CN110698826A - Preparation method of high-barrier polylactic acid film containing three-dimensional barrier network - Google Patents
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Abstract
The invention discloses a preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network, which comprises the following raw materials: polylactic acid, polyethylene oxide, graphene oxide; comprises the following steps: s1, preparing polylactic acid microspheres; s2, preparing a graphene oxide/polyethylene oxide dispersion liquid; s3, coating with solution; and S4, hot-press forming. According to the invention, polylactic acid microspheres are used as templates, the coating of graphene oxide sheets with excellent barrier property on the surfaces of the polylactic acid microspheres is realized through solution coating of a polyethylene oxide solution system, barrier microcells, namely graphene oxide/polyethylene oxide @ polylactic acid composite microspheres, are constructed, then a three-dimensional graphene oxide network is constructed in a polylactic acid matrix through hot press molding, and the polymer composite film with excellent oxygen barrier property is prepared under the condition of extremely low graphene oxide content.
Description
Technical Field
The invention relates to the field of polymer packaging films, in particular to a preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network.
Background
Currently, barrier packaging materials are increasingly used in the fields of food packaging, pharmaceutical packaging, electronic device packaging, etc. (Yoo B M, et al. journal of Applied Polymer Science, 2014, 131: 939628.). Among them, polymer films are the mainstream materials for barrier packaging due to their advantages of light weight, low cost, easy processing, etc. However, a single polymer film has limited barrier properties, cannot meet the use requirements of different commodities, and causes problems such as food deterioration, drug failure, and shortened shelf life of electronic devices (Cui Y B, et al. It is reported that the loss of food, medicine and the like in developing countries, which is caused by poor barrier property of packaging, is as high as 30% -40% after processing, storage, transportation and circulation until reaching the hands of consumers, so that the development of polymer packaging materials with high barrier property has become a focus problem in the contemporary packaging industry and the plastic industry.
Numerous studies have shown that the nanosheet filler compounding technique is an effective means of improving the barrier properties of polymer composite films (Tan B, et al. journal of Membrane Science, 2016, 514: 595-. These studies suggest that its superior barrier properties are due to the "tortuous path effect". The polymer composite film is composed of a polymer matrix permeable to gas molecules and a layered nanofiller impermeable to gas molecules. Because the layered nanofiller exists as a "nano-barrier" and gas molecules can only diffuse in the matrix along a tortuous path when passing through the polymer composite film, the barrier properties of the polymer composite film can be improved by orders of magnitude. The barrier properties of polymer composite films are mainly related to three factors: the intrinsic barrier properties of the polymer matrix, the interfacial properties, and the intrinsic properties of the nanofiller (e.g. aspect ratio, degree of exfoliation, state of dispersion, degree of orientation).
The inherent properties of nanofillers are the primary factors that determine the barrier properties of polymer composite films. The layered nanofiller has a more significant effect on improving the barrier properties of the composite film than spherical and fibrous nanofillers because it has the largest aspect ratio and thus the most tortuous diffusion path for gas molecules in the film (Wolf C, et al. journal of membrane Science, 2018, 556: 393-418.). The existing widely used barrier filler mainly comprises clay, hydrotalcite, graphene and derivatives thereof. Among them, graphene oxide (gosss) has a very large specific surface area to thickness ratio, most of gas molecules and liquid molecules cannot diffuse on the surface of its sheet layer, so that the intrinsic barrier property is very excellent, and at the same time, a large amount of oxygen-containing functional groups on its surface are beneficial to improving the interfacial bonding between gosss and polar polymer matrix (He H, equivalent chemical Physics Letter, 1998, 287:53-56.), promoting complete exfoliation and uniform dispersion of gosss in the polymer matrix, thereby giving the material excellent barrier property.
Besides considering the geometric morphology of the filler, the micro-dispersion morphology is also a key factor for determining the barrier performance of the polymer composite film. The higher the degree of exfoliation and the more uniform the dispersion, the outstanding barrier properties and other functionalities can be imparted to the polymer composite film. For gas permeation processes, however, the focus of research should be more focused on the efficient packing of layered nanofillers rather than uniform dispersion to build a dense gas barrier network to achieve the highest barrier efficiency of the filler. This is because effective stacking allows for a larger aspect ratio barrier, thus giving the polymer composite film a lower permeability coefficient at very low filler content. Layer-by-layer self-assembly is a typical example of designing an effective stacking 'nano brick wall' microstructure through the process of alternately depositing polymer and nano-sheet layer filler, and because the layered nano-filler is arranged in parallel along the direction parallel to the surface of the film to form an effective lap joint and highly oriented micro-morphology, the barrier property can be greatly improved under the condition of low filler content (Yang Y H, et al. advanced Materials, 2013, 25: 493). Inspired by the construction of three-dimensional filler networks in systems by electrically and thermally conductive composites (Pang H, et al progress in Polymer Science, 2014, 39:1908-1933 Wang Z G, et al composites Science and Technology, 2018, 162:7-13.), a three-dimensional continuous closed barrier network is constructed in a matrix, promising the preparation of high barrier polymer composite films.
Based on the above, the environment-friendly polylactic acid (PLA) is used as a matrix, the excellent barrier property of GONSs is combined, meanwhile, polyethylene oxide (PEO) is introduced to assist in forming in the hot pressing process, a good interface is given to the film, and the high-barrier polymer composite film containing the three-dimensional barrier network is prepared. The GONSs are subjected to solution coating process, PLA microspheres are used as templates to construct barrier micro units on the surfaces of the PLA microspheres in a self-assembling mode, the barrier micro units are further subjected to hot press molding to construct a three-dimensional GONSs network in a PLA matrix, and therefore the barrier performance of the PLA to oxygen is greatly improved under the condition of low filler content. The construction of the special structure promotes the application of the polymer composite film in the field of barrier packaging.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network, which has the advantages of simple preparation process, low production cost and industrial production potential.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network comprises the following raw materials and reagents: raw materials: polylactic acid, polyethylene oxide, graphene oxide; reagent: emulsifier, water, dichloromethane; the preparation method comprises the following steps:
s1, preparation of polylactic acid microspheres: dissolving polylactic acid at room temperature to obtain a clear solution, adding a water-soluble emulsifier into deionized water, mixing the two solutions, stirring at room temperature to obtain a stable polylactic acid emulsion, continuously stirring for a period of time, solidifying the polylactic acid after the solvent is volatilized, and filtering, washing and drying to obtain the polylactic acid microspheres.
S2, preparing a graphene oxide/polyethylene oxide dispersion liquid: and ultrasonically stirring graphite oxide in ionized water to promote graphene oxide to be fully peeled and dispersed in the water to form stable dispersion liquid, then adding polyethylene oxide powder into the dispersion liquid, and stirring and dissolving at room temperature to obtain the graphene oxide/polyethylene oxide dispersion liquid.
S3, solution coating: and (4) adding the polylactic acid microspheres prepared in the step S1 into the dispersion liquid prepared in the step S2, heating and stirring, removing water, and coating the surfaces of the polylactic acid microspheres with graphene oxide in the process of gradually volatilizing water to obtain the graphene oxide/polyethylene oxide @ polylactic acid composite microspheres.
S4, hot press forming: and (4) carrying out two-step hot press molding on the composite microspheres prepared in the step S3, and finally cooling to room temperature to obtain the target product.
Preferably, according to the operation procedure in S1, the weight average molecular weight of the polylactic acid is 20-30 ten thousand, the polylactic acid solvent can be dichloromethane or trichloromethane, the concentration of the polylactic acid solution is 0.01-1g/ml,
preferably, according to the operation procedure in S1, the water-soluble emulsifier can be polyvinyl alcohol, Tween 80, gelatin, polyvinylpyrrolidone, the concentration of the water-soluble emulsifier is 0.01-1g/ml, the rotation speed of the mechanical stirring for preparing the microspheres is 200-500rpm,
preferably, the polyethylene oxide has a weight average molecular weight of 5 to 20 ten thousand according to the procedure in S2, the graphite oxide is prepared by a modified Hummers method, the concentration of the graphene oxide dispersion may be 0.5mg/ml to 5mg/ml,
preferably, according to the operation step in S3, the solution coating temperature is 25 to 100 ℃, and the weight ratio of the graphene oxide, the polyethylene oxide and the polylactic acid is (0.005 to 0.1): (5-10): (95-90),
preferably, according to the operation steps in S4, the preheating and first-step pressing temperature in the hot press molding process may be 160-,
the invention has the beneficial effects that:
(1) the GONSs are used as the barrier filler, the GONSs have extremely large diameter-thickness ratio and specific surface area, so that the GONSs are endowed with excellent barrier property, and a large number of oxygen-containing functional groups on the surface enable the GONSs to have good compatibility with a polar matrix.
(2) The GONSs with excellent barrier property are coated on the surfaces of the PLA microspheres in a solution coating process to construct barrier microcells, the barrier microcells are further stacked in a hot press molding process, the GONSs are selectively distributed at interface positions among the PLA microspheres to mutually form a three-dimensional closed barrier network in a system, and the composite film is endowed with excellent barrier property under the condition of extremely low filler content, so that the novel method for preparing the high-barrier polymer composite film through structural design is provided.
(3) The invention introduces the polymer PEO with lower melting point into the system, and assists in forming when hot-pressed at the temperature near the melting point of PLA, thereby being beneficial to constructing a more complete three-dimensional barrier network in the system, having good compatibility with the PLA and endowing the film with good interface performance.
(4) The invention adopts the method of solution coating and hot press molding, has simple preparation process and low production cost, and has the potential of industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a scanning electron microscope image of PLA microspheres;
FIG. 2 is a scanning electron microscope image (a) and a scanning electron microscope image (b) of a GONSs/PEO @ PLA composite microsphere prepared by solution coating;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a cross section (a) of the GONSs/PEO/PLA composite film and a SEM magnified image of the cross section (b).
Detailed Description
The following examples are given to illustrate the invention. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and other persons skilled in the art who have the above-mentioned invention may make insubstantial modifications and adjustments while remaining within the scope of the present invention. The preparation of PLA microspheres, the preparation of GONSs/PEO dispersion, solution coating and hot press molding are carried out, and the invention is described by taking PLA with the weight-average molecular weight of 22.5 ten thousand and PEO with the weight-average molecular weight of 10 ten thousand as examples.
The graphite oxide used in the following examples was prepared in the laboratory from expandable graphite by a modified Hummers method. Firstly, 500ml of concentrated sulfuric acid is added into 10g of expandable graphite, 70g of potassium permanganate is slowly added into the expandable graphite under the condition of stirring, during the process, the temperature of the system is maintained at 35-40 ℃, then about 500ml of deionized water is slowly added dropwise, in the process, the temperature of the mixed liquid is prevented from being too high due to the release of a large amount of heat by the concentrated sulfuric acid through dilution, then adding a 30% hydrogen peroxide dilute solution under stirring, wherein the solution is heated and generates a large amount of bubbles, the color is changed from brown to golden yellow, filtering the obtained suspension, washing for 3 times by using a hydrochloric acid solution with the volume ratio of 1:10 to remove sulfate ions and metal ions in the viscous substances, collecting the paste on the filter paper and dispersing the paste in deionized water, repeatedly washing by centrifugation at 7000 plus 9000rpm until the supernatant is neutral, and then centrifuging at 2000 plus 4000rpm to remove the non-exfoliated graphite oxide. And (5) freeze-drying and dehydrating to obtain the graphite oxide.
Examples 1 to 24 (see Table 1)
The invention relates to a preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network, which comprises the following raw materials and reagents: raw materials: polylactic acid, polyethylene oxide, graphene oxide; reagent: emulsifier, water, dichloromethane; the preparation method comprises the following steps:
s1, preparation of polylactic acid microspheres: dissolving polylactic acid at room temperature, wherein the weight-average molecular weight of the polylactic acid is 20-30 ten thousand, the polylactic acid solvent can be dichloromethane and trichloromethane, the concentration of the polylactic acid solution is 0.01-1g/ml, obtaining a clear solution, simultaneously adding a water-soluble emulsifier into deionized water, the water-soluble emulsifier can be polyvinyl alcohol, tween 80, gelatin and polyvinylpyrrolidone, the concentration of the water-soluble emulsifier is 0.01-1g/ml, mixing the two solutions, stirring at room temperature to obtain a stable polylactic acid emulsion, then, continuously stirring for a period of time, volatilizing the solvent, solidifying the polylactic acid, filtering, washing and drying to obtain polylactic acid microspheres, and the rotation speed of the mechanical stirring for preparing the microspheres is 200-500 rpm.
S2, preparing a graphene oxide/polyethylene oxide dispersion liquid: the preparation method comprises the steps of ultrasonically stirring graphite oxide in ionized water, preparing the graphite oxide by an improved Hummers method, promoting graphene oxide to be fully peeled and dispersed in the water to form a stable dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid can be 0.5-5 mg/ml, then adding polyethylene oxide powder into the dispersion liquid, wherein the weight average molecular weight of the polyethylene oxide is 5-20 ten thousand, and stirring and dissolving at room temperature to obtain the graphene oxide/polyethylene oxide dispersion liquid.
S3, solution coating: adding the polylactic acid microspheres prepared in the step S1 into the dispersion liquid prepared in the step S2, heating and stirring, removing water, coating graphene oxide on the surfaces of the polylactic acid microspheres in the process of gradually volatilizing water, wherein the solution coating temperature is 25-100 ℃, so that graphene oxide/polyethylene oxide @ polylactic acid composite microspheres are obtained, and the weight ratio of graphene oxide to polyethylene oxide to polylactic acid is (0.005-0.1): (5-10): (95-90).
S4, hot press forming: and (2) performing two-step hot-press molding on the composite microspheres prepared in the step S3, wherein the preheating and first-step pressing temperatures in the hot-press molding process can be 160-170 ℃, the second-step pressing temperature in the hot-press molding process can be 170-190 ℃, finally cooling to room temperature to obtain a target product, and finally rapidly cooling to room temperature to obtain the target product, which is shown in Table 1.
Comparative example
The process comprises the following steps:
s1, preparation of polylactic acid microspheres: dissolving polylactic acid at room temperature to obtain a clear solution, selecting dichloromethane as a solvent, dissolving a water-soluble emulsifier in deionized water, selecting polyvinyl alcohol as an emulsifier, mixing the two solutions, stirring at room temperature, wherein the stirring speed can be 300rpm, so as to obtain a stable polylactic acid emulsion, continuously stirring for a period of time, wherein the time can be 4-10h, solidifying the polylactic acid after the solvent is volatilized, and filtering, washing and drying to obtain the polylactic acid microspheres.
S2, hot press forming: the polylactic acid microspheres prepared in step S1 can be first preheated at 160-.
TABLE 1 formulations and Molding Hot Press temperatures for examples 1-24 and comparative example 1
TABLE 2 oxygen Barrier Properties of examples 1-24 vs. comparative example 1
The above PLA is not limited to 22.5 million in weight average molecular weight, PEO is not limited to 10 million in weight average molecular weight, and the emulsifier is not limited to polyvinyl alcohol, and the weight ratio of gosss, PEO, and PLA may be (0.05-0.1): (0-10): (100-10) the GONSs in the amount of (0.005-0.1) by weight, the barrier properties can be greatly improved. In the operation S4, the thermoforming process is performed in two steps to construct a good three-dimensional barrier network and obtain a good quality composite film, in the operation S4, the preheating temperature and the first thermoforming temperature are preferably 160-.
In order to examine the particle size and surface morphology of the PLA microspheres, the PLA microspheres are observed by a scanning electron microscope (model Inspec-F, FEI company) (figure 1), and the result shows that the PLA microspheres are irregular spherical particles with the particle size of about 50-70 μm and the average particle size of 61.9 μm, and the size of the microspheres is far larger than that of GONSs (about 800nm), so that the GONSs can be coated on the surfaces of the PLA microspheres, and non-PLA microspheres are deposited on the surfaces of the GONSs. The construction of the barrier microcell, i.e., GONSs/PEO @ PLA composite microspheres directly affects the formation of the three-dimensional barrier network, so that a scanning electron microscope is used for representing the surface morphology of the composite microspheres, as shown in FIG. 2, it is found that GONSs are successfully coated on the surface of PLA microspheres, compared with pure PLA microspheres, the composite microspheres have a rougher surface, meanwhile, the typical wrinkle morphology of GONSs is observed on the surface of the microspheres, and the GONSs can be successfully coated on the surface of polylactic acid microspheres because oxygen-containing functional groups on the surface of the GONSs and polylactic acid can form dipole-dipole interaction, in order to evaluate that the preparation method can successfully construct the three-dimensional barrier network in a system, the cross-sectional morphology of the composite film is further observed by adopting the scanning electron microscope, as shown in FIG. 3, it is found that GONSs are selectively distributed at the positions of PLA microsphere interface to form a three-dimensional closed, meanwhile, the PLA microspheres are greatly deformed in the hot press molding process, so that the PLA microspheres are in the shape of an irregular polygon. The successful construction of the three-dimensional continuous closed barrier network realizes effective overlapping between the layered nano fillers to obtain the barrier units with larger diameter-thickness ratio, and has more barrier barriers due to the existence of the closed network when gas molecules are diffused in all directions in the composite film, so that the composite film can be endowed with excellent barrier performance under the condition of low filler content.
In order to investigate the barrier property of the GONSs/PEO/PLA composite film, VAC-V is adopted2The barrier performance of the examples and the comparative examples was tested by a gas permeameter (Labthink, Jinan, China), and the results are shown in Table 2, after a three-dimensional GONSs three-dimensional barrier network was constructed in a PLA matrix, the barrier performance of the composite film was greatly improved at 160 and 1, respectivelyWhen pressed at 70 ℃, the oxygen permeability coefficient of only 0.05 parts of GONSs added compared to pure PLA is 9.200X 10-15cm3cm cm-2s-1Pa-1Reduced to 1.969X 10-15cm3cm cm-2s-1Pa-1. The introduction of PEO can assist in the forming process, and simultaneously endow the composite film with good interface performance, and further improve the barrier performance of the composite film, but the barrier performance is poor, when the content is too high, the barrier performance is reduced, the hot press forming temperature is a key parameter for constructing a three-dimensional barrier network in a PLA matrix, a two-step hot press forming process is a better mode, the first-step hot press forming process is carried out at a lower temperature of 160-, because GONSs is expensive, the industrial conversion process of the GONSs-based composite material is limited, the preparation method of the film has a promoting effect on the GONSs, and meanwhile, the preparation method adopts a solution coating and hot-press forming method, so that the preparation process is simple, the production cost is low, and the potential of industrial production is realized.
Claims (6)
1. A preparation method of a high-barrier polylactic acid film containing a three-dimensional barrier network is characterized by comprising the following steps: the raw materials and reagents used are as follows: raw materials: polylactic acid, polyethylene oxide, graphene oxide; reagent: emulsifier, water, dichloromethane; the preparation method comprises the following steps:
s1, preparation of polylactic acid microspheres: dissolving polylactic acid at room temperature to obtain a clear solution, adding a water-soluble emulsifier into deionized water, mixing the two solutions, stirring at room temperature to obtain a stable polylactic acid emulsion, continuously stirring for a period of time, solidifying the polylactic acid after the solvent is volatilized, and filtering, washing and drying to obtain polylactic acid microspheres;
s2, preparing a graphene oxide/polyethylene oxide dispersion liquid: ultrasonically stirring graphite oxide in ionized water to promote graphene oxide to be fully peeled and dispersed in the water to form stable dispersion liquid, then adding polyethylene oxide powder into the dispersion liquid, and stirring and dissolving at room temperature to obtain graphene oxide/polyethylene oxide dispersion liquid;
s3, solution coating: adding the polylactic acid microspheres prepared in the step S1 into the dispersion liquid prepared in the step S2, heating and stirring, removing water, and coating the surfaces of the polylactic acid microspheres with graphene oxide in the process of gradually volatilizing water to obtain graphene oxide/polyethylene oxide @ polylactic acid composite microspheres;
s4, hot press forming: and (4) carrying out two-step hot press molding on the composite microspheres prepared in the step S3, and finally cooling to room temperature to obtain the target product.
2. The preparation method of the high-barrier polylactic acid film containing the three-dimensional barrier network according to claim 1, characterized by comprising the following steps: according to the operation procedure in S1, the weight average molecular weight of the polylactic acid is 20-30 ten thousand, the polylactic acid solvent can be dichloromethane or trichloromethane, and the concentration of the polylactic acid solution is 0.01-1 g/ml.
3. The preparation method of the high-barrier polylactic acid film containing the three-dimensional barrier network according to claim 1, characterized by comprising the following steps: according to the operation procedure in S1, the water-soluble emulsifier can be polyvinyl alcohol, Tween 80, gelatin, polyvinylpyrrolidone, the concentration of the water-soluble emulsifier is 0.01-1g/ml, and the rotation speed of the mechanical stirring for preparing the microspheres is 200-500 rpm.
4. The preparation method of the high-barrier polylactic acid film containing the three-dimensional barrier network according to claim 1, characterized by comprising the following steps: according to the operation procedure in S2, the polyethylene oxide has a weight average molecular weight of 5 to 20 ten thousand, the graphite oxide is prepared by a modified Hummers method, and the concentration of the graphene oxide dispersion may be 0.5mg/ml to 5 mg/ml.
5. The preparation method of the high-barrier polylactic acid film containing the three-dimensional barrier network according to claim 1, characterized by comprising the following steps: according to the operation step in S3, the solution coating temperature is 25-100 ℃, and the weight ratio of the graphene oxide, the polyethylene oxide and the polylactic acid is (0.005-0.1): (5-10): (95-90).
6. The preparation method of the high-barrier polylactic acid film containing the three-dimensional barrier network according to claim 1, characterized by comprising the following steps: according to the operation steps in S4, the preheating and first-step pressing temperature in the hot press molding process can be 160-170 ℃, and the second-step pressing temperature in the hot press molding process can be 170-190 ℃.
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