CN107955172B - Photosensitive nano particle, intelligent light-operated nano barrier composite material containing photosensitive nano particle and preparation method of intelligent light-operated nano barrier composite material - Google Patents
Photosensitive nano particle, intelligent light-operated nano barrier composite material containing photosensitive nano particle and preparation method of intelligent light-operated nano barrier composite material Download PDFInfo
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Abstract
A photosensitive nanoparticle, an intelligent light-operated nano barrier composite material containing the photosensitive nanoparticle and a preparation method thereof are disclosed, wherein the preparation raw materials of the photosensitive nanoparticle mainly comprise: the graphene oxide is prepared by reacting cyclodextrin with graphene oxide to obtain cyclodextrin modified graphene oxide, wherein the mass ratio of cyclodextrin to graphene oxide is 20-1: 1; the azobenzene and the silsesquioxane react to obtain azobenzene functionalized silsesquioxane, wherein the molar ratio of the silsesquioxane to the azobenzene is 2: 1-3; the photosensitive nanoparticles are assembled by coupling the cyclodextrin modified graphene oxide and the azobenzene functionalized silsesquioxane, wherein the mass ratio of the cyclodextrin modified graphene oxide to the azobenzene functionalized silsesquioxane is 5: 1-25. The technical effect that the air permeability blocking performance of the plastic packaging material can be intelligently regulated and controlled under the illumination condition is achieved.
Description
Technical Field
The invention belongs to the field of functional polymer composite materials, and particularly relates to photosensitive nanoparticles, an intelligent light-operated nano barrier composite material containing the photosensitive nanoparticles and a preparation method of the intelligent light-operated nano barrier composite material.
Technical Field
China is a world packaging manufacturing and consuming nation, and plastic packaging plays an irreplaceable role as a vitality force (the total value accounts for more than 30 percent) of the packaging industry in various fields of food, beverage, daily necessities and industrial and agricultural production. In recent years, with policy guidance such as national energy conservation and emission reduction and industrial transformation and upgrading and the realistic problems of increasingly intensified new technology competition, technical barriers and the like in international trade, the development of high-performance, functional and intelligent packaging materials has become a consensus in the packaging industry of China.
The gas barrier properties of a material refer to the ability of the material to permeate or block a gas under certain conditions. As is well known, in the industries of food, medicine, precision electronic components and the like, the gas barrier property of a packaging material is very important, and it directly affects the storage life, preservation environment, sales environment and the like of a product. Most common plastic packaging materials, such as PP, PVC, PE, PET, PA and the like, are only suitable for packaging common commodities due to poor gas barrier performance (all belong to low-medium common barrier materials), and the added value of products is low. Therefore, the improvement of the gas barrier property of common plastic packaging materials and the expansion of the application field of plastic packaging become research hotspots in recent years. Beijing printing college Chenqiang et al [ Wang, H; yang, L.Z; chen, Q; plasma sciences and Technology,2014,16,37-40 ] form a dense inorganic silicon oxide layer on the surface of PET by using a microwave-assisted Plasma chemical vapor deposition method, so that the gas permeability of the polymer is greatly reduced. The barrier permeability of PET material to carbon dioxide is improved by more than 7 times by evaporating an inorganic silica barrier layer on the surface of a PET beer bottle by Nippon Nisshinbo mechanical Co., Ltd and Sidel company of France. In addition, many patents (CN205602346U, CN106280306A, CN206335933U) adopt multilayer coextrusion and multilayer compounding methods to achieve the improvement of gas barrier property of common polymer-based materials. Although the surface evaporation and multilayer coextrusion can obviously improve the performance of the polymer material, the defects of complex processing technology, high processing equipment requirement, easy falling of an evaporation layer, easy breakage in bending and the like generally exist, and the application range and the field of the surface evaporation and multilayer coextrusion are limited to a certain extent.
In addition, with the rapid development of the economic society and the continuous improvement of the life quality requirements of people, the commodity package with single function can not meet the requirements of people. For example, fresh-cut fruits and vegetables, fresh and live fishes and the like need to dynamically adjust the barrier property of the packaging material according to the respiration of the commodity and different requirements on the air permeability of the package in different stages of transportation and storage. Therefore, the development and development of the intelligent adjustable novel permeability-resistant packaging material is a new bright spot in the packaging industry of China and has wide market application prospect.
Disclosure of Invention
Aiming at the defects that the processing technology of the existing permeability-resistant plastic packaging material is complex, a surface evaporation coating is easy to fall off, the permeability resistance of the material cannot be dynamically regulated and the like, the invention adopts the nano composite technology and controls the directional motion of nano components in the matrix of the composite packaging material through visible light-ultraviolet light, thereby realizing the photosensitive nanoparticles with the permeability resistance of the plastic packaging material which can be intelligently regulated and controlled under the illumination condition.
In order to solve the technical problems, the invention adopts the technical scheme that: a photosensitive nanoparticle is prepared from the following raw materials: the graphene oxide is prepared by reacting cyclodextrin with graphene oxide to obtain cyclodextrin modified graphene oxide, wherein the mass ratio of cyclodextrin to graphene oxide is 20-1: 1; the azobenzene and the silsesquioxane react to obtain azobenzene functionalized silsesquioxane, wherein the molar ratio of the silsesquioxane to the azobenzene is 2: 1-3; the photosensitive nanoparticles are assembled by coupling the cyclodextrin modified graphene oxide and the azobenzene functionalized silsesquioxane, wherein the mass ratio of the cyclodextrin modified graphene oxide to the azobenzene functionalized silsesquioxane is 5: 1-25.
The preparation process of the photosensitive nanoparticles comprises the following steps:
(1.1) firstly, uniformly dispersing graphene oxide serving as a raw material in deionized water to form a suspension with the mass concentration of 1-5%, and then adjusting the pH value of the suspension to 7-10;
(1.2) adding epoxy chloropropane, wherein the mass ratio of the Epoxy Chloropropane (ECH) to the graphene oxide is 10: 1-1: 1, continuously stirring for 0.5-4 h at the temperature of 60-85 ℃, centrifuging, separating and washing for 3-8 times;
(1.3) ultrasonically dispersing the graphene oxide in a carbonate buffer solution, adding cyclodextrin, wherein the mass ratio of cyclodextrin to graphene oxide is 20: 1-1: 1, continuously reacting for 1-6 h at the temperature of 45-80 ℃, centrifuging, separating, and washing for 3-8 times to obtain cyclodextrin modified graphene oxide (CD-GO).
The specific preparation process of the azobenzene functionalized silsesquioxane of the photosensitive nanoparticles comprises the following steps:
(2.1) firstly, taking 4-phenylazo phenol or a derivative thereof and epoxy chloropropane as raw materials, carrying out reflux reaction on the 4-phenylazo phenol or the derivative thereof and the epoxy chloropropane in an organic solvent for 1-6 hours by taking alkali as a catalyst, wherein the molar ratio of the 4-phenylazo phenol or the derivative thereof to the epoxy chloropropane is 1: 1.5-5;
(2.2) after the reaction is finished, separating and drying to obtain a compound I (formula VI), dissolving the silsesquioxane and the compound I in an organic solvent in a molar ratio of 2: 1-3, and reacting at the temperature of 70-110 ℃ for 1-6 h to obtain the azobenzene functionalized silsesquioxane (azo-POSS, formula (III)).
The photosensitive nanoparticles of the present invention are specifically prepared by the following steps: dissolving and dispersing cyclodextrin modified graphene oxide and azobenzene functionalized silsesquioxane in a mass ratio of 5: 1-25 in deionized water and ethanol at room temperature, mixing and stirring at 40-50 ℃ for 0.5-1.5 h, separating and drying to obtain the target photosensitive nanoparticles.
The graphene oxide is prepared by a chemical oxidation method (Hummers oxidation method).
The catalyst (alkali) in the step (2.1) of the invention is one or more of triethylamine, ethylenediamine, ammonia water and potassium carbonate.
The organic solvent in step (2.1) of the present invention is one or more of ethyl acetate, dichloromethane, ethanol, tetrahydrofuran, xylene, and dimethylformamide.
The azobenzene functionalized silsesquioxane has a chemical structural formula, wherein R group is one of methyl, phenyl, isobutyl, isooctyl and trifluoropropyl; -R1～-R5The group is one of hydrogen, methyl, ethyl, methoxyl and phenyl.
R in the chemical structural formula of the compound I1～R5The group is one of hydrogen, methyl, ethyl, methoxyl and phenyl.
The azobenzene functionalized silsesquioxane disclosed by the invention has a specific structural formula shown as the following formula (III):
the compound I of the invention has a specific structural formula shown as the following formula (VI):
the invention also provides an intelligent regulation and control nano composite material containing the photosensitive nanoparticles, and the raw materials of the composite material comprise: 80-90 parts of polymer matrix, 1-5 parts of photosensitive nanoparticles and 3-10 parts of auxiliary agent.
The polymer matrix is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylidene fluoride, polyether sulfone resin, polyether ether ketone and polylactic acid.
The auxiliary agent is one or more of dimethyl phthalate, dibutyl phthalate, gelatin and agar.
The invention relates to an intelligent control nano composite material, which comprises the following preparation processes: firstly, uniformly dispersing and dissolving photosensitive nanoparticles and an auxiliary agent in a polymer matrix solution with the concentration of 20-60% under the assistance of ultrasonic intermittent oscillation; then pouring the mixture into a mold, and drying the mixture for 4 to 24 hours at the temperature of between 40 and 80 ℃ to prepare the intelligent light-operated nano barrier composite material; the interval time of the intermittent oscillation is 10s, the ultrasound is 0.5-3 h), and the ultrasound power is 200-800W.
The polymer matrix solution of the intelligent control nano composite material adopts one or more solvents of chloroform, dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl pyrrolidone, ethanol and deionized water. The invention has the advantages and beneficial effects that:
1. the invention designs and synthesizes a novel nano-composite (photosensitive nano-particle) with a nano-sheet structure which can be dynamically regulated and controlled under the illumination condition for the first time; the synthesis of the photosensitive nanoparticles is to combine nano-graphene and polyhedral oligomeric silsesquioxane (POSS) together through the host-guest coupling effect between azobenzene and cyclodextrin. The Cyclodextrin (CD) adopted by the invention is a cyclic oligomer formed by combining D-glucopyranose units through alpha-1, 4 glycosidic bonds, has a typical hollow cylindrical structure (the edge of a cylinder has hydrophilicity, and the interior of the cylinder is a hydrophobic cavity), and can form a 'host-guest' inclusion compound with guest molecules with proper properties and matched structures. For azobenzene compounds, cyclodextrin easily identifies and includes trans (trans) azobenzene, but cannot include cis (cis) azobenzene, and azobenzene compounds can realize cis-trans configuration interconversion under the alternating action of ultraviolet light and visible light; therefore, the oriented movement of the nanometer component can be realized under the illumination condition through the graphene and the POSS which are coupled together by azobenzene and cyclodextrin host-guest, so that the controllable adjustment of the barrier property is realized.
2. Compared with the surface vapor deposition inorganic coating and multilayer coextrusion composite modification technology, the nano composite technology increases the diffusion path of gas in a polymer matrix by introducing a difficult-to-permeate nano component, thereby improving the barrier property of the material; the graphene is a novel nano carbon material which is formed by single-layer carbon atoms and has a lamellar structure, the single-layer thickness of the graphene is only 1nm, and the graphene has ultrahigh strength, excellent electric and heat conducting properties, a room-temperature quantum Hall effect and room-temperature ferromagnetism; more importantly, the defect-free graphene has impermeability to all gas molecules and is a carbon material with zero permeability coefficient; the cage type silsesquioxane (POSS) is an inorganic inner core (SiO) composed of silicon and oxygen elements1.5)8The intramolecular organic-inorganic hybrid cage compound formed by the compound and the extranuclear organic group R has the diameter of a single POSS molecule of about 1.5nm, is close to or equal to the size of most polymer chain segments, and can be fused with the polymer on the molecular level; POSS is easy to crystallize among molecules, and can form a compact inorganic silicon oxide layer which is difficult to permeate gases like SiOx, so that the gas barrier property of the material can be effectively improved by introducing graphene (figure 2 is a schematic structural diagram of graphene) and POSS (figure 3 is a schematic structural diagram of POSS) nano-components.
3. According to the invention, the cyclodextrin modified graphene can enhance the interfacial bonding force between the graphene and the polymer matrix, so that the graphene has better compatibility and more uniform distribution in the polymer matrix, and further the gas barrier property of the material is greatly improved. Azobenzene and cyclodextrin subject-object complexation are adopted to combine two excellent barrier nano-components of graphene and POSS together, so that a synergistic gas barrier effect with 1+1 > 2 can be generated, and the gas barrier performance of the material is remarkably improved. The photosensitive nanoparticles composed of graphene and POSS can realize directional coupling-splitting of a nanostructure under the illumination condition, so that dynamic regulation and control of gas barrier performance of the material are realized.
4. The intelligent nano composite material has simple and convenient processing technology and can be prepared by utilizing the existing processing equipment.
Drawings
FIG. 1 is a schematic representation of the cyclodextrin-azobenzene "host-guest" interaction.
Fig. 2 is a schematic diagram of the molecular structure of graphene.
FIG. 3 is a schematic molecular structure of POSS.
FIG. 4 scanning electron micrographs of photosensitive nanoparticles.
FIG. 5 infrared spectra of GO and POSS and derivatized nanoparticles.
FIG. 6azo-POSS1H NMR spectrum
FIG. 7 is a spectrum of visible-UV absorption of photosensitive nanoparticles.
Detailed Description
For further understanding of the present invention, preferred embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to only the following examples.
Example 1 Cyclodextrin-modified graphene oxide CD-GO
Ultrasonically dispersing 1g of graphene oxide GO in 100g of deionized water, controlling the pH value to be 7, then adding 10g of epichlorohydrin ECH, continuously stirring for 3 hours at the temperature of 65 ℃, and then centrifuging, separating and washing with saturated saline for 3 times. And then ultrasonically dispersing the graphene oxide in a carbonate buffer solution (pH is 6), adding 20g of beta-cyclodextrin CD, continuously reacting for 6 hours at the temperature of 70 ℃, centrifuging, separating, and washing with saturated saline for 3 times to obtain cyclodextrin modified graphene oxide CD-GO, wherein an infrared spectrogram is shown in FIG. 5.
Example 2 Azobenzene-functionalized silsesquioxane azo-POSS
Adding 10mmol of 4-phenylazo phenol, 30mmol of epichlorohydrin ECH, 50mL of tetrahydrofuran and 15mmol of triethylamine into a three-neck flask in sequence, heating to reflux, continuously reacting for 3h, removing the solvent and the redundant ECH through rotary evaporation after the reaction is finished, and purifying the obtained crude product through silica gel column chromatography (a developing agent is petroleum ether: ethyl acetate ═ 1:8) to obtain the azobenzene containing the epoxy group. Then 1.5mmol of amino POSS and 1mmol of azobenzene containing epoxy group are added into 50mL of anhydrous dimethylformamide solvent at the same time, the reaction is continued for 5h at the temperature of 70 ℃, the solvent is evaporated off after the reaction is finished, the obtained crude product is purified by silica gel column chromatography (the developing agent is petroleum ether: ethyl acetate 1:8) to obtain the azobenzene functionalized silsesquioxane azo-POSS, and an infrared spectrogram (figure 5) and a hydrogen nuclear magnetic spectrogram (figure 6) can confirm that azo-POSS is successfully prepared in the embodiment.
EXAMPLE 3 Assembly of CD-GO with azo-POSS coupling to photosensitive nanoparticles
Respectively dissolving and dispersing 1g of CD-GO and 2g of azo-POSS in deionized water and ethanol at room temperature, then mixing the two, heating to 45 ℃, violently stirring for 1h, centrifugally separating (the rotating speed is 8000 rpm), and drying in vacuum to obtain target photosensitive nanoparticles, wherein an electron microscope picture is shown in the attached figure 4 specifically, an infrared spectrum is shown in the attached figure 5, and a visible light-ultraviolet light absorption spectrum is shown in the attached figure 7; the present example indeed yielded the assembly of CD-GO coupled with azo-POSS into photosensitive nanoparticles, fully characterized by the above figures.
Embodiment 4 intelligently light-controllable nanocomposite material with barrier property
Firstly, 20g of polyvinyl alcohol is dissolved in 50mL of hot water at 90 ℃, then 0.2g of photosensitive nanoparticles and 1g of dimethyl phthalate are added into the polyvinyl alcohol solution under the assistance of ultrasound (the ultrasonic power is 800W), the mixture is ultrasonically dispersed for 0.5h, then the polymer solution is poured into a mold, the mold is placed under 245nm ultraviolet light and dried for 24h at the temperature of 50 ℃, and the intelligent light-controlled nano barrier composite material is obtained, wherein an electron microscope picture is specifically shown in figure 7.
Embodiment 5 Intelligent light-controllable nanocomposite with barrier property
Firstly, 10g of polylactic acid is dissolved in 30mL of chloroform solution, then 0.05g of photosensitive nanoparticles, 0.075g of photosensitive nanoparticles and 0.10g of photosensitive nanoparticles are added into the polylactic acid solution under the assistance of ultrasound (with the ultrasound power of 800W) respectively, the photosensitive nanoparticles are subjected to ultrasonic dispersion for 0.5h, then the polymer solution is poured into a mold, the mold is placed under two different illumination environments (visible light and ultraviolet light 365nm), and the drying is carried out for 24h at the temperature of 50 ℃ to obtain a series of intelligent light-controlled nano barrier composite materials PLA/GO-POSS. The light-operated resistance to water vapor and oxygen permeability of the composite material is shown in table 1, and the nano composite material prepared by the embodiment has obvious intelligent light-operated resistance.
The properties of the inventive examples are shown in table 1 below:
TABLE 1 Intelligent nanocomposite Water vapor and oxygen permeability coefficients
Note: oxygen gas barrier test conditions: temperature T is 25 deg.C, humidity RH is 0%
Water vapor barrier property test conditions: the temperature T is 25 ℃, and the humidity RH is 50%
The ultraviolet light wavelength is 365nm, and the irradiation is carried out for 15 min.
Claims (10)
1. A photosensitive nanoparticle characterized by: the preparation raw materials of the particle mainly comprise: the graphene oxide is prepared by reacting cyclodextrin with graphene oxide to obtain cyclodextrin modified graphene oxide, wherein the mass ratio of cyclodextrin to graphene oxide is 20-1: 1; the azobenzene and the silsesquioxane react to obtain azobenzene functionalized silsesquioxane, wherein the molar ratio of the silsesquioxane to the azobenzene is 2: 1-3; the photosensitive nanoparticles are assembled by coupling the cyclodextrin modified graphene oxide and the azobenzene functionalized silsesquioxane, wherein the mass ratio of the cyclodextrin modified graphene oxide to the azobenzene functionalized silsesquioxane is 5: 1-25.
2. Photosensitive nanoparticles according to claim 1, characterized in that: the specific preparation process of the cyclodextrin modified graphene oxide comprises the following steps:
(1.1) firstly, uniformly dispersing graphene oxide serving as a raw material in deionized water to form a suspension with the mass concentration of 1-5%, and then adjusting the pH value of the suspension to 7-10;
(1.2) adding epoxy chloropropane, wherein the mass ratio of the Epoxy Chloropropane (ECH) to the graphene oxide is 10: 1-1: 1, continuously stirring for 0.5-4 h at the temperature of 60-85 ℃, centrifuging, separating and washing for 3-8 times;
(1.3) ultrasonically dispersing the graphene oxide in a carbonate buffer solution, adding cyclodextrin, continuously reacting for 1-6 h at the temperature of 45-80 ℃ at the mass ratio of cyclodextrin to graphene oxide of 20: 1-1: 1, centrifuging, separating, and washing for 3-8 times to obtain the cyclodextrin modified graphene oxide.
3. Photosensitive nanoparticles according to claim 1, characterized in that: the specific preparation process of the azobenzene functionalized silsesquioxane comprises the following steps:
(2.1) firstly, taking 4-phenylazo phenol or a derivative thereof and epoxy chloropropane as raw materials, carrying out reflux reaction on the 4-phenylazo phenol or the derivative thereof and the epoxy chloropropane in an organic solvent for 1-6 hours by taking alkali as a catalyst, wherein the molar ratio of the 4-phenylazo phenol or the derivative thereof to the epoxy chloropropane is 1: 1.5-5;
(2.2) after the reaction is finished, separating and drying to obtain a compound I, dissolving the silsesquioxane and the compound I in an organic solvent according to a molar ratio of 2: 1-3, and reacting at 70-110 ℃ for 1-6 h to obtain the azobenzene functionalized silsesquioxane.
4. Photosensitive nanoparticles according to claim 3, characterized in that: the catalyst in the step (2.1) is one or more of triethylamine, ethylenediamine, ammonia water and potassium carbonate; the organic solvent in the step (2.1) is one or more of ethyl acetate, dichloromethane, ethanol, tetrahydrofuran, xylene and dimethylformamide.
5. Photosensitive nanoparticles according to claim 3, characterized in that: the specific structural formula of the compound I is shown as the following formula (VI):
r in chemical structural formula of compound I1～R5The group is one of hydrogen, methyl, ethyl, methoxy and phenyl;
the azobenzene functionalized silsesquioxane has a specific structural formula shown as the following formula (III):
wherein the R group is one of methyl, phenyl, isobutyl, isooctyl and trifluoropropyl; -R1～-R5The group is one of hydrogen, methyl, ethyl, methoxyl and phenyl.
6. Photosensitive nanoparticles according to claim 1, characterized in that: the specific preparation process of the photosensitive nanoparticles comprises the following steps: dissolving and dispersing cyclodextrin modified graphene oxide and azobenzene functionalized silsesquioxane in a mass ratio of 5: 1-25 in deionized water and ethanol at room temperature, mixing and stirring at 40-50 ℃ for 0.5-1.5 h, separating and drying to obtain the target photosensitive nanoparticles.
7. A smart nanocomposite material comprising photosensitive nanoparticles according to any one of claims 1 to 6, wherein: the composite material comprises the following raw materials: 80-90 parts of polymer matrix, 1-5 parts of photosensitive nanoparticles and 3-10 parts of auxiliary agent.
8. The smart regulating nanocomposite material containing photosensitive nanoparticles according to claim 7, characterized in that: the polymer matrix is one or more of polyvinyl alcohol, polyethylene glycol, polyvinylidene fluoride, polyether sulfone resin, polyether ether ketone and polylactic acid; the auxiliary agent is one or more of dimethyl phthalate, dibutyl phthalate, gelatin and agar.
9. The method of claim 8, wherein the photosensitive nanoparticle-containing intelligent control nanocomposite material is prepared by: the preparation process comprises the following steps: firstly, uniformly dispersing and dissolving photosensitive nanoparticles and an auxiliary agent in a polymer matrix solution with the concentration of 20-60% under the assistance of ultrasonic intermittent oscillation; then pouring the mixture into a mold, and drying the mixture for 4 to 24 hours at the temperature of between 40 and 80 ℃ to prepare the intelligent light-operated nano barrier composite material; the intermittent oscillation interval time is 10s, the ultrasonic wave is 0.5-3 h, and the ultrasonic power is 200-800W.
10. The method of claim 9, wherein the photosensitive nanoparticle-containing intelligent control nanocomposite material is prepared by: the polymer matrix solution adopts one or more solvents selected from chloroform, dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl pyrrolidone, ethanol and deionized water.
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