CN115975355B - PET-based composite film with high barrier strength and toughness, and preparation method and application thereof - Google Patents
PET-based composite film with high barrier strength and toughness, and preparation method and application thereof Download PDFInfo
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- CN115975355B CN115975355B CN202211709245.2A CN202211709245A CN115975355B CN 115975355 B CN115975355 B CN 115975355B CN 202211709245 A CN202211709245 A CN 202211709245A CN 115975355 B CN115975355 B CN 115975355B
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 88
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- 238000002844 melting Methods 0.000 description 15
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention belongs to the technical field of polymer composite materials, and discloses a PET (polyethylene terephthalate) based composite film with high barrier strength and toughness, a preparation method and application thereof. The PET-based composite film comprises the following components: PET resin, PEN resin, POSS particle modified surface modified montmorillonite, citric acid triglyceride and epoxidized soybean oil. The PET-based composite film has high toughness and high barrier property, wherein the breaking elongation is 154.6-184.6%, the tensile strength is 52.8-85.6MPa, the transverse tearing strength is 153.2-198.4MPa, the longitudinal tearing strength is 196.5-231.4MPa, the oxygen permeability of the PET-based composite film with the thickness of 25 μm is 27.7-47.5cm 3/(m2 -24 h-0.1 MPa, the water vapor permeability is 5.1-8.2 g/(m 2 -24 hr-MPa), and the light transmittance is 84.6-88.3%.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a PET (polyethylene terephthalate) based composite film with high barrier strength and toughness, a preparation method and application.
Background
In the field of packaging products, especially packaging films, a great deal of plastic materials, such as PE, PP, PET films, are still the main stream of packaging films, and the plastic materials from petroleum base have excellent processability, good mechanical properties and better barrier property of partial materials such as PET. Although the performance is superior, a certain difference exists in the field with higher requirements on partial performance indexes, such as barrier property, the oxygen permeability of a pure 25 mu mPET film is 100-200cm 3/(m2.24 h.0.1 MPa, the water vapor permeability is 10-20 g/(m 2.24 hr.MPa), the requirements on gas beverage and certain specific chemical products can not be met, and partial special modification modes are adopted, such as a multilayer compounding method, and a similar three-layer structure is constructed: "PET/Barrier/PET" or five layers: the multilayer structure of "PET/barrier layer/PET/group barrier layer/PET", but this approach often requires consideration of bonding and compatibility between the layers; or a physical and chemical deposition method is adopted to realize film plating on the surface, such as covering an aluminum film, but the method reduces the transparency of the film and increases the process difficulty. Partial modification methods such as blending and copolymerization are also often used, and problems such as unsatisfactory performance or complex material process remain. Therefore, the development of the high-barrier film material prepared by the simpler process has more excellent performance and still has huge commercial and application values.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a PET-based composite film with high barrier strength and toughness, the oxygen transmittance of the PET-based composite film with the thickness of 25 mu m is 27.7-47.5cm 3/(m2 & 24h & 0.1MPa, the water vapor transmittance is 5.1-8.2 g/(m 2 & 24hr & MPa), and the problem of insufficient water-oxygen barrier property of a pure PET film material is solved.
A first aspect of the present invention provides a PET-based composite film comprising the following components: PET resin, PEN resin, POSS (polyhedral oligomeric silsesquioxane) particle modified surface modified montmorillonite, citric acid triglyceride and epoxidized soybean oil.
Preferably, the PET-based composite film comprises the following components in parts by mass: 100 parts of PET resin, 10-20 parts of PEN resin, 3-6 parts of POSS particle modified surface modification lamellar montmorillonite, 3-6 parts of citric acid triglyceride and 2-4 parts of epoxidized soybean oil.
Preferably, the molecular weight of the PET resin is 20000-35000.
Preferably, the molecular weight of the PET resin is 28000-32000.
Preferably, the PET resin has a melting point of 255-270 ℃, a crystallization temperature of 120-140 ℃, a glass transition temperature of 70-90 ℃, and a heat shrinkage (150 ℃ for 30 min) of 0.5-1.
Preferably, the PEN resin has a molecular weight of 32000 to 54000.
Preferably, the PEN resin has a molecular weight of 44000 to 48000.
Preferably, the PEN resin has a melting point of 260-280 ℃, a crystallization temperature of 180-200 ℃, a glass transition temperature of 115-125 ℃, and a heat shrinkage (150 ℃ for 30 min) of 0.2-0.5.
Preferably, in the POSS particle modified surface modification montmorillonite, the mass of the POSS particles accounts for 20-40% of the mass of the surface modification montmorillonite.
Preferably, the montmorillonite material selected for the surface modification lamellar montmorillonite is sodium-based montmorillonite.
Preferably, the surface modification montmorillonite has a particle size of 200-400 mesh.
Preferably, the POSS particle modified surface modification montmorillonite is POSS particle modified surface modification montmorillonite with a certain end group structure.
Preferably, the POSS particles comprise at least one of eight-arm tetramethylammonium ion POSS particles, eight-arm acrolein propyl ester POSS particles, and eight-arm glycidyl methacrylate POSS particles.
Preferably, the molecular structural formula of the eight-arm tetramethylammonium ion POSS particles is as follows:
preferably, the eight-arm propyl acrylate POSS particles have the following molecular structural formula:
preferably, the eight-arm glycidyl methacrylate POSS particles have the following molecular structural formula:
preferably, the surface modification montmorillonite comprises at least one of cetyltrimethylammonium bromide modification montmorillonite, polyether polyol modification montmorillonite and silane modification montmorillonite.
Preferably, the preparation method of the cetyl trimethyl ammonium bromide modified lamellar montmorillonite comprises the following steps: dissolving sodium montmorillonite in deionized water to form 5-10wt% suspension, and stirring uniformly; adding cetyl trimethyl ammonium bromide, stirring for 2-6 hours, and standing for hydration for 24-48 hours to obtain cetyl trimethyl ammonium bromide modified montmorillonite; wherein, the mass of the hexadecyl trimethyl ammonium bromide accounts for 8-16 percent of the mass of the montmorillonite.
Preferably, the preparation method of the polyether polyol modified lamellar montmorillonite comprises the following steps: dissolving polyether glycol in dimethylacetamide to form a solution, adding aqueous suspension of cetyltrimethylammonium bromide modified montmorillonite into the solution, mixing the aqueous suspension and the aqueous suspension, stirring at a rotating speed of 100-200rmp, heating to 90 ℃ for dehydration, realizing surface modification, grinding and sieving to obtain polyether polyol modified montmorillonite; wherein, the mass percentage of polyether glycol accounts for 10-30% of the mass percentage of cetyl trimethyl ammonium bromide modified lamellar montmorillonite; the aqueous suspension of cetyltrimethylammonium bromide modified montmorillonite refers to: cetyl trimethyl ammonium bromide modified montmorillonite is dissolved in deionized water to form 5-10wt% suspension.
Preferably, the preparation method of the silane modified lamellar montmorillonite comprises the following steps: adding chlorosilane into sodium montmorillonite, adding dimethylacetamide or other polar dispersing agents, heating to 60 ℃, stirring and refluxing for 36-48h, filtering the product, washing with acetone for 2-4 times, washing with 95wt% ethanol to remove chloride ions on the surface of the montmorillonite until silver ammonia is detected to be free of precipitate, vacuum drying at 100 ℃ for 6-10 h, and grinding to obtain silane modified montmorillonite.
Preferably, the POSS particle modified surface modification montmorillonite comprises at least one of eight-arm tetramethyl ammonium ion POSS particle modified cetyl trimethyl ammonium bromide modified montmorillonite, eight-arm acrolein propyl ester POSS particle modified polyether polyol modified montmorillonite, and eight-arm glycidyl methacrylate POSS particle modified silane modified montmorillonite.
Preferably, the preparation method of the POSS particle modified surface modification lamellar montmorillonite comprises the following steps: dispersing POSS particles and surface modification montmorillonite in hydrophilic or lipophilic dispersing agent, heating to 50 deg.C, stirring for 6-8 hr, filtering, washing and drying to obtain POSS particle modified surface modification montmorillonite.
Preferably, the thickness of the PET-based composite film is 20-80 μm.
The second aspect of the invention provides a method for preparing the PET-based composite film, which comprises the following steps:
Uniformly mixing the PET resin, the PEN resin and the citric acid triglyceride to obtain a mixture;
uniformly mixing the mixture, the POSS particle modified surface modification lamellar montmorillonite and the epoxidized soybean oil, and performing melt extrusion to obtain a master batch;
and carrying out melt casting on the master batch to form a film, thereby obtaining the PET-based composite film.
Preferably, the parameters of the melt extrusion include: the melt extrusion temperature is 260-280 ℃, the screw rotation speed is 150-200rad/min, and the residence time is 1-2min.
Preferably, the parameters of the melt-cast film include: the processing temperature is 275-290 ℃, the rotating speed of a casting roller is 0.8-1.2m/min, the rotating speed of a traction roller is 1.2-1.5m/min, the synchronous coefficient of the traction roller is 1-1.5, the tension of a winding roller is 3.2-4.5Kg, the synchronous coefficient of the winding roller is 0.2-0.5, and the temperature of a cooling roller is 20-70 ℃.
Preferably, the cooling roller comprises a cooling roller No. 1, a cooling roller No. 2 and a cooling roller No. 3; the temperature of the No. 1 cooling roller is 60-70 ℃, the temperature of the No. 2 cooling roller is 40-60 ℃, and the temperature of the No. 3 cooling roller is 20-40 ℃.
A third aspect of the invention provides the use of a PET-based composite film according to the invention in packaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) The PET-based composite film adopts a small amount of PEN with more benzene ring structures similar to PET structures to blend, so that the strength and the barrier property of the material are improved to a certain extent; the wider glass transition temperature and melting point range is beneficial to the processing and flowing of materials; meanwhile, the POSS particle modified surface modification lamellar montmorillonite is adopted as an additive, and the terminal multi-arm structure in the POSS particle effectively links the surface of the lamellar montmorillonite through the surface modification of the lamellar montmorillonite, so that the intercalation of the POSS particle is realized, the dispersion of the montmorillonite and the increase of interlayer spacing are further promoted, and the barrier property of the material is greatly improved; the POSS particles can realize uniform dispersion of the POSS particles and the montmorillonite due to the lipophilicity, and further serve as stress dispersion points, so that the mechanical property of the material is improved; the citric acid triglyceride and the epoxidized soybean oil are introduced to effectively improve the processability and plasticity of the material, so that the uniformity of the material and the dispersion of the nano particles are promoted.
(2) The PET-based composite film has high toughness and high barrier property, wherein the breaking elongation is 154.6-184.6%, the tensile strength is 52.8-85.6MPa, the transverse tearing strength is 153.2-198.4MPa, the longitudinal tearing strength is 196.5-231.4MPa, the oxygen permeability of the PET-based composite film with the thickness of 25 μm is 27.7-47.5cm 3/(m2 & 24h & 0.1MPa, the water vapor permeability is 5.1-8.2 g/(m 2 & 24hr & MPa), the light transmittance is 84.6-88.3%, and the PET-based composite film can be used in the high-end packaging field with high requirements on mechanical property and barrier property.
(3) The invention adopts a casting extrusion film forming method after melt extrusion granulation to form a film, comprehensively considers the thermal property and orientation of materials, promotes the orientation of the film in the longitudinal direction through traction and tension setting, and realizes the improvement of crystallization effect through the control of extrusion residence time and cooling roller temperature.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents, apparatus used in the examples below were obtained from conventional commercial sources, unless otherwise specified, or may be obtained by methods known in the art.
Example 1
The PET-based composite film comprises the following components in parts by mass: 100 parts of PET resin, 10 parts of PEN resin, 3 parts of POSS particle modified surface modified lamellar montmorillonite, 4 parts of citric acid triglyceride and 3.5 parts of epoxidized soybean oil.
The preparation method of the PET-based composite film comprises the following steps:
(1) Uniformly mixing PET resin, PEN resin and citric acid triglyceride at 50 ℃ at a rotating speed of 200rmp to obtain a mixture;
(2) Uniformly mixing the mixture, POSS particle modified surface modification lamellar montmorillonite and epoxidized soybean oil at a rotating speed of 150rmp, putting the mixture into a double-screw extruder, carrying out melt extrusion, and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 260 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Melting and casting the master batch to form a film to obtain a PET-based composite film; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 275 ℃, the rotating speed of the casting roller is 1.1m/min, the rotating speed of the traction roller is 1.4m/min, the synchronous coefficient of the traction roller is 1.3, the tension of the winding roller is 4.2Kg, the synchronous coefficient of the winding roller is that the temperature of the cooling roller No. 0.35,1 is 65 ℃, the temperature of the cooling roller No. 2 is 45 ℃, and the temperature of the cooling roller No. 3 is 30 ℃.
In this embodiment, the following components are used:
the PET resin is polyethylene terephthalate resin, the molecular weight of the PET resin is 28000, the melting point is 258 ℃, and the crystallization temperature is 130 ℃; the glass transition temperature is 74-82 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.7.
The PEN resin is polyethylene naphthalate resin, the molecular weight of the PEN resin is 48000, the melting point of the PEN resin is 275 ℃, and the crystallization temperature of the PEN resin is 192 ℃; the glass transition temperature is 120-124 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.35.
The POSS particle modified surface modification montmorillonite is eight-arm tetramethyl ammonium ion POSS particle modified cetyl trimethyl ammonium bromide modified montmorillonite, the adopted montmorillonite is sodium montmorillonite, and the particle size is 200-300 meshes; the distance between polymers after intercalation modification of eight-arm tetramethyl ammonium ion POSS particles can reach 150-300nm.
The preparation method of the hexadecyl trimethyl ammonium bromide modified lamellar montmorillonite comprises the following steps: dissolving sodium montmorillonite in deionized water to form 8wt% suspension, and stirring uniformly; adding cetyl trimethyl ammonium bromide, stirring for 4 hours, standing and hydrating for 36 hours; wherein, the mass of the hexadecyl trimethyl ammonium bromide accounts for 12 percent of the mass of the sodium montmorillonite.
Eight-arm tetramethyl ammonium ion POSS particle modified cetyl trimethyl ammonium bromide modified lamellar montmorillonite, and the preparation method comprises the following steps: dispersing eight-arm tetramethyl ammonium ion POSS particles and hexadecyl trimethyl ammonium bromide modified lamellar montmorillonite in tetrahydrofuran dispersant to prepare 12wt% suspension, heating to 50 ℃, stirring for 8 hours, and then filtering, washing and drying; wherein, the mass of the eight-arm tetramethyl ammonium ion POSS particles accounts for 32 percent of the mass of the cetyl trimethyl ammonium bromide modified lamellar montmorillonite; the particle size of the hexadecyl trimethyl ammonium bromide modified lamellar montmorillonite is 300 meshes.
Example 2
The PET-based composite film comprises the following components in parts by mass: 100 parts of PET resin, 15 parts of PEN resin, 4.5 parts of POSS particle modified surface modification lamellar montmorillonite, 4.5 parts of citric acid triglyceride and 3.5 parts of epoxidized soybean oil.
The preparation method of the PET-based composite film comprises the following steps:
(1) Uniformly mixing PET resin, PEN resin and citric acid triglyceride at 50 ℃ at a rotating speed of 200rmp to obtain a mixture;
(2) Uniformly mixing the mixture, POSS particle modified surface modification lamellar montmorillonite and epoxidized soybean oil at a rotating speed of 150rmp, putting the mixture into a double-screw extruder, carrying out melt extrusion, and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 270 ℃, the screw rotation speed is 160rad/min, and the residence time is 2min;
(3) Melting and casting the master batch to form a film to obtain a PET-based composite film; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 280 ℃, the rotating speed of the casting roller is 1m/min, the rotating speed of the traction roller is 1.4m/min, the synchronous coefficient of the traction roller is 1.4, the tension of the winding roller is 4.5Kg, the synchronous coefficient of the winding roller is 0.4,1, the temperature of the cooling roller is 60 ℃, the temperature of the cooling roller is 50 ℃, and the temperature of the cooling roller is 25 ℃.
In this embodiment, the following components are used:
The PET resin is polyethylene terephthalate resin, the molecular weight of the PET resin is 32000, the melting point is 262 ℃, and the crystallization temperature is 128 ℃; the glass transition temperature is 72-80 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.8.
The PEN resin is polyethylene naphthalate resin, the molecular weight of the PEN resin is 44000, the melting point of the PEN resin is 271 ℃, and the crystallization temperature of the PEN resin is 185 ℃; the glass transition temperature is 118-122 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.4.
The POSS particle modified surface modification montmorillonite is eight-arm acrolein propyl ester POSS particle modified polyether polyol modified montmorillonite, the adopted montmorillonite is sodium montmorillonite, and the particle size is 250-350 meshes; the distance between polymers after the eight-arm acrolein propyl ester POSS particles are intercalated and modified can reach 200-350nm.
The preparation method of the polyether polyol modified montmorillonite comprises the following steps: dissolving polyether glycol in dimethylacetamide to form a solution, adding aqueous suspension of cetyltrimethylammonium bromide modified lamellar montmorillonite into the solution, stirring at a rotating speed of 150rmp after mixing, heating to 90 ℃ for dehydration, realizing surface modification, grinding and sieving; wherein, the mass percentage of polyether glycol accounts for 20 percent of the mass percentage of cetyl trimethyl ammonium bromide modified lamellar montmorillonite; the aqueous suspension of cetyltrimethylammonium bromide modified montmorillonite refers to: cetyl trimethylammonium bromide modified montmorillonite was dissolved in deionized water to form an 8wt% suspension.
Eight-arm acrolein propyl ester POSS particle modified polyether polyol modified lamellar montmorillonite, and the preparation method thereof comprises the following steps: dispersing eight-arm acrolein propyl ester POSS particles and polyether polyol modified lamellar montmorillonite in dimethylacetamide to prepare 10wt% suspension, heating to 50 ℃, stirring for 8 hours, refluxing, filtering, washing and drying; wherein, the mass of the eight-arm acrolein propyl ester POSS particles accounts for 35 percent of the mass of the polyether polyol modified lamellar montmorillonite; the particle size of the polyether polyol modified montmorillonite is 350 meshes.
Example 3
The PET-based composite film comprises the following components in parts by mass: 100 parts of PET resin, 20 parts of PEN resin, 6 parts of POSS particle modified surface modification lamellar montmorillonite, 4.5 parts of citric acid triglyceride and 3.5 parts of epoxidized soybean oil.
The preparation method of the PET-based composite film comprises the following steps:
(1) Uniformly mixing PET resin, PEN resin and citric acid triglyceride at 50 ℃ at a rotating speed of 200rmp to obtain a mixture;
(2) Uniformly mixing the mixture, POSS particle modified surface modification lamellar montmorillonite and epoxidized soybean oil at a rotating speed of 150rmp, putting the mixture into a double-screw extruder, carrying out melt extrusion, and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 280 ℃, the screw rotation speed is 200rad/min, and the residence time is 2min;
(3) Melting and casting the master batch to form a film to obtain a PET-based composite film; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 290 ℃, the rotating speed of the casting roller is 0.8m/min, the rotating speed of the traction roller is 1.2m/min, the synchronous coefficient of the traction roller is 1.5, the tension of the winding roller is 4.2Kg, the synchronous coefficient of the winding roller is 0.5, the temperature of the No.1 cooling roller is 65 ℃, the temperature of the No.2 cooling roller is 55 ℃, and the temperature of the No.3 cooling roller is 35 ℃.
In this embodiment, the following components are used:
the PET resin is polyethylene terephthalate resin, the molecular weight of the PET resin is 30000, the melting point is 260 ℃, and the crystallization temperature is 133 ℃; the glass transition temperature is 75-82 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.75.
The PEN resin is polyethylene naphthalate resin, the molecular weight of the PEN resin is 44000, the melting point of the PEN resin is 271 ℃, and the crystallization temperature of the PEN resin is 185 ℃; the glass transition temperature is 118-122 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.4.
The POSS particle modified surface modification montmorillonite is eight-arm glycidyl methacrylate POSS particle modified silane modified montmorillonite, the adopted montmorillonite is sodium montmorillonite, and the particle size is 250-350 meshes; the distance between polymers after the intercalation modification of the eight-arm glycidyl methacrylate POSS particles can reach 200-300nm.
The preparation method of the silane modified lamellar montmorillonite comprises the following steps: adding chlorosilane into sodium montmorillonite, adding into dimethylacetamide, heating to 60 ℃, stirring and refluxing for 48 hours, filtering the product, washing with acetone for 4 times, washing with 95wt% ethanol to remove chloride ions on the montmorillonite surface until silver ammonia is detected to be free of precipitate, vacuum drying at 100 ℃ for 6-10 hours, and grinding to obtain the product; wherein, the mass ratio of chlorosilane to sodium montmorillonite is 6.5:10.
The preparation method of the eight-arm glycidyl methacrylate POSS particle modified silane modified lamellar montmorillonite comprises the following steps: uniformly dispersing eight-arm glycidyl methacrylate POSS particles and silane modified lamellar montmorillonite in dimethylacetamide, heating to 50 ℃, stirring for 8 hours, and then filtering, washing and drying; wherein, the mass of the eight-arm glycidyl methacrylate POSS particles accounts for 35 percent of the mass of the silane modified lamellar montmorillonite; the grain diameter of the silane modified montmorillonite is 350 meshes.
Comparative example 1 (differing from example 1 in the use of surface-modified montmorillonite)
The PET-based composite film comprises the following components in parts by mass: 100 parts of PET resin, 10 parts of PEN resin, 3 parts of surface-modified montmorillonite, 4 parts of citric acid triglyceride and 3.5 parts of epoxidized soybean oil.
The preparation method of the PET-based composite film comprises the following steps:
(1) Uniformly mixing PET resin, PEN resin and citric acid triglyceride at 50 ℃ at a rotating speed of 200rmp to obtain a mixture;
(2) Uniformly mixing the mixture, the surface modification montmorillonite and the epoxidized soybean oil at a rotating speed of 150rmp, putting the mixture into a double-screw extruder, carrying out melt extrusion, and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 260 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Melting and casting the master batch to form a film to obtain a PET-based composite film; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 275-290 ℃, the rotating speed of a casting roller is 1.1m/min, the rotating speed of a traction roller is 1.4m/min, the synchronous coefficient of the traction roller is 1.3, the tension of a winding roller is 4.2Kg, the synchronous coefficient of the winding roller is that the temperature of the cooling roller No. 0.35,1 is 65 ℃, the temperature of the cooling roller No. 2 is 45 ℃, and the temperature of the cooling roller No. 3 is 30 ℃.
In this comparative example, the components used are specifically as follows:
the PET resin is polyethylene terephthalate resin, the molecular weight of the PET resin is 28000, the melting point is 258 ℃, and the crystallization temperature is 130 ℃; the glass transition temperature is 74-82 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.7.
The PEN resin is polyethylene naphthalate resin, the molecular weight of the PEN resin is 48000, the melting point of the PEN resin is 275 ℃, and the crystallization temperature of the PEN resin is 192 ℃; the glass transition temperature is 120-124 ℃; the heat shrinkage (150 ℃ C., 30 min) was 0.35.
The surface modification montmorillonite is hexadecyl trimethyl ammonium bromide modification montmorillonite, the adopted montmorillonite is sodium montmorillonite, the grain diameter is 200-300 meshes, and the preparation method comprises the following steps: dissolving sodium montmorillonite in deionized water to form 8wt% suspension, and stirring uniformly; adding cetyl trimethyl ammonium bromide, stirring for 4 hours, standing and hydrating for 36 hours; wherein, the mass of the hexadecyl trimethyl ammonium bromide accounts for 12 percent of the mass of the sodium montmorillonite.
Performance testing
The PET-based composite films prepared in examples 1 to 3 and comparative example 1 were subjected to the related mechanical properties and water-oxygen barrier property tests, and the results are shown in Table 1.
TABLE 1
Compared with example 1, the comparative example 1 adopts the surface modification montmorillonite which is not modified by POSS particles, and the dispersibility of the surface modification montmorillonite is reduced, so that the transverse and longitudinal tearing strength and the oxygen and water vapor transmittance of the prepared PET-based composite film are obviously reduced.
Compared with example 1, example 2 increases the amount of PEN resin and POSS particle modified surface modification montmorillonite, the elongation at break is reduced, the strength is improved due to the increase of the amount of PEN resin, and the barrier property is improved due to the increase of nano particles and PEN.
Compared with example 2, example 3 increases the dosage of PEN resin and POSS particle modified surface modification montmorillonite, the strength is further improved, the barrier property is slightly improved, but the cost is relatively improved.
While the preferred embodiment of the present application has been described in detail, the application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the application, and these modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (9)
1. The PET-based composite film is characterized by comprising the following components in parts by weight: 100 parts of PET resin, 10-20 parts of PEN resin, 3-6 parts of POSS particle modified surface modification lamellar montmorillonite, 3-6 parts of citric acid triglyceride and 2-4 parts of epoxidized soybean oil.
2. The PET-based composite film according to claim 1, wherein the molecular weight of the PET resin is 20000 to 35000.
3. The PET-based composite film of claim 1, wherein the PEN resin has a molecular weight of 32000-54000.
4. The PET-based composite film according to claim 1, wherein in the POSS particle modified surface modification montmorillonite, the mass of POSS particles is 20-40% of the mass of the surface modification montmorillonite, and the particle size of the surface modification montmorillonite is 200-400 mesh.
5. The PET-based composite film of claim 1, wherein the POSS particle-modified surface-modified montmorillonite comprises at least one of eight-arm tetramethylammonium ion POSS particle-modified cetyltrimethylammonium bromide-modified montmorillonite, eight-arm methacrylate POSS particle-modified polyether polyol-modified montmorillonite, eight-arm glycidyl methacrylate POSS particle-modified silane-modified montmorillonite.
6. The method for producing a PET-based composite film according to any one of claims 1 to 5, comprising the steps of:
Uniformly mixing the PET resin, the PEN resin and the citric acid triglyceride to obtain a mixture;
uniformly mixing the mixture, the POSS particle modified surface modification lamellar montmorillonite and the epoxidized soybean oil, and performing melt extrusion to obtain a master batch;
and carrying out melt casting on the master batch to form a film, thereby obtaining the PET-based composite film.
7. The method of claim 6, wherein the parameters of melt extrusion include: the melt extrusion temperature is 260-280 ℃, the screw rotation speed is 150-200rad/min, and the residence time is 1-2min.
8. The method according to claim 6, wherein the parameters of the melt-cast film formation include: the processing temperature is 275-290 ℃, the rotating speed of a casting roller is 0.8-1.2m/min, the rotating speed of a traction roller is 1.2-1.5m/min, the synchronous coefficient of the traction roller is 1-1.5, the tension of a winding roller is 3.2-4.5Kg, the synchronous coefficient of the winding roller is 0.2-0.5, and the temperature of a cooling roller is 20-70 ℃.
9. Use of the PET-based composite film of any one of claims 1-5 in packaging.
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