CN114835840B - Antioxidant uvioresistant microsphere, preparation method and application - Google Patents
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Abstract
The invention provides an antioxidant uvioresistant microsphere, a preparation method and application, and belongs to the technical field of high polymer materials. Firstly, maleic anhydride copolymer microspheres are prepared by a simple and efficient self-stabilization precipitation polymerization method, and the microspheres can be obtained by centrifugation or filtration purification after the reaction is finished; then, ethylenediamine is used for carrying out amination modification on the microsphere, and then the phenolic acid antioxidant is grafted to the surface of the amination microsphere through EDC/NHS mediated amidation reaction to obtain the antioxidant uvioresistant microsphere. The prepared microspheres can be used for preparing antioxidant ultraviolet shielding composite materials, and have great application potential in the fields of food packaging materials, sun protection and skin care, coatings and the like.
Description
Technical Field
The invention belongs to the field of functional composite materials, and particularly relates to an antioxidant uvioresistant microsphere, a preparation method and application thereof in a composite material.
Background
Ultraviolet rays play a crucial role in the maintenance and development of life on the earth, can trigger photosynthesis, convert energy in sunlight into biochemical energy necessary for maintaining the life of the earth, and can promote the synthesis of vitamin D in a human body. In addition, ultraviolet rays are widely used in the fields of detection, photography, optical sensors, sterilization, medical diagnosis and treatment, and polymer processing. However, excessive uv radiation can not only be detrimental to human health, but can also destroy the structure and properties of many polymeric materials. The most direct and effective method of uv protection is the addition of uv screening agents to materials or personal care products. But commonly used inorganic UV screeners such as TiO 2 ZnO can generate a plurality of free radicals through photoactivation reaction after absorbing ultraviolet light, most of organic micromolecule ultraviolet absorbers have poor photostability, and the free radicals can be generated due to photodegradation reaction under the irradiation of the ultraviolet light. The free radicals not only can cause damage to human health, but also can accelerate the photooxidation degradation of the material when the free radicals exist in the polymer material, and the service life of the material is shortened.
One of the solutions to the above problems is to add antioxidants to products, which at low concentrations can retard or prevent molecular degradation caused by undesirable free radical reactions and radical-related oxidation, protecting the human body or materials from active oxygen. Phenolic acid compounds are important antioxidants, are secondary metabolites of plants and fungi, can protect the plants from being damaged by ultraviolet rays, insects, viruses and bacteria, and mainly derive from hydroxyl on a benzene ring in the capacity of scavenging free radicals. In addition to antioxidant and antibacterial properties, phenolic acid compounds and derivatives thereof also have anti-glycemic, anti-hypertensive, anti-inflammatory, and anti-thrombotic properties. In addition, many phenolic acid compounds also have good ultraviolet absorption effect, so that the phenolic acid compounds have great application potential in the aspect of ultraviolet shielding materials. However, most antioxidants are unstable to ultraviolet and oxygen and are prone to migration and heat stability when applied to food packaging or polymersPoor in performance and the like. Encapsulation of small molecule antioxidants into stable carriers or chemical bonding to polymers or inorganic materials is an effective approach to solve the above problems. Paper ACS apple Mater Interfaces 2012,4 (12), 6609-6617 covalently links antioxidant Gallic Acid (GA) to silane coupling agent modified Silica (SiO) silica (SiO 09-6617) 2 ) On the surface of the nano-particle, an efficient and stable antioxidant SiO is obtained 2 GA hybrid nanoparticles, but the study does not mention the uv-resistant effect of the material. Paper Biomacromolecules 2018,19 (9), 3883-3893 prepares microcapsules and nanocapsules of mixed polyphenols, sulfonate lignins and tannins by a layer-by-layer (LbL) procedure, sequentially depositing polyelectrolytes having opposite charges. Although these microcapsules and nanocapsules have high antioxidant activity and good ultraviolet shielding properties, the method is cumbersome to prepare and is not suitable for large-scale production.
The maleic anhydride copolymer microspheres can be prepared by a simple, efficient and environment-friendly self-stabilizing precipitation polymerization method, and the surfaces of the maleic anhydride copolymer microspheres have anhydride groups with high reactivity, so that the possibility is provided for further functionalization. At present, antioxidant uvioresistant microspheres based on maleic anhydride polymers have not yet seen relevant research reports.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an antioxidant uvioresistant microsphere, a preparation method and application thereof in a composite material. Firstly, preparing maleic anhydride copolymer microspheres by a simple, efficient and environment-friendly self-stabilization precipitation polymerization method, and after the reaction is finished, centrifuging or filtering and purifying to obtain a product; then, ethylenediamine is used for carrying out amination modification on the microspheres, then the phenolic acid antioxidant is grafted to the surfaces of the aminated microspheres through EDC/NHS mediated amidation reaction, and after the reaction is finished, the antioxidant and uvioresistant microspheres can be obtained through centrifugation or filtration purification. And then compounding the microspheres and a general high polymer material by a solution blending or melt blending method to prepare the antioxidant and uvioresistant composite material. The method is simple to operate, economical, efficient and suitable for industrial production.
The specific technical scheme of the invention is as follows:
in a first aspect, a preparation method of an antioxidant uvioresistant microsphere is provided, which comprises the following steps:
(1) Adding maleic anhydride, vinyl monomer, cross-linking agent and initiator into a solvent, performing ultrasonic dissolution to obtain a uniform reaction system, reacting the reaction system under the protection of inert gas, centrifuging or filtering and purifying after the reaction is finished, and drying to obtain maleic anhydride copolymer microspheres;
(2) Dispersing the maleic anhydride copolymer microspheres in the step (1) in a mixed solution of ethanol and water in a volume ratio of 1. And after the reaction is finished, centrifuging or filtering and purifying the product, and drying to obtain the aminated maleic anhydride copolymer microspheres.
(3) Dispersing the aminated maleic anhydride copolymer microspheres in the step (1) in deionized water. Meanwhile, phenolic acid antioxidants are dissolved in ethanol; and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide EDC was dissolved in MES buffer at pH 5-6. Then, adding a phenolic acid antioxidant solution into a buffer solution, adding N-hydroxysuccinimide NHS into the reaction solution, and reacting in an ice-water bath; then, the obtained reaction solution is added into an aminated maleic anhydride copolymer microsphere dispersion liquid, and reaction is carried out at room temperature. After the reaction is finished, centrifuging or filtering for purification, and then drying to obtain the antioxidant uvioresistant microspheres.
In the step (1), the maleic anhydride in the reaction system is 0.1-1mol/L, the vinyl monomer concentration is 0.1-1mol/L, and the initiator dosage is 0.5-5wt% of the total mass of the maleic anhydride and the vinyl monomer. The molar ratio of the cross-linking agent to the maleic anhydride is (5-30): 100.
In the step (1), the reaction temperature is 60-90 ℃ under the protection of inert gas, and the reaction time is 1-12h.
In the step (1), the vinyl monomer is one or a combination of more than two of styrene, alpha-methylstyrene, alpha-ethylstyrene, 4-ethylstyrene, p-methoxystyrene, p-methylstyrene, allyl benzene, vinyl toluene, indene, methylindene, benzofuran and methylbenzofuran.
In the step (1), the crosslinking agent is one or a combination of more than two of divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate.
In the step (1), the solvent is one or a mixture of more than two of butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, ethyl butyrate, isoamyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate and isoamyl phenylacetate.
In the step (1), the initiator is azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
In the step (2), the reaction time is 4-12h.
In the step (2), the content of the maleic anhydride copolymer microspheres in the mixed solution of ethanol and water is 20-100mg/mL; the dosage of the ethylenediamine is as follows: 0.5-2mL/g maleic anhydride copolymer microspheres.
In the step (3), the content of the aminated maleic anhydride copolymer microspheres in deionized water is 20-50mg/mL; the dosage of the phenolic acid antioxidant is 3-5mmol/g of aminated maleic anhydride copolymer microspheres; the molar ratio of the phenolic acid antioxidant to EDC and NHS is 1; the volume ratio of the deionized water to the ethanol to the MES buffer is 2.
In the step (3), the phenolic acid antioxidant is one or a combination of more than two of caffeic acid, 4-coumaric acid, ferulic acid, sinapic acid, gallic acid, protocatechuic acid and vanillic acid.
In the step (3), the temperature of the ice-water bath is 0 ℃; the reaction time in ice-water bath is 0.5-1h. The reaction time is 24-48h at room temperature.
In a second aspect, the antioxidant uvioresistant microspheres prepared by the method are provided, and the particle size of the antioxidant uvioresistant microspheres is 250-1300nm.
In a third aspect, an application of the antioxidant ultraviolet resistant microspheres prepared by the method is provided, which specifically comprises the following steps:
and mixing the antioxidant uvioresistant microspheres with a polymer matrix to prepare the antioxidant uvioresistant composite material, wherein the antioxidant uvioresistant microspheres account for 0.5-5 parts by weight of the polymer matrix 100 parts by weight.
The polymer matrix is one or the combination of more than two of polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyurethane, polyethylene, polyvinyl chloride and polypropylene.
The antioxidant uvioresistant composite material can be applied to the fields of food packaging materials, sun protection and skin care and coatings.
The preparation method of the antioxidant uvioresistant composite material is selected from any one of the following two types:
the first method is as follows: dissolving a polymer matrix in the solution, adding the antioxidant uvioresistant microspheres, uniformly mixing, pouring in a mold or blade-coating on a substrate, volatilizing and drying to prepare the antioxidant uvioresistant composite material;
the second method comprises the following steps: and melting and blending the polymer matrix and the antioxidant uvioresistant microspheres at the temperature of 70-190 ℃ to prepare the antioxidant uvioresistant composite material.
The invention at least comprises the following beneficial effects:
1. the phenolic acid modified maleic anhydride copolymer microspheres prepared by the invention have excellent antioxidant effect and ultraviolet shielding performance, can be dispersed in water and various organic solvents, and expand the application range of phenolic acid antioxidants.
2. The preparation method of the antioxidant uvioresistant microsphere is simple, the particle size of the microsphere is easy to regulate and control, the monodispersity is good, and the preparation method is suitable for large-scale production.
3. The high ultraviolet shielding performance can be realized by adding a very small amount of the antioxidant ultraviolet resistant microspheres in the polymer matrix, and the microspheres are not easy to migrate out of the polymer matrix.
Drawings
FIG. 1 is a scanning electron micrograph of an antioxidant UV resistant microsphere of example 1;
FIG. 2 shows the experimental results of the DPPH radical scavenging rate of the uvioresistant antioxidant microspheres, free caffeic acid and blank aminated microspheres in example 1.
FIG. 3 is a graph of the UV transmission spectrum of an antioxidant UV resistant PVB composite film of example 5;
Detailed Description
The sources of reagents used in the examples of the present invention are commercially available except where otherwise specified.
It is to be understood that the description herein is madeIs/are as followsThe detailed description is merely illustrative and explanatory of the invention and is not restrictive thereof. In addition to the starting materials used in the examples of the present invention, starting materials having the same functional groups as the starting materials used in the examples or containing the same structural units involved in the present invention, with equivalent substitution of the starting materials components, are intended to be included in the scope of the present invention. The present invention is further illustrated by the following specific examples.
The invention provides a drawing of the detection results of part of the embodiments, other embodiments and comparative examples adopt the same detection method, and a person skilled in the art can directly and unambiguously determine the content of the embodiments of the invention by using the detection method provided by the invention.
The antioxidant and uvioresistant microspheres provided by the embodiment of the invention can be dispersed in water and various organic solvents, have wide application range and excellent antioxidant and uvioresistant effects, and are suitable for large-scale production.
Preparing the antioxidant uvioresistant microspheres:
example 1
(1) Preparation of maleic anhydride copolymer microspheres: weighing 5.21g of styrene, 4.90g of maleic anhydride, 0.52g of divinylbenzene (the molar ratio is 100; general formula (N) 2 After 30min, the three-neck flask is placed in an oil bath kettle at 70 ℃, after 6h of reaction under the nitrogen atmosphere, the product is centrifuged for 5min at 10000r/min, and is washed with absolute methanol for three times and then placed in a vacuum stateDrying in an air oven to obtainMaleic anhydride copolymer microspheres 1；
(2) Amination of the microsphere: weighing 2gMaleic anhydride copolymer microspheres 1Then, 60mL of a mixed solution of ethanol and water (volume ratio 1. After the reaction is finished, centrifuging the product at 10000r/min for 5min, washing the product with anhydrous methanol for three times, and then placing the product in a vacuum oven for drying to obtain the productAminated maleic anhydride copolymer microspheres 1。
(3) Preparing the antioxidant uvioresistant microspheres: mixing 1gAminated maleic anhydride copolymer microspheres 1Dispersed in 20mL of deionized water. Meanwhile, caffeic acid (0.72g, 4mmol) was dissolved in 10mL ethanol; and EDC (0.77g, 4 mmol) was dissolved in 20mL MES buffer (pH 5.5). Subsequently, a caffeic acid solution was added to the buffer, and then NHS (0.46g, 4 mmol) was added to the reaction solution and reacted in an ice-water bath for 1h; the resulting reaction solution was then added to the microsphere dispersion and reacted at room temperature for 24h. After the reaction is finished, centrifuging for 5min at 10000r/min, washing for three times by water and ethanol respectively, and then drying in vacuum to obtainOxidation resistance Uvioresistant microsphere 1The particle sizes are shown in Table 1. The scanning electron microscope photograph of the antioxidant uvioresistant microsphere is shown in figure 1. The results of the antioxidant performance test of the antioxidant uvioresistant microspheres are shown in figure 2.
And (3) testing the oxidation resistance: the antioxidant performance of the microspheres was evaluated by DPPH free radical scavenging experiments. Mixing 1mL of 600 mu mol/L freshly prepared DPPH ethanol solution and 40-400 mu L of phenolic acid solution or anti-ultraviolet antioxidant microsphere solution containing equal amount of phenolic acid, and fixing the volume to 20mL, wherein the final concentration of DPPH is 30 mu mol/L, and the final concentration range of phenolic acid is 2-20 mu mol/L. The sample was stirred at 25 ℃ for 30min in the dark, centrifuged and the supernatant was taken for determination of the absorbance at 517 nm. Aminated maleic anhydride copolymer microspheres were used as controls.
Example 2
(1) Preparation of maleic anhydride copolymer microspheres: 5.21g of styrene, 4.90g of maleic anhydride and 0.99g of ethylene glycol dimethacrylate (molar ratio 100100mL of ethyl butyrate is ultrasonically dissolved and then connected with a reaction system, and the concentrations of styrene and maleic anhydride are respectively 0.5mol/L; general formula (N) 2 After 30min, placing the three-neck flask in an oil bath kettle at 80 ℃, reacting for 3h under the nitrogen atmosphere, centrifuging the product at 10000r/min for 5min, washing with anhydrous methanol for three times, and placing the product in a vacuum oven for drying to obtain the productMaleic anhydride copolymer microspheres 2；
(2) Amination of the microsphere: weighing 2gMaleic anhydride copolymer microspheres 2Then, 40mL of a mixed solution of ethanol and water (volume ratio 1. After the reaction is finished, centrifuging the product at 10000r/min for 5min, washing the product with anhydrous methanol for three times, and then placing the product in a vacuum oven for drying to obtain the productAminated maleic anhydride copolymer microspheres 2。
(3) Preparing the antioxidant uvioresistant microspheres: mixing 1gAminated maleic anhydride copolymer microspheres 2Dispersed in 20mL of deionized water. Meanwhile, 4-coumaric acid (0.66g, 4 mmol) is dissolved in 10mL ethanol; and EDC (0.77g, 4 mmol) was dissolved in 20mL MES buffer (pH 5). Subsequently, 4-coumaric acid solution was added to the buffer solution, and then NHS (0.46g, 4 mmol) was added to the reaction solution and reacted in an ice-water bath for 1h; the resulting reaction solution was then added to the microsphere dispersion and reacted at room temperature for 24h. After the reaction is finished, centrifuging for 5min at 10000r/min, washing for three times by water and ethanol respectively, and then drying in vacuum to obtainOxidation resistance Uvioresistant microspheres 2The particle sizes are shown in Table 1.
Example 3
(1) Preparation of maleic anhydride copolymer microspheres: weighing 5.91g of alpha-methylstyrene, 4.90g of maleic anhydride, 0.52g of a crosslinking agent divinylbenzene (the molar ratio is 100; general formula (N) 2 After 30min, placing the three-neck flask in a 70 ℃ oil bath, reacting for 6h under the nitrogen atmosphere, centrifuging the product at 10000r/min for 5min, washing with anhydrous methanol for three times, and placing the product in a vacuum oven for drying to obtain the productCopolymerization of maleic anhydrideObject microsphere 3；
(2) Amination of the microsphere: weighing 2gMaleic anhydride copolymer microspheres 3Then, 60mL of a mixed solution of ethanol and water (volume ratio 1. After the reaction is finished, centrifuging the product at 10000r/min for 5min, washing the product with anhydrous methanol for three times, and then placing the product in a vacuum oven for drying to obtain the productAminated maleic anhydride copolymer microspheres 3。
(3) Preparing the antioxidant uvioresistant microspheres: mixing 1gAminated maleic anhydride copolymer microspheres 3Dispersed in 20mL of deionized water. Meanwhile, caffeic acid (0.54g, 3mmol) was dissolved in 10mL ethanol; EDC (0.57g, 3 mmol) was dissolved in 20mL MES buffer (pH 5). Subsequently, caffeic acid solution was added to the buffer solution, and after stirring at room temperature for 10min, NHS (0.35g, 3mmol) was added to the reaction solution and reacted in an ice-water bath for 0.5h; the resulting reaction solution was then added to the microsphere dispersion and reacted at room temperature for 48h. After the reaction is finished, centrifuging for 5min at 10000r/min, washing for three times by water and ethanol respectively, and then drying in vacuum to obtainAntioxidant uvioresistant microsphere 3The particle diameters are shown in Table 1.
Example 4
(1) Preparation of maleic anhydride copolymer microspheres: weighing 2.95g of alpha-methylstyrene, 2.45g of maleic anhydride, 0.33g of divinylbenzene (the molar ratio is 100; general formula (N) 2 After 30min, placing the three-neck flask in an oil bath kettle at 70 ℃, reacting for 6h under the nitrogen atmosphere, centrifuging the product 13000r/min for 5min, washing with anhydrous methanol for three times, and placing the product in a vacuum oven for drying to obtain the productMaleic anhydride copolymer microspheres 4；
(2) Amination of the microspheres: weighing 2gMaleic anhydride copolymer microspheres 4Then, 60mL of a mixed solution of ethanol and water (volume ratio: 1). After the reaction is finished, the product is centrifuged at 13000r/min for 5min, washed with anhydrous methanol for three times and then placed in a vacuum ovenDrying to obtainAminated maleic anhydride copolymer microspheres 4。
(3) Preparing the antioxidant uvioresistant microspheres: mixing 1gAminated maleic anhydride copolymer microspheres 4Dispersed in 20mL of deionized water. Meanwhile, ferulic acid (0.97g, 5mmol) was dissolved in 10mL of ethanol; and EDC (0.96g, 5 mmol) was dissolved in 20mL MES buffer (pH 6). Subsequently, ferulic acid solution was added to the buffer, and then NHS (0.58g, 5 mmol) was added to the reaction solution and reacted in an ice-water bath for 1h; the resulting reaction solution was then added to the microsphere dispersion and reacted at room temperature for 24h. After the reaction is finished, the mixture is centrifuged at 13000r/min for 5min, washed by water and ethanol for three times respectively, and then dried in vacuum to obtainOxidation resistance Uvioresistant microspheres 4The particle diameters are shown in Table 1.
Preparation of antioxidant uvioresistant composite material
Example 5
Preparing an antioxidant and uvioresistant polyvinyl butyral (PVB) composite film: heating and dissolving PVB in ethanol, and adding the prepared PVBAntioxidant uvioresistant microsphere 1(the microspheres account for 5wt% of the composite material by mass), uniformly dispersing, pouring into a polystyrene culture dish, naturally airing for a period of time, and then placing into a 40 ℃ oven for drying to obtain the microsphere composite materialAntioxidant and anti-violet Outer PVB composite filmThe film thickness was 100 μm, and the results of the optical property test and the oxidation resistance test are shown in Table 2. The ultraviolet transmission spectrum of the antioxidant ultraviolet-resistant PVB composite film is shown in figure 3.
And (3) testing the oxidation resistance: 0.2g of the antioxidant uvioresistant PVB composite membrane is taken and soaked in 5mL of ethanol for 24h, 1mL of supernatant is taken and added with 3mL of ethanol solution (100 mu M) of DPPH, and the final concentration of the DPPH solution is 75 mu M. After standing the reaction mixture in the dark for 60min, the absorbance at 517nm was measured. The DPPH radical clearance (RSA) is calculated according to the following formula:
A 0 as absorbance of the solution to which the sample was added, A 1 Absorbance of solution for adding different samples。
The average light transmittance of the film in different ultraviolet regions (UVA, UVB, UVC) can be calculated according to the following formula:
where T (λ) is the average spectral transmittance of the film, d λ is the bandwidth, and λ represents the wavelength.
Example 6
Preparing an antioxidant and uvioresistant polyvinyl alcohol (PVA) composite membrane: dissolving PVA in water under heating, and adding the prepared PVAAntioxidant uvioresistant microsphere 2(the mass ratio of the microspheres in the composite material is 3 wt%), uniformly dispersing, pouring into a polystyrene culture dish, naturally airing for a period of time, and then placing into a 40 ℃ oven for drying to obtain the microsphere composite materialAntioxidant uvioresistant PVA composite Laminated filmThe film thickness was 100 μm, and the results of the optical property test and the oxidation resistance test are shown in Table 2. The oxidation resistance test and the average light transmittance of the film in different ultraviolet regions were calculated as in example 5.
Example 7
Preparing an antioxidant and uvioresistant Polyurethane (PU) composite membrane: diluting the aqueous polyurethane to a solid content of 10%, and adding the aqueous polyurethaneAntioxidant uvioresistant microsphere 3(the mass ratio of the microspheres in the composite material is 1 wt%), after being dispersed uniformly, the microspheres are poured into a polystyrene culture dish, naturally dried for a period of time, and then dried in a drying oven at 40 ℃ to obtain the composite materialAntioxidant and uvioresistant PU composite filmThe film thickness was 100 μm, and the results of the optical property test and the oxidation resistance test are shown in Table 2. Antioxidant performance test and average light transmittance of film in different ultraviolet regionsThe calculation was the same as in example 5.
Example 8
Preparing an antioxidant and uvioresistant polyvinyl chloride (PVC) composite membrane: dissolving PVC in tetrahydrofuran and adding the preparedAntioxidant uvioresistant microsphere 4(the mass ratio of the microspheres in the composite material is 0.5 wt%), after being dispersed uniformly, the microspheres are poured into a glass culture dish, naturally aired for a period of time, and then placed in a 40 ℃ oven for drying for 24 hours to obtain the composite materialAntioxidant uvioresistant PVC composite Laminated filmThe film thickness was 100 μm, and the results of the optical property test and the oxidation resistance test are shown in Table 2. The oxidation resistance test and the average light transmittance of the film in different ultraviolet regions were calculated as in example 5.
Comparative example 1
Heating and dissolving PVB in ethanol, pouring the PVB into a polystyrene culture dish according to the final film-forming thickness of 100 mu m, naturally airing for a period of time, and then placing the PVB in an oven at 40 ℃ for drying for 24 hours to obtain a pure PVB film, wherein the results of the optical performance test and the oxidation resistance test of the pure PVB film are listed in Table 2. The oxidation resistance test and the average transmittance of the film in different ultraviolet regions were calculated as in example 5.
Comparative example 2
Prepared in example 1 (1)Maleic anhydride copolymer microspheres 1Instead of in example 5Antioxidant uvioresistant micro Ball 1The optical property test and the antioxidant property test results of the PVB composite film prepared under the same conditions as in example 5 are shown in table 2. The oxidation resistance test and the average light transmittance of the film in different ultraviolet regions were calculated as in example 5.
Comparative example 3
Prepared in example 1 (2)Aminated maleic anhydride copolymer microspheres 1Instead of in example 5Antioxidant and antioxidant Ultraviolet microspheres 1The optical and antioxidant properties of the PVB composite film were measured and reported in table 2, while maintaining the other conditions in example 5. The oxidation resistance test and the average transmittance of the film in different ultraviolet regions were calculated as in example 5.
TABLE 1
TABLE 2
The particle size of the uvioresistant antioxidant microsphere is 250-1300nm, and compared with the traditional ultraviolet absorbent and micromolecular antioxidant, the uvioresistant antioxidant microsphere can be dispersed in water and various organic solvents, so that the application in different fields is expanded; and the introduction of phenolic acid antioxidants enhances the absorption of the microspheres on ultraviolet rays, and the high ultraviolet shielding performance can be realized by adding a very small amount of the antioxidant ultraviolet-resistant microspheres in a polymer matrix.
In conclusion, compared with the traditional ultraviolet absorbent and antioxidant, the uvioresistant antioxidant microsphere disclosed by the invention has obvious advantages and has good application prospects in the fields of food packaging materials, sun protection and skin care, coatings and the like.
Those of ordinary skill in the art will understand that: the present invention is not limited to the above embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the antioxidant uvioresistant microspheres is characterized by comprising the following steps:
(1) Adding maleic anhydride, vinyl monomer, cross-linking agent and initiator into a solvent, performing ultrasonic dissolution to obtain a uniform reaction system, reacting the reaction system under the protection of inert gas, centrifuging or filtering and purifying after the reaction is finished, and drying to obtain maleic anhydride copolymer microspheres;
in the reaction system, the concentration of maleic anhydride is 0.1-1mol/L, the concentration of vinyl monomer is 0.1-1mol/L, and the amount of the initiator is 0.5-5wt% of the total mass of the maleic anhydride and the vinyl monomer; the molar ratio of the cross-linking agent to the maleic anhydride is (5-30): 100; the reaction temperature is 60-90 ℃ under the protection of inert gas, and the reaction time is 1-12h;
the vinyl monomer is one or the combination of more than two of styrene, alpha-methylstyrene, alpha-ethylstyrene, 4-ethylstyrene, p-methoxystyrene, p-methylstyrene, allyl benzene, indene, methylindene, benzofuran and methylbenzofuran;
in the step (1), the crosslinking agent is one or a combination of more than two of divinylbenzene, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate;
in the step (1), the solvent is one or a mixture of more than two of butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, ethyl butyrate, isoamyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate and isoamyl phenylacetate;
in the step (1), the initiator is azobisisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide;
(2) Dispersing the maleic anhydride copolymer microspheres in the step (1) in a mixed solution of ethanol and water in a volume ratio of 1; after the reaction is finished, centrifuging or filtering and purifying the product, and drying to obtain the aminated maleic anhydride copolymer microspheres;
the content of the maleic anhydride copolymer microspheres in a mixed solution of ethanol and water is 20-100mg/mL; the dosage of the ethylenediamine is 0.5-2mL/g maleic anhydride copolymer microspheres, and the reaction time is 4-12h;
(3) Dispersing the aminated maleic anhydride copolymer microspheres in the step (2) in deionized water; meanwhile, phenolic acid antioxidants are dissolved in ethanol; dissolving 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide EDC in MES buffer solution with the pH of 5-6; then, adding a phenolic acid antioxidant solution into a buffer solution, adding N-hydroxysuccinimide NHS into the buffer solution, and reacting in an ice-water bath; then adding the obtained reaction solution into an amination maleic anhydride copolymer microsphere dispersion liquid, and reacting at room temperature; after the reaction is finished, centrifuging or filtering and purifying, and then drying to obtain the antioxidant uvioresistant microspheres;
the content of the aminated maleic anhydride copolymer microspheres in deionized water is 20-50mg/mL; the dosage of the phenolic acid antioxidant is 3-5mmol/g of aminated maleic anhydride copolymer microspheres; the molar ratio of the phenolic antioxidant to EDC and NHS is 1; the volume ratio of the deionized water to the ethanol to the MES buffer is 2; in the step (3), the temperature of the ice-water bath is 0 ℃; the reaction time in ice-water bath is 0.5-1h; the reaction time is 24-48h at room temperature; the phenolic acid antioxidant is one or more of caffeic acid, 4-coumaric acid, ferulic acid, sinapic acid, gallic acid, protocatechuic acid, and vanillic acid.
2. An antioxidant uvioresistant microsphere, which is characterized by being prepared by the preparation method of claim 1, and the particle size of the antioxidant uvioresistant microsphere is 250-1300nm.
3. The application of the antioxidant uvioresistant microspheres is characterized in that the antioxidant uvioresistant microspheres are prepared by the preparation method of any one of claims 1-2, and the specific application is as follows: and mixing the antioxidant uvioresistant microspheres with a polymer matrix to prepare the antioxidant uvioresistant composite material, wherein the antioxidant uvioresistant microspheres account for 0.5 to 5 parts by weight of 100 parts by weight of the polymer matrix.
4. The use of the microspheres according to claim 3, wherein the polymer matrix is one or a combination of two or more of polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyurethane, polyethylene, polyvinyl chloride, and polypropylene; the antioxidant uvioresistant composite material can be applied to the fields of food packaging materials, sun protection and skin care and coatings.
5. The use of the antioxidant uvioresistant microsphere according to claim 3, wherein the antioxidant uvioresistant composite material is prepared by a preparation method selected from any one of the following two methods:
the first method is as follows: dissolving a polymer matrix in the solution, adding the antioxidant uvioresistant microspheres, uniformly mixing, pouring in a mold or blade-coating on a substrate, volatilizing and drying to prepare the antioxidant uvioresistant composite material;
the second method comprises the following steps: and melting and blending the polymer matrix and the antioxidant uvioresistant microspheres at the temperature of 70-190 ℃ to prepare the antioxidant uvioresistant composite material.
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