesion coating is composed of a copolymer of two monomers, namely, borneol Acrylate (BA) and polyethylene glycol diacrylate (PEGDA), so as to construct an amphiphilic stereochemical antimicrobial high-molecular coating, and the coating has good antimicrobial adhesion. The preparation method of the coating mainly comprises the following steps: firstly, preparing a monomer and a photoinitiator into a solution with a certain concentration, then, modifying the feeding bottle in two steps by using a light grafting method, wherein the photoinitiator is fixed on the surface of the feeding bottle in the first step, and the monomer is grafted by surface free radical initiation polymerization in the second step. The preparation method is simple, and the obtained grafted coating is safe and stable; the advantages of the borneol polyacrylate and the polyethylene glycol diacrylate can be fully exerted, and the adhesion of microorganisms is synergistically prevented; the coating is applied to surface modification of the feeding bottle, and can ensure that the grafted coating has a smooth structure.
Drawings
The invention is described in further detail below with reference to the accompanying drawings:
fig. 1 shows the molecular structure of the polymers constituting the non-releasing antimicrobial adhesion coating.
FIG. 2 is a scanning electron micrograph of a grafted PBA-PPEGDA coating on the surface of a polypropylene film according to example 2.
FIG. 3 is a schematic illustration of a process for preparing a non-releasing antimicrobial adherent coating according to the present invention.
FIG. 4 is a graph comparing the results of fungal (Aspergillus niger) contamination of the surface of a hollow white bottle sample of example 5 with the surface of a bottle sample grafted with a PBA-PPEGDA coating.
FIG. 5 is a graph comparing the results of plate counts of the number of adherent bacteria (Staphylococcus aureus) on the surface of the hollow white baby bottle sample of example 5 and the surface of the baby bottle sample grafted with the PBA-PPEGDA coating.
Detailed Description
In order that the invention may be readily understood, the invention will be described in detail below with reference to the accompanying drawings. Before the present invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
I. Terminology
The terms "about," "substantially," and "primarily" as used herein in connection with a range of a component, concentration, temperature, or other physical or chemical property or characteristic, cover a variation that may exist in the upper and/or lower limit of the range of the property or characteristic, including, for example, variations caused by rounding off, measurement methods, or other statistical variation. As used herein, a numerical value associated with an amount, weight, etc., is defined as "about" all values of each particular value plus or minus 1%. For example, the term "about 10%" should be interpreted as "9% to 11%".
II. Description of the embodiments
As described above, in the two methods for preparing the polymer antibacterial material, the antibacterial component is added in the preparation process, so that the difficulty of the production process is high, and the utilization rate of the antibacterial component is low; after the polymer is processed and formed, the antibacterial component is loaded on the surface, so that the antibacterial component is released, the effect durability is poor, and even the released antibacterial component affects the food safety and the like. In addition, it is difficult to have both fungal and bacterial resistance in the existing antibacterial materials.
At present, the research on the antimicrobial property of borneol only stays on the modification of a substrate by using borneol alone, and has obvious antimicrobial effect, but the antimicrobial property of the surface of a grafted material cannot be realized by photoinitiated polymerization of acrylic monomers of borneol. The existing grafting method is limited to groups with high reactivity, the operation steps are relatively complex, and unnecessary resource waste can be caused in the production process.
In view of the above, the present inventors have made extensive studies on an efficient and stable non-releasing antimicrobial adhesion coating and a method for preparing the same. The invention is designed and found that the borneol acrylate and the polyethylene glycol diacrylate are grafted on the surface of a high polymer material and copolymerized to prepare the borneol-based non-release antibacterial polymer coating, and the coating mainly consists of the copolymer of the borneol acrylate and the polyethylene glycol diacrylate and has good antibacterial performance. The present inventors have applied the non-releasing antimicrobial polymer coating to a packaging material to obtain the present invention.
The application of the non-release type antimicrobial adhesive coating in the antibacterial milk bottle can be understood as a method for grafting the non-release type antimicrobial adhesive coating on the surface of the milk bottle, which comprises the steps of grafting borneol acrylate and polyethylene glycol diacrylate on the surface of the milk bottle through photoinitiated polymerization to obtain the non-release type antimicrobial adhesive coating by copolymerization, so as to obtain the milk bottle with the non-release type antimicrobial adhesive coating; wherein, the polymer forming the non-release type antimicrobial adhesion coating is formed by copolymerizing two monomers of borneol acrylate and polyethylene glycol diacrylate, and the molecular structure is shown in a formula (I) (see figure 1):
In the formula (I), n is the number of repeated units of the polymer, and the value is a positive integer;
specifically, the method for grafting the non-release type antimicrobial adhesion coating on the surface of the feeding bottle comprises the steps of grafting borneol acrylate and polyethylene glycol diacrylate on the surface of the feeding bottle through a photoinitiator to generate surface free radicals, and copolymerizing the surface of the feeding bottle to obtain the non-release type antimicrobial adhesion coating, so that the feeding bottle with the non-release type antimicrobial adhesion coating is obtained.
The feeding bottle comprises a feeding bottle of PP (polypropylene) or PET (Polyethylene terephthalate, polyester), and the surface of the feeding bottle comprises an inner surface of the feeding bottle and an outer surface of the feeding bottle.
In the invention, the borneol acrylate is one or more of L-borneol acrylate, D-borneol acrylate and Iso-borneol acrylate.
In the invention, the molecular weight of the polyethylene glycol diacrylate is 200-1000.
The invention creatively selects the hydrophilic polyethylene glycol diacrylate monomer as the cyclic complementary molecule to form the antimicrobial adhesion coating with local amphipathy, thereby realizing the effect of synergistically enhancing the antimicrobial adhesion.
In the present invention, the photoinitiator includes benzophenone and/or isopropylthioxanthone.
The inventors conducted an antimicrobial adhesion test on a non-releasing antimicrobial adhesion coating, and the results showed that:
(1) When the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate in the non-release antimicrobial adhesive coating is (0.3-3) to 1, the anti-adhesive coating has excellent anti-adhesive effect on fungi; when the mole fraction of borneol acrylate is less than 0.25 or more than 0.75, the antifungal adhesion effect is reduced to various degrees; in particular, when borneol acrylate and polyethylene glycol diacrylate are used alone, a complete antifungal adhesion effect cannot be achieved.
(2) When the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate in the non-release antimicrobial adhesion coating is (0.3-3) to 1, the antibacterial adhesion effect is optimal; in particular, when borneol acrylate and polyethylene glycol diacrylate are used alone, a good antibacterial adhesion effect cannot be achieved.
As can be seen from the above, the non-releasing antimicrobial adhesive coating provided by the present invention can effectively inhibit fungi and bacteria from adhering to the surface thereof; preferably, the molar ratio of borneol acrylate to polyethylene glycol diacrylate in the non-release antimicrobial adhesive coating is (0.3-3) to 1; further preferably, the mole fraction of the borneol acrylate in the non-releasing antimicrobial adhesion coating is 0.25 to 0.75.
The invention realizes the grafting modification of the feeding bottle made of PP/PET materials. The antibacterial coating with a cross-linked structure is synthesized in two steps by an ultraviolet grafting method. The coating is connected with the surface of the milk bottle through chemical bonds, and has good stability. The monomer borneol acrylate is used as a hydrophobic chain segment and a stereochemical chain segment, and the polyethylene glycol diacrylate is used as a hydrophilic chain segment. The hydrophilic chain segment is polyethylene glycol diacrylate, so that grafting efficiency and surface grafting flatness can be ensured, and a grafted coating with excellent performance can be prepared by adjusting the proportion of the polyethylene glycol diacrylate to the borneol acrylate.
From the above, it can be seen that the antimicrobial coating provided by the present invention is a non-releasing material that affects microbial adhesion by the molecular structure of the coating surface, rather than releasing the antimicrobial agent, and is a safe, environment-friendly coating. Thus, the use of the non-release antimicrobial adherent coating in the antimicrobial packaging material of the present invention also includes the use of a baby bottle having a non-release antimicrobial adherent coating in a maternal product that requires antimicrobial activity.
The flow chart of the method for preparing the non-release type antimicrobial adhesive coating on the antibacterial feeding bottle by using the method is shown in figure 3, and as can be seen from figure 3, the method grafts the borneol acrylate and the polyethylene glycol diacrylate on the surface of the feeding bottle with C-H bonds on the surface through the photoinitiator, and the non-release type antimicrobial adhesive coating is formed on the surface of the feeding bottle through the graft copolymerization of the borneol acrylate and the polyethylene glycol diacrylate.
The technical scheme for preparing the non-release type antimicrobial adhesion coating is as follows:
(1) Preparing photoinitiator solution and monomer mixed solution
Dissolving a photoinitiator in ethanol, performing vortex and ultrasonic treatment, and then introducing nitrogen to remove oxygen to obtain a photoinitiator solution; preferably, the concentration of the photoinitiator solution is between 0.1 and 0.5g/mL; further preferably, the photoinitiator comprises benzophenone and/or isopropyl thioxanthone, still further preferably, the photoinitiator is benzophenone and isopropyl thioxanthone.
Dissolving a borneol acrylate monomer and a polyethylene glycol diacrylate monomer in ethanol, performing vortex and ultrasonic treatment, and then introducing nitrogen to remove oxygen to obtain a mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer; preferably, in the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer, the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate is (0.3-3) to 1.
The concentration of the prepared mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer is 50-80% (v/v). This is understood to mean that the total volume of both the monomers borneol acrylate and polyethylene glycol diacrylate is the volume percentage of the monomer mixed solution.
(2) Dispersing the photoinitiator solution on the surface of the feeding bottle, and carrying out illumination, washing and drying in a nitrogen atmosphere to obtain the feeding bottle with the surface modified by the photoinitiator;
(3) And dispersing the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer on the surface of the photoinitiated modified feeding bottle, and carrying out illumination, washing and drying in a nitrogen atmosphere to prepare the feeding bottle with the surface grafted with the non-release antimicrobial adhesion coating.
In some specific embodiments, in the step (2), benzophenone (BP) and Isopropyl Thioxanthone (ITX) are used as photoinitiators, and the photoinitiator is dispersed and adsorbed on the surface of the feeding bottle by dipping, coating or spraying, and the photoinitiator-modified feeding bottle is obtained by irradiating ultraviolet light for a certain time in a nitrogen atmosphere.
In some further specific embodiments, the feeding bottle is first soaked in ethanol, sonicated to remove impurities, and vacuum dried for use. And then the prepared photoinitiator solution is subjected to ultrasonic treatment and nitrogen is bubbled for a period of time, so that the oxygen is fully dissolved. Then dispersing and adsorbing the photoinitiator on the surface of the feeding bottle by adopting a dipping or coating or spraying method, irradiating for a period of time in a nitrogen atmosphere by ultraviolet light, soaking the feeding bottle in ethanol solution, and removing unreacted photoinitiator. Finally, the milk bottle modified by the photoinitiator is obtained by vacuum drying.
In still further specific embodiments, the borneol acrylate and polyethylene glycol diacrylate are first mixed with ethanol monomer solution of certain concentration in different proportions, then sonicated and sparged with nitrogen for a period of time to substantially deoxygenate. Then dispersing and adsorbing the monomer mixed solution on the surface of the feeding bottle with the surface modified by the photoinitiator by adopting a dipping or coating or spraying method, irradiating for a period of time in a nitrogen atmosphere by ultraviolet light, sequentially soaking in dichloromethane and ethanol solution, and removing ungrafted monomers and homopolymers by ultrasonic. Finally, the milk bottle with the surface grafted with the non-release antimicrobial adhesion coating is obtained by vacuum drying.
In some embodiments of the present invention, a specific method of preparing a baby bottle having a non-releasing antimicrobial adherent coating on its surface is as follows:
1. preparation work
(1) Soaking the feeding bottle in ethanol for 10h and performing ultrasonic treatment for 30min to remove impurities on the surface of the film, and drying to obtain the feeding bottle to be modified.
(2) The photoinitiator isopropyl thioxanthone and benzophenone are prepared into 0.1-0.5g/mL ethanol solution according to the molar ratio of (1-5) to 1, and then the ethanol solution is treated by ultrasonic treatment and nitrogen is introduced to remove oxygen.
(3) Preparing a solution with the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate of (0.3-3) to 1 and the monomer solution concentration of 50-80% (volume fraction), and using the borneol acrylate and the polyethylene glycol diacrylate as a control, carrying out ultrasound, and introducing nitrogen to remove oxygen.
2. The first step of modification preparation process of the feeding bottle comprises the following steps:
dispersing and adsorbing the photoinitiator on the surface of the feeding bottle by adopting a dipping or coating or spraying method, preheating a high-pressure mercury lamp for 1min, rotating and irradiating the feeding bottle for 5-10min in a nitrogen atmosphere, taking out and soaking the feeding bottle in ethanol solution for 5-10h for cleaning, drying, and removing unreacted photoinitiator to obtain the feeding bottle with the surface modified by the photoinitiator.
3. The second grafting preparation process of the feeding bottle comprises the following steps:
dispersing and adsorbing 50-200 mu L of monomer solution on the surface of a milk bottle by adopting a dipping or coating or spraying method, preheating a high-pressure mercury lamp for 1min, radiating the milk bottle in a nitrogen atmosphere for 5-10min in a rotating way, sequentially putting the milk bottle into a dichloromethane solution and an ethanol solution, respectively cleaning for 5-10h, carrying out ultrasonic treatment for 20-30min each time to remove unreacted monomers and homopolymers, and drying to remove the solvent to obtain the milk bottle with the antimicrobial coating.
The invention combines the hydrophilic and hydrophobic chain segments with the stereochemical strategy through light grafting, is easy to implement, and can be applied to the feeding bottle with the antimicrobial requirement.
The reaction efficiency is reflected in the present invention by the grafting ratio calculated by the following formula:
percent grafting = [ (film mass after grafting-film mass before grafting)/total mass of monomer charged ] ×100%
The antibacterial or antimicrobial test method in the invention is as follows:
determination of antifungal adhesion properties: cutting blank substrate (such as milk bottle) and substrate grafted with non-release antimicrobial adhesive composite coating into round sample with diameter of 10.0+ -0.1 mm, irradiating front and back sides under ultraviolet lamp for 1 hr for sterilization, and co-culturing with fungi.
Specifically, the film with composite coating layer is flatly attached to malt extract agar medium, and then 10 μl fungus liquid [ fungus spore liquid, containing spores (1-5) ×10 ] is added dropwise at a distance of 1-2cm from the material 8 personal/mL]Culturing at 30deg.C under constant temperature and humidity for 8 days at relative humidity of 85% + -5%, observing and recording the surface contamination of the substrate material with a camera. The mildew-proof effect evaluation criteria are shown in table 1, wherein the test is judged to be effective when the mold growth is not observed by the naked eye on the surface of the blank test sample when the coverage area of the mold on the surface of the control sample is more than 60% (i.e., the mildew-proof effect reaches level 4), and otherwise the test is not effective.
TABLE 1 evaluation criteria for mildew resistance
| Mold growth condition | Mildew resistant grade |
| No obvious mould growth under magnifying glass | 0 |
| Mold growth is rare or local, and the coverage area on the surface of the sample is less than 10 percent | 1 |
| The coverage area of mould on the surface of the sample is less than 30 percent (10 to 30 percent) | 2 |
| The coverage area of the mould on the surface of the sample is less than 60 percent (30 to 60 percent) | 3 |
| The coverage area of mould on the surface of the sample reaches or exceeds 60 percent | 4 |
Determination of antibacterial adhesion properties: cutting a blank substrate (such as a milk bottle) and a substrate grafted by a non-release antimicrobial adhesive composite coating into a round sample with the diameter of 10.0+/-0.1 mm, irradiating the front and the back of the sample for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing the sample with bacteria.
Specifically, the bacterial concentration was first formulated to be 10 7 CFU/mL PBS bacterial suspension, the blank substrate material and the substrate material grafted by the non-release antimicrobial adhesion composite coating are immersed in 1mL of bacteria with the concentration of 10 7 Culturing in PBS (phosphate buffered saline) with CFU/mL at 4deg.C for 24 hr, taking out, washing with sterile physiological saline for three times, and removing with filter paperCleaning solution, placing in 1.8mL of sterile physiological saline, performing ultrasonic treatment for 15min, coating 100 μl of plate, culturing at 37+ -2deg.C for 24h, performing plate colony counting, and calculating antibacterial adhesion rate according to formula (III):
R(％)＝[(A-B)/A]×100％ (III)
In formula (III):
antibacterial adhesion rate of R-test specimen;
the A-substrate material and bacterial liquid act for 24 hours, and then the surface bacteria adhesion quantity (CFU/mL) is obtained;
and (3) carrying out surface bacterial adhesion quantity (CFU/mL) after the base material grafted by the B-non-release type antimicrobial adhesion coating acts on the bacterial liquid for 24 hours.
Examples
The present invention will be specifically described below by way of specific examples. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, are commercially available.
The species for antifungal experiments or antibacterial experiments include:
aspergillus niger (Aspergillus niger) (ATCC 16404); staphylococcus aureus (Staphylococcus aureus) (ATCC 25923); wherein the term "ATCC" refers to American type culture Collection (American Type Culture Collection). All the strains are purchased in China center for type culture Collection of microorganisms, and each strain is independently used as an experimental strain to perform an antifungal experiment or an antibacterial experiment on a sample to be tested.
Malt extract (wort) agar medium used in the antifungal experiments, nutrient agar medium for bacterial counting in the antibacterial experiments, and TSB medium (trypticase soy peptone liquid medium) for preparing bacterial liquids were all purchased from beijing obbo biotechnology limited.
Example 1:
preparation of a grafted PBA-PPEGDA coating of a polyacrylonitrile membrane:
(1) Solution preparation
Preparation of photoinitiator solution: 4.2300g of isopropyl thioxanthone and 0.6066g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower (ND 400, rui Cheng instruments Co., hangzhou) to fully deoxidize, and a photoinitiator solution is obtained.
Preparation of the monomer solution: 2.08mL BA,2.00mL PEGDA (relative molecular weight 200) was uniformly mixed (molar ratio of BAP to PEGDA: 1), and then 0.8mL of the mixed monomer and 0.2mL of ethanol were sucked and placed in a brown sample bottle to carry out ultrasonic treatment, and then nitrogen was introduced to remove oxygen for 20 minutes, thereby obtaining a monomer solution.
(2) Preparation of photoinitiator-modified Polyacrylonitrile films
Soaking polyacrylonitrile membrane in ethanol for 10h, removing impurities by ultrasonic treatment for 30min, washing the surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering the quartz plate with a polyacrylonitrile film. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10h, drying in a vacuum drying oven, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyacrylonitrile membrane.
(3) Preparation of Polyacrylonitrile Membrane with PBA-PPEGDA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the membrane, irradiating for 8min, sequentially putting the reaction device into dichloromethane solution and ethanol solution, respectively cleaning for 10h, carrying out ultrasonic treatment for 30min after each soaking to remove unreacted monomers and homopolymers, and drying to remove the solvent to obtain the polyacrylonitrile membrane with the PBA-PPEGDA coating, wherein the grafting efficiency of the monomers reaches 50 percent.
Determination of antifungal adhesion properties:
cutting the polyacrylonitrile film with the coating and the film without grafting into round pieces with the diameter of 1cm, irradiating the round pieces for 1h on the front side and the back side under an ultraviolet lamp for sterilization, then co-culturing the round pieces and the aspergillus niger in the same wort agar culture medium, dripping 10 mu L of aspergillus niger spore liquid on the position 1-2cm away from the material on the surface of the film with the grafting layer upwards, and culturing for 8 days to observe the surface pollution condition of the material. The results show that there is no obvious mold growth under the magnifier, which corresponds to the mold-proof grade 0, and the magnifier has excellent antifungal adhesion effect.
Comparative example 1: preparation of grafted PBA coating of polyacrylonitrile film:
(1) Solution preparation
Preparation of photoinitiator solution: 4.2300g of isopropyl thioxanthone and 0.6066g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: mixing 0.8mL of BA and 0.2mL of ethanol, placing the mixture into a brown sample bottle for ultrasonic treatment, and then introducing nitrogen to deoxidize for 20min to obtain a monomer solution (the mol ratio of BAP to PEGDA is 1:0).
(2) Preparation of photoinitiator-modified Polyacrylonitrile films
Soaking polyacrylonitrile membrane in ethanol for 10h, removing impurities by ultrasonic treatment for 30min, washing the surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering the quartz plate with a polyacrylonitrile film. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10h, drying in a vacuum drying oven, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyacrylonitrile membrane.
(3) Preparation of Polyacrylonitrile Membrane with PBA coating
According to the reaction model in the step (2), 100 mu L of monomer solution is dispersed on the surface of the membrane, the same irradiation is carried out for 8min, the reaction device is put into dichloromethane solution for cleaning for 10h, ultrasonic treatment is carried out for 30min after soaking, so as to remove unreacted monomer and homopolymer, and the polyacrylonitrile membrane with the PBA coating is obtained after drying and solvent removal, wherein the grafting efficiency of the monomer is 1.6%.
Determination of antifungal adhesion properties:
cutting the polyacrylonitrile film with the coating and the film without grafting into round pieces with the diameter of 1cm, irradiating the round pieces for 1h on the front side and the back side under an ultraviolet lamp for sterilization, then co-culturing the round pieces and the aspergillus niger in the same wort agar culture medium, dripping 10 mu L of aspergillus niger spore liquid on the position 1-2cm away from the material on the surface of the film with the grafting layer upwards, and culturing for 8 days to observe the surface pollution condition of the material. The results showed that the coverage of the mould on the surface of the sample was 27.3%, corresponding to mould-proof rating 2, which did not give a complete anti-fungal adhesion effect.
Comparative example 2:
preparation of a grafted PPEGDA coating of a polyacrylonitrile membrane:
(1) Solution preparation
Preparation of photoinitiator solution: 4.2300g of isopropyl thioxanthone and 0.6066g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: 0.8mL of PEGDA (relative molecular weight 200) was taken, and 0.2mL of ethanol was mixed and placed in a brown sample bottle for ultrasonic treatment, and then deoxygenated with nitrogen for 20min to obtain a monomer solution (molar ratio of BAP to PEGDA was 0:1).
(2) Preparation of a photoinitiator modified polyacrylonitrile film the polyacrylonitrile film was soaked in ethanol for 10h, and the impurities were removed by ultrasound for 30min, the surface was rinsed with ethanol and dried in vacuo. And supporting the quartz plate bottom layer, and covering the quartz plate with a polyacrylonitrile film. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10h, drying in a vacuum drying oven, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyacrylonitrile membrane.
(3) Preparation of Polyacrylonitrile Membrane with PPEGDA coating
According to the reaction model in the step (2), 100 mu L of monomer solution is dispersed on the surface of the membrane, the membrane is irradiated for 8min, the reaction device is put into ethanol solution for cleaning for 10h, after soaking, ultrasonic treatment is carried out for 30min, so as to remove unreacted monomer and homopolymer, and the polyacrylonitrile membrane with the PPEGDA coating is obtained after drying and removing the solvent, wherein the grafting efficiency of the monomer is 53%.
Determination of antifungal adhesion properties:
cutting the polyacrylonitrile film with the coating and the film without grafting into round pieces with the diameter of 1cm, irradiating the round pieces for 1h on the front side and the back side under an ultraviolet lamp for sterilization, then co-culturing the round pieces and the aspergillus niger in the same wort agar culture medium, dripping 10 mu L of aspergillus niger spore liquid on the position 1-2cm away from the material on the surface of the film with the grafting layer upwards, and culturing for 8 days to observe the surface pollution condition of the material. The coverage rate of the mould on the surface of the sample is 3.9%, which corresponds to the mould-proof grade 1, and the mould-proof grade cannot completely play a role in resisting fungal adhesion.
Example 2: preparation of a grafted PBA-PPEGDA coating of a polyethylene film:
(1) Solution preparation
Preparation of photoinitiator solution: 2.5400g of isopropyl thioxanthone and 1.8220g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: after 2.08mLBA and 4.00mLPEGDA (relative molecular weight 400) are uniformly mixed (the mol ratio of BAP to PEGDA is 1:1), 0.65mL of mixed monomer and 0.35mL of ethanol are sucked, and the mixture is placed in a brown sample bottle for ultrasonic treatment, and then nitrogen is introduced to remove oxygen for 20min, so that a monomer solution is obtained.
(2) Preparation of photoinitiator-modified polyethylene films
Soaking polyethylene film in ethanol for 10 hr, removing impurities by ultrasonic treatment for 30min, washing surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering a polyethylene film on the quartz plate. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10 hours, putting into a vacuum drying oven for drying, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyethylene film.
(3) Preparation of polyethylene film with PBA-PPEGDA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the film, irradiating for 8min, sequentially putting the reaction device into dichloromethane solution and ethanol solution, respectively cleaning for 10h, carrying out ultrasonic treatment for 30min after each soaking to remove unreacted monomers and homopolymers, and drying to remove the solvent to obtain the polyethylene film with the single-sided PBA-PPEGDA coating.
The ungrafted side of the coating was grafted in the same manner to give a polyethylene film with a double-sided PBA-PPEGDA coating, the grafting efficiency of the monomer being 94.6%. The reaction has the advantages of simple operation and high reaction efficiency.
The obtained PBA-PPEGDA coating was observed by a scanning electron microscope (Hitachi S-4700 scanning electron microscope, hitachi group, japan), and the result is shown in FIG. 2, and an obvious graft layer structure was observed, which indicates that the synthesis of the PBA-PPEGDA coating was successful.
Determination of antifungal adhesion properties:
cutting a blank polyethylene film and a polyethylene film modified by a non-release type antimicrobial adhesion composite coating into a round sample with the diameter of 10.0+/-0.1 mm, irradiating the front and the back of the round sample for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing the round sample with fungi for 8 days to observe the surface pollution condition of the material. The modified film surface has no obvious mould growth, corresponds to mould-proof grade 0, and has excellent antifungal adhesion effect.
Determination of antibacterial adhesion properties:
cutting the polyethylene film with coating and ungrafted polyethylene film into round pieces with diameter of 1cm, irradiating the front and back sides under ultraviolet lamp for 1 hr for sterilizationAnd (3) culturing with staphylococcus aureus. First, staphylococcus aureus 10 is prepared 7 And (3) immersing 1mL of the bacterial suspension in the CFU/mL PBS bacterial suspension, fully contacting and co-culturing the bacterial suspension with the material for 24 hours at the temperature of 4 ℃, taking out the material, washing the material with sterile physiological saline for three times, finally removing the washing liquid with filter paper, placing the material in 1.8mL of sterile physiological saline, carrying out ultrasonic treatment for 15 minutes, coating 100 mu L of flat plate, culturing for 24 hours at the temperature of 37 ℃, and calculating the colony number of the flat plate. The antibacterial adhesion rate of the staphylococcus aureus is 99.89%.
Comparative example 3:
preparation of grafted PBA coating of polyethylene film:
(1) Solution preparation
Preparation of photoinitiator solution: 2.5400g of isopropyl thioxanthone and 1.8220g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: mixing 0.65mL of BA and 0.35mL of ethanol, placing the mixture into a brown sample bottle for ultrasonic treatment, and then introducing nitrogen to deoxidize for 20min to obtain a monomer solution (the mol ratio of BAP to PEGDA is 1:0).
(2) Preparation of photoinitiator-modified polyethylene films
Soaking polyethylene film in ethanol for 10 hr, removing impurities by ultrasonic treatment for 30min, washing surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering a polyethylene film on the quartz plate. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10 hours, putting into a vacuum drying oven for drying, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyethylene film.
(3) Preparation of polyethylene film with PBA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the film, irradiating for 8min, putting the reaction device into dichloromethane solution for cleaning for 10h, carrying out ultrasonic treatment for 30min after soaking to remove unreacted monomer and homopolymer, and drying to remove the solvent to obtain the polyethylene film with the single-sided PBA coating.
The ungrafted side of the coating was grafted in the same manner to give a polyethylene film with a double-sided PBA coating, the grafting efficiency of the monomer being 30.0%.
Determination of antifungal adhesion properties:
cutting a blank polyethylene film and a polyethylene film modified by a PBA coating into round samples with the diameter of 10.0+/-0.1 mm, irradiating the front and the back of the samples for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing the samples with fungi for 8 days to observe the pollution condition of the surfaces of the materials. Mould is observed in both the blank film and the polyethylene film modified by the PBA coating, which corresponds to mould-proof grade 1, and the full anti-fungal adhesion effect cannot be achieved.
Determination of antibacterial adhesion properties:
cutting the polyethylene film with the coating and the polyethylene film without grafting into circular sheets with the diameter of 1cm, irradiating the front side and the back side for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing with staphylococcus aureus. Firstly, preparing staphylococcus aureus with concentration of 10 7 And (3) immersing 1mL of the bacterial suspension in the CFU/mL PBS bacterial suspension, fully contacting and co-culturing the bacterial suspension with the material for 24 hours at the temperature of 4 ℃, taking out the material, washing the material with sterile physiological saline for three times, finally removing the washing liquid with filter paper, placing the material in 1.8mL of sterile physiological saline, carrying out ultrasonic treatment for 15 minutes, coating 100 mu L of flat plate, culturing for 24 hours at the temperature of 37 ℃, and calculating the colony number of the flat plate.
The result shows that the polyethylene film with the grafted coating has a certain antibacterial adhesion effect, but has poor adhesion resistance, and the antibacterial adhesion rate of the polyethylene film to staphylococcus aureus is 84.3%.
Comparative example 4:
grafted PEGDA coating preparation of polyethylene film:
(1) Solution preparation of photoinitiator solution: 2.5400g of isopropyl thioxanthone and 1.8220g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: 0.65mL of PEGDA (relative molecular weight 400) was taken, 0.35mL of ethanol was mixed and placed in a brown sample bottle for ultrasonic treatment, and then deoxygenated by introducing nitrogen for 20min to obtain a monomer solution (molar ratio of BAP to PEGDA was 0:1).
(2) Preparation of photoinitiator-modified polyethylene films
Soaking polyethylene film in ethanol for 10 hr, removing impurities by ultrasonic treatment for 30min, washing surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering a polyethylene film on the quartz plate. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 8min. And taking out the model, soaking in ethanol solution for 10 hours, putting into a vacuum drying oven for drying, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyethylene film.
(3) Preparation of polyethylene film with PPEGDA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the film, irradiating for 8min, putting the reaction device into ethanol solution for cleaning for 10h, carrying out ultrasonic treatment for 30min after soaking to remove unreacted monomer and homopolymer, and drying to remove the solvent to obtain the polyethylene film with the single-sided PEGDA coating.
The ungrafted coating side was grafted in the same manner to obtain a polyethylene film with a double-sided PPEGDA coating, the grafting efficiency of the monomer was 93.4%.
Determination of antifungal adhesion properties:
cutting a blank polyethylene film and a polyethylene film modified by a PPEGDA coating into a round sample with the diameter of 10.0+/-0.1 mm, irradiating the front and back sides of the round sample for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing the round sample with fungi for 8 days to observe the pollution condition of the surface of the material. Mould is observed in the blank film and the polyethylene film modified by the PPEGDA coating, and the blank film and the polyethylene film correspond to mould proof grade 1, so that the full anti-fungal adhesion effect cannot be achieved.
Determination of antibacterial adhesion properties:
cutting the polyethylene film with the coating and the polyethylene film without grafting into circular sheets with the diameter of 1cm, irradiating the front side and the back side for 1h under an ultraviolet lamp for sterilization treatment, and then co-culturing with staphylococcus aureus. Firstly, preparing staphylococcus aureus with concentration of 10 7 And (3) immersing 1mL of the bacterial suspension in the CFU/mL PBS bacterial suspension, fully contacting and co-culturing the bacterial suspension with the material for 24 hours at the temperature of 4 ℃, taking out the material, washing the material with sterile physiological saline for three times, finally removing the washing liquid with filter paper, placing the material in 1.8mL of sterile physiological saline, carrying out ultrasonic treatment for 15 minutes, coating 100 mu L of flat plate, culturing for 24 hours at the temperature of 37 ℃, and calculating the colony number of the flat plate. The antibacterial adhesion rate of the staphylococcus aureus is 86.1 percent.
Example 3:
Preparation of a grafted PBA-PPEGDA coating of a polyethylene terephthalate film:
(1) Solution preparation of photoinitiator solution: 0.84g of isopropyl thioxanthone and 3.0333g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex and ultrasonic are carried out for 20min to fully dissolve the materials, finally the materials are bubbled for 20min by a nitrogen blower, and the materials are fully deoxidized to obtain a photoinitiator solution.
Preparation of the monomer solution: 1.56mLBA and 2.50mLPEGDA (relative molecular weight 1000) are mixed (the mol ratio of BAP to PEGDA is 3:1) and then are evenly dissolved by ultrasound, 0.5mL of mixed monomer and 0.5mL of ethanol are sucked, and the mixture is placed in a brown sample bottle for ultrasound treatment, and then nitrogen is introduced to remove oxygen for 20min, so as to obtain monomer solution.
(2) Preparation of photoinitiator-modified polyethylene terephthalate films
The polyethylene terephthalate film was soaked in ethanol for 10 hours, and the impurities were removed by ultrasound for 30 minutes, the surface was rinsed with ethanol, and vacuum dried. And supporting the quartz plate bottom layer, and covering the quartz plate with a polyethylene terephthalate film. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 5min. And taking out the model, soaking in ethanol solution for 5 hours, putting into a vacuum drying oven for drying, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polyethylene terephthalate film.
(3) Preparation of polyethylene terephthalate film with PBA-PPEGDA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the membrane, irradiating for 5min, sequentially putting the reaction device into dichloromethane solution and ethanol solution, respectively cleaning for 5h, carrying out ultrasonic treatment for 20min after each soaking to remove unreacted monomers and homopolymers, and drying to remove the solvent to obtain the polyethylene terephthalate membrane with the PBA-PPEGDA coating, wherein the grafting efficiency of the monomers reaches 90 percent.
Determination of antifungal adhesion properties:
cutting the polyethylene terephthalate film with the coating and the film which is not grafted into a circular sheet with the diameter of 1cm, irradiating the front and the back of the circular sheet for 1h under an ultraviolet lamp for sterilization treatment, then co-culturing the circular sheet and the film with the grafted layer in the same wort agar culture medium, placing the circular sheet with the grafted layer upwards at a position 1-2cm away from the center of a culture dish, then dripping 10 mu L of Aspergillus niger spore liquid into the center of the culture dish, and culturing for 8 days to observe the surface pollution condition of a material. As a result, the anti-mildew agent reaches the mildew-proof grade of 0 and has excellent anti-fungus adhesion effect.
Example 4: preparation of a grafted PBA-PPEGDA coating of a polypropylene film:
(1) Preparing a solution:
preparation of photoinitiator solution: 0.6600g of isopropyl thioxanthone and 0.3400g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: after 1.04mLBA and 3.00mLPEGDA (relative molecular weight 200) were uniformly mixed (molar ratio of BAP to PEGDA: 1:3), 0.8mL of the mixed monomer and 0.2mL of ethanol were sucked and put into a brown sample bottle for ultrasonic treatment, and then nitrogen was introduced to remove oxygen for 20min, thereby obtaining a monomer solution.
(2) Preparation of photoinitiator-modified Polyacrylonitrile films
Soaking polypropylene film in ethanol for 10 hr, removing impurities by ultrasonic treatment for 30min, washing surface with ethanol, and vacuum drying. And supporting the quartz plate bottom layer, and covering a polypropylene film on the quartz plate. 100. Mu.L of the photoinitiator solution was pipetted onto the membrane surface by a pipette, a further quartz plate was covered over the membrane, the bubbles were removed by gentle pressure, and a liquid interlayer was formed. After the high-pressure mercury lamp was preheated for 1min, the obtained reaction device model was put under the high-pressure mercury lamp and irradiated for 10min. And taking out the model, soaking in ethanol solution for 8 hours, putting into a vacuum drying oven for drying, and removing the unreacted photoinitiator and solvent to obtain the photoinitiator modified polypropylene film.
(3) Preparation of Polyacrylonitrile Membrane with PBA-PPEGDA coating
According to the reaction model in the step (2), dispersing 100 mu L of monomer solution on the surface of the film, irradiating for 10min, sequentially putting the reaction device into dichloromethane solution and ethanol solution, respectively cleaning for 8h, carrying out ultrasonic treatment for 25min after each soaking to remove unreacted monomers and homopolymers, and drying to remove the solvent to obtain the polypropylene film with the PBA-PPEGDA coating. After the reaction, the monomer was found to remain after the reaction, and was not in the form of a liquid, and all the monomer was grafted and fixed to the surface of the substrate. The reaction has the advantages of simple operation and high reaction efficiency.
Determination of antifungal adhesion properties:
cutting the polypropylene film with the coating and the film without grafting into round pieces with the diameter of 1cm, irradiating the round pieces for 1h on the front side and the back side under an ultraviolet lamp for sterilization treatment, then co-culturing the round pieces and the aspergillus niger in the same wort agar culture medium, placing the surface of the film with the grafting layer upwards at a position 1-2cm away from the center of a culture dish, then dripping 10 mu L of aspergillus niger spore liquid into the center of the culture dish, and culturing for 8 days to observe the surface pollution condition of the material. As a result, the anti-mildew agent reaches the mildew-proof grade of 0 and has excellent anti-fungus adhesion effect.
Example 5:
preparing a PP/PET feeding bottle with a PBA-PPEGDA coating grafted on the surface:
(1) Preparing a solution:
preparation of photoinitiator solution: 4.2300g of isopropyl thioxanthone and 0.6066g of benzophenone are weighed into a brown sample bottle, then 10mL of ethanol is added, vortex is carried out, ultrasound is carried out for 20min to fully dissolve the mixture, finally the mixture is bubbled for 20min by a nitrogen blower, and the mixture is fully deoxygenated, thus obtaining a photoinitiator solution.
Preparation of the monomer solution: 2.08mL BA,2.00mL PEGDA (relative molecular weight 200) was uniformly mixed (molar ratio of BAP to PEGDA: 1), and then 0.8mL of the mixed monomer and 0.2mL of ethanol were sucked and placed in a brown sample bottle to carry out ultrasonic treatment, and then nitrogen was introduced to remove oxygen for 20 minutes, thereby obtaining a monomer solution.
(2) Preparation of PP/PET milk bottle with photoinitiator modified surface
Soaking the milk bottle in ethanol for 10 hr, removing impurities by ultrasonic treatment for 30min, washing the surface with ethanol, and vacuum drying. Dispersing and adsorbing the photoinitiator solution on the inner and outer surfaces of the feeding bottle by a dipping or coating or spraying method, preheating a high-pressure mercury lamp for 1min, rotating and irradiating the feeding bottle for 8min in a nitrogen atmosphere, taking out the feeding bottle, and soaking the feeding bottle in an ethanol solution for 10h to obtain the PP/PET feeding bottle with the surface modified by the photoinitiator.
(3) Preparation of PP/PET feeding bottle with PBA-PPEGDA coating on surface
According to the method of the step (2), a dipping or coating or spraying method is adopted to disperse and adsorb monomer solution on the inner surface and the outer surface of the feeding bottle, after a high-pressure mercury lamp is preheated for 1min, the feeding bottle is rotated and irradiated for 8min in nitrogen atmosphere, the feeding bottle is taken out, and is sequentially put into a dichloromethane solution and an ethanol solution to be respectively washed for 10h, after each soaking, ultrasonic treatment is carried out for 30min, unreacted monomers and homopolymers are removed, and the feeding bottle with a PBA-PPEGDA coating is obtained after drying and solvent removal. After the reaction, the monomer is not remained after the reaction, and the monomer is not in a liquid form, so that all the monomer is grafted and fixed on the surface of the feeding bottle. The reaction has the advantages of simple operation and high reaction efficiency.
Determination of antifungal adhesion properties:
cutting a blank feeding bottle and a non-release antimicrobial adhesion coating modified feeding bottle into round samples with the diameter of 10.0+/-0.1 mm, irradiating the front and back sides of the feeding bottle under an ultraviolet lamp for 1h for sterilization treatment, and then co-culturing the feeding bottle and fungi for 8 days to observe the surface pollution condition of the material. There was no significant mold growth under the magnifier, which corresponds to mold resistance rating 0, which has excellent antifungal adhesion effect (see fig. 4).
Determination of antibacterial adhesion properties:
Cutting blank feeding bottle and non-release antimicrobial coating modified feeding bottle into round pieces with diameter of 1cm, irradiating front and back sides under ultraviolet lamp for 1 hr for sterilization, and co-culturing with Staphylococcus aureus. Firstly, preparing staphylococcus aureus with concentration of 10 7 And (3) immersing 1mL of the bacterial suspension in the CFU/mL PBS bacterial suspension, fully contacting and co-culturing the bacterial suspension with the material for 24 hours at the temperature of 4 ℃, taking out the material, washing the material with sterile physiological saline for three times, finally removing the washing liquid with filter paper, placing the material in 1.8mL of sterile physiological saline, carrying out ultrasonic treatment for 15 minutes, coating 100 mu L of flat plate, culturing for 24 hours at the temperature of 37 ℃, and calculating the colony number of the flat plate. The results showed that the antimicrobial adhesion of the non-releasing antimicrobial adhesion coating-modified baby bottle to staphylococcus aureus was 99.31% (see fig. 5).
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (11)
1. The application of the non-release type antimicrobial adhesion coating in the antibacterial milk bottle comprises grafting borneol acrylate and polyethylene glycol diacrylate on the surface of the milk bottle through photoinitiated polymerization to obtain the non-release type antimicrobial adhesion coating, thus obtaining the milk bottle with the non-release type antimicrobial adhesion coating; wherein, the polymer forming the non-release type antimicrobial adhesion coating is formed by copolymerizing two monomers of borneol acrylate and polyethylene glycol diacrylate, and the molecular structure is shown as a formula (I):
in the formula (I), n is the number of the repeated units of the polymer, and the value is a positive integer;
the feeding bottle comprises a feeding bottle made of PP or PET;
the non-releasing antimicrobial adhesion coating is capable of preventing fungi and bacteria from adhering; the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate in the non-release antimicrobial adhesive coating is (0.3-3): 1, a step of; the mole fraction of the borneol acrylate in the non-releasing antimicrobial adhesion coating is 0.25-0.75.
2. The use according to claim 1, wherein the borneol acrylate is one or more of L-borneol acrylate, D-borneol acrylate and Iso-borneol acrylate; and/or, the molecular weight of the polyethylene glycol diacrylate is 200-1000.
3. Use according to claim 1, characterized in that the photoinitiator for the photoinitiated polymerization comprises benzophenone and/or isopropylthioxanthone; and/or, the surface of the feeding bottle comprises an inner surface of the feeding bottle and an outer surface of the feeding bottle.
4. The use according to any one of claims 1-3, wherein the use comprises,
step C, dispersing the photoinitiator solution on the surface of the feeding bottle, and carrying out illumination, washing and drying in a nitrogen atmosphere to obtain the feeding bottle with the surface modified by the photoinitiator;
step D, dispersing a mixed solution of a borneol acrylate monomer and a polyethylene glycol diacrylate monomer on the surface of the feeding bottle with the surface modified by the photoinitiator, and carrying out illumination, washing and drying in a nitrogen atmosphere to obtain the feeding bottle with the surface provided with the non-release type antimicrobial adhesion coating;
and, the surface of the feeding bottle includes an inner surface of the feeding bottle and an outer surface of the feeding bottle.
5. The use according to claim 4, wherein the photoinitiator solution is obtained by dissolving a photoinitiator in ethanol, vortexing, sonicating, and then deoxygenating by introducing nitrogen; the concentration of the photoinitiator solution is 0.1-0.5g/mL; the photoinitiator comprises benzophenone and/or isopropyl thioxanthone.
6. The use according to claim 4, wherein the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer is obtained by dissolving the borneol acrylate monomer and the polyethylene glycol diacrylate monomer in ethanol, performing vortex and ultrasonic treatment, and then introducing nitrogen to remove oxygen; in the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer, the molar ratio of the borneol acrylate to the polyethylene glycol diacrylate is (0.3-3) 1; the concentration of the mixed solution of the borneol acrylate monomer and the polyethylene glycol diacrylate monomer is 50-80 v/v%.
7. The use according to claim 4, wherein,
the light source of illumination is a high-pressure mercury lamp with the power of 200-1000W, and the illumination time is 5-10min;
and/or, in step C, the washing comprises soaking with an ethanol solution at room temperature for 5-10 hours;
and/or, in the step D, the washing comprises soaking with dichloromethane and ethanol solution for 5-10h at room temperature, and carrying out ultrasonic treatment for 20-30min after each soaking.
8. The use according to any one of claims 5-6, characterized in that,
the light source of illumination is a high-pressure mercury lamp with the power of 200-1000W, and the illumination time is 5-10min;
And/or, in step C, the washing comprises soaking with an ethanol solution at room temperature for 5-10 hours;
and/or, in the step D, the washing comprises soaking with dichloromethane and ethanol solution for 5-10h at room temperature, and carrying out ultrasonic treatment for 20-30min after each soaking.
9. The use according to claim 4, wherein in step C the feeding bottle is a pre-treated feeding bottle; the pretreatment method of the milk bottle comprises the steps of soaking the milk bottle in ethanol for 10 hours, carrying out ultrasonic treatment for 30 minutes, washing the milk bottle with ethanol, and carrying out vacuum drying.
10. Use according to any one of claims 5-6, wherein in step C the feeding bottle is a pre-treated feeding bottle; the pretreatment method of the milk bottle comprises the steps of soaking the milk bottle in ethanol for 10 hours, carrying out ultrasonic treatment for 30 minutes, washing the milk bottle with ethanol, and carrying out vacuum drying.
11. A feeding bottle with a non-releasing antimicrobial adherent coating on the surface, obtainable in the use according to any one of claims 1-10.
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Application publication date: 20211221 Assignee: Liuyang Jiangnan Plastic Products Co.,Ltd. Assignor: BAOSHENG CO.,LTD. Contract record no.: X2023980045983 Denomination of invention: Application of Non Release Antibacterial Adhesive Coatings in Antibacterial Milk Bottles Granted publication date: 20230502 License type: Common License Record date: 20231108 |