CN115093681A - High-barrier PET material and preparation method thereof - Google Patents
High-barrier PET material and preparation method thereof Download PDFInfo
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- CN115093681A CN115093681A CN202210808994.4A CN202210808994A CN115093681A CN 115093681 A CN115093681 A CN 115093681A CN 202210808994 A CN202210808994 A CN 202210808994A CN 115093681 A CN115093681 A CN 115093681A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to the technical field of materials, and discloses a high-barrier PET material and a preparation method thereof, wherein the components comprise 100 parts by weight of PET resin and C 3 N 4 ‑SC CO 2 0.1-1.5 parts of antioxidant and 0.3-1 part of antioxidant; c 3 N 4 ‑SC CO 2 Is g-C 3 N 4 Mixing with the mixed solution, and subjecting to supercritical CO 2 The treated product is obtained by mixing a mixed solution containing deionized water, ethanol and a silane coupling agent; the preparation method comprises the following steps: c 3 N 4 ‑SC CO 2 Blending with PET resin, and then performing melt extrusion granulation to obtain the high-barrier PET material. The high-barrier PET material prepared by the invention has better gas barrier propertyThe performance and balance barrier property and mechanical property are considered at the same time; the preparation process is simple, suitable for use and easy for large-scale production.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a high-barrier PET material and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is a common thermoplastic polymer material,has excellent properties such as good mechanical properties, and good performance on CO 2 、O 2 Good barrier property, high tensile strength and the like, and is an environment-friendly material, and is widely applied to various packaging materials and film materials, and the proportion of the material is gradually increased and the material is rapidly developed in recent years.
Common high barrier resins such as EVOH (ethylene vinyl alcohol copolymer) and PEN (polyethylene naphthalate) are expensive and cannot be applied on a large scale. Although PVDC (polyvinylidene chloride) is widely used, its use is limited because it contains chlorine, HCl gas is decomposed during heating and combustion, and its impact resistance is poor. Compared with PET, PET has wide market prospect, but the gas barrier property, transparency, heat resistance and the like of the PET material obtained under the existing process condition still need to be further improved. Under the current market conditions, PET has good characteristics and high cost performance, so that the PET has good market prospect.
The existing method for improving the gas barrier property of PET mainly comprises a surface coating method, a multilayer compounding method, a blending method or a copolymerization method and the like, but the processes of other methods except the blending method are complex. Polyethylene terephthalate (PET) nanocomposites of different graphene (RGO) content were prepared by melt blending and micro injection molding by Guoshiyun et al. The gas barrier property of the PET/RGO nano composite material under different injection pressure conditions is researched, and the result shows that compared with pure PET, the oxygen permeability of the composite material is reduced by 85% by adding RGO with the mass fraction of 0.5%. When the barrier property of PET is improved by adopting a multilayer method, such as adding a barrier layer in a PET bottle or using a surface coating method, although the barrier property is improved by the method, the processing technology is complex, the product is difficult to recycle, the cost is relatively high, and the method becomes a bottleneck of large-scale application and popularization.
Disclosure of Invention
< problems to be solved by the present invention >
The current PET gas barrier property is insufficient.
< technical solution adopted in the present invention >
In view of the above technical problems, the present invention aims to provide a high-barrier PET material and a preparation method thereof.
The specific contents are as follows:
the invention provides a high-barrier PET material, which comprises 100 parts by weight of PET resin and C 3 N 4 -SC CO 2 0.1-1.5 parts of antioxidant and 0.3-1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Mixing with the mixed solution, and subjecting to supercritical CO 2 The mixed solution of the treated product contains deionized water, ethanol and a silane coupling agent.
Secondly, the invention provides a preparation method of a high-barrier PET material, which comprises the following steps:
C 3 N 4 -SC CO 2 blending with PET resin, and then performing melt extrusion granulation to obtain the high-barrier PET material.
< technical mechanism adopted in the present invention >
By subjecting the prepared g-C 3 N 4 Carrying out supercritical CO 2 The treatment has the following effects: using SC CO 2 High permeability, high solubility and high diffusivity of molecules, high permeability, high diffusivity of g-C 3 N 4 The two-dimensional sheet layer is stripped, and meanwhile, the agglomeration is reduced; the second action is as follows: using SC CO 2 The non-polar nature of the molecule, which is readily soluble in ethanol and not readily soluble in water, creates a two-phase interface, thus microscopically g-C 3 N 4 Exists at the boundary of two phase interfaces, causes the existence of micro-area shearing force when increasing pressure, and leads g-C to be in the action of the shearing force 3 N 4 Peeling to form a laminated structure; meanwhile, the silane coupling agent is easily dissolved in water and absolute ethyl alcohol, so that the silane coupling agent is in SC CO 2 Can permeate ethanol molecules and silane coupling agent molecules into g-C under the action of molecules 3 N 4 The interlayer and the intralayer are provided with defective holes, so that the compatibility of an inorganic phase and an organic phase in subsequent reaction is improved;
< advantageous effects achieved by the present invention >
The high-barrier PET material prepared by the invention has good gas barrier property and balanced barrier property and mechanical property; the preparation process is simple, is suitable for use and is easy for large-scale production.
Drawings
FIG. 1 shows supercritical CO 2 The connection structure of the device is shown schematically.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The invention provides a high-barrier PET material, which comprises 100 parts by weight of PET resin and C 3 N 4 -SC CO 2 0.1-1.5 parts of antioxidant and 0.3-1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Mixing with the mixed solution, and subjecting to supercritical CO 2 And (3) the treated product is prepared by mixing a mixed solution containing deionized water, ethanol and a silane coupling agent.
In the present invention, C 3 N 4 -SC CO 2 Is prepared by the process of 3 N 4 Adding into the mixed solution, stirring while ultrasonic treating, and placing in supercritical CO 2 In equipment, treating for 5-10 h at 5-30 MPa and 40-80 ℃, slowly releasing pressure to obtain a treatment solution, centrifuging the treatment solution, taking supernatant, and drying to obtain C 3 N 4 -SC CO 2 。
Supercritical CO 2 Plant by CO 2 The gas cylinder, the pressure controller, the gas inlet connecting system, the high-pressure reaction kettle, the pressure relief valve and the cooling frame; supercritical CO 2 The schematic diagram of the connection structure of the device is shown in fig. 1.
In the invention, the volume ratio of ethanol to deionized water is 1: 1-4.
In the present invention, the silane coupling agent is present in g-C 3 N 4 0.3 to 5% by mass.
In the present invention, g-C 3 N 4 The preparation method comprises the steps of placing a nitrogen-containing precursor in a crucible, heating to 500-580 ℃ at the speed of 5-20 ℃/min, preserving heat for 2-4 h, cooling to room temperature at the speed of 5-20 ℃/min, and grinding to obtain an intermediate;
soaking the intermediate in 2-5 mol/L nitric acid solution for 2-4 h, ultrasonically dispersing for 20-50 min in the soaking process, repeatedly washing the soaked mixed solution with deionized water for many times until the mixed solution is neutral, and drying to obtain g-C 3 N 4 。
In the present invention, the nitrogen-containing precursor includes at least one of urea, dicyandiamide, or melamine.
In the present invention, the antioxidant includes at least one of antioxidant 1010, antioxidant 1076, or antioxidant 618.
Secondly, the invention provides a preparation method of a high-barrier PET material, which comprises the following steps:
C 3 N 4 -SC CO 2 blending with PET resin, and then performing melt extrusion granulation to obtain the high-barrier PET material.
In the invention, the extrusion temperature is 260-300 ℃, and the rotating speed is 10-50 r/min.
In summary,
(1) the invention utilizes a high-temperature polymerization method to synthesize graphite-phase carbon nitride g-C with a two-dimensional lamellar structure by regulating and controlling polymerization temperature, time and heating rate 3 N 4 。
(2) The invention utilizes supercritical CO 2 Process as a nonpolar solvent for transferring a silane coupling agent to g-C 3 N 4 And slowly releasing pressure in the inner hole and the interlayer. Using SC CO 2 The nonpolar nature of the compound makes the compound have weaker dissolving capacity on polar substances, so the compound can be mutually soluble with ethanol and insoluble in water, and the system is mainly divided into two phases: SC CO 2 Ethanol phase and aqueous phase. g-C of blocks 3 N 4 Dispersed in SC CO 2 In water and ethanol systems, g-C is used to minimize the interfacial free energy in the system 3 N 4 Will first exist in SC CO 2 At the interface between the ethanol phase and the aqueous phase. With further increase in pressure, CO 2 The molecules can intercalateInto g-C 3 N 4 Inter-laminar, volume expansion of (2), during which the solution is in SC CO 2 The ethanol and the silane coupling agent molecules dissolved in the ethanol are also carried into the g-C 3 N 4 Between the sheets, with increasing pressure, blocks g-C 3 N 4 The g-C is extruded at the interface of two phases to generate shearing force 3 N 4 And stripping to form a sheet layer.
(3) The invention aims to solve the problems of insufficient barrier property, mechanical property, scratch resistance and the like of the PET material. By using g-C 3 N 4 Amino and unsaturated amino at triazine ring and defect position by supercritical CO 2 Process treatment of g-C 3 N 4 When the space between the sheets is opened, the silane coupling agent is transferred between inorganic phase layers and in a defect hole, and when the reaction extrusion is carried out, the hydroxyl end groups of PET and g-C can be reacted 3 N 4 The second is to utilize silane coupling agent to connect organic phase and inorganic phase, so that the interaction force between the organic phase and the inorganic phase is enhanced, and the interlayer spacing of the inorganic phase is opened, thereby being beneficial to g-C of PET molecular chain and lamella 3 N 4 The intercalation and the stripping structure are formed, and the compatibility of the intercalation and the stripping structure is improved, so that the gas barrier property and the mechanical property of the composite material are obviously improved under the condition of low addition amount (less than 1%) of the inorganic filler.
< example >
Example 1
(1)g-C 3 N 4 Preparation of
Weighing 10g of melamine in a crucible;
placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the speed of 15 ℃/min, then preserving the heat for 3h, then lowering the temperature to room temperature at the speed of 15 ℃/min, taking out the crucible, and grinding the obtained light yellow product into powder by using an agate mortar;
soaking the light yellow powder in 2-5 mol/L nitric acid solution for 3h, performing ultrasonic dispersion for 30min in the soaking process, repeatedly washing the soaked mixed solution with deionized water for multiple times until the mixed solution is neutral, and drying to obtain the g-C 3 N 4 。
(2)C 3 N 4 -SC CO 2 Preparation of
G to C 3 N 4 Adding 3 g of the mixture into 40mL of mixed solution, wherein the mixed solution is a blend of absolute ethyl alcohol, deionized water and a silane coupling agent; wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1:2, and the adding amount of the silane coupling agent is g-C 3 N 4 2 percent of the addition amount (mass fraction). Adding into the solution, stirring while ultrasonic treating for 30min, and placing in supercritical CO 2 Treating at 15MPa and 60 deg.C for 7 hr, and slowly releasing pressure; after pressure relief, the treated product containing g-C is taken out 3 N 4 The mixed solution is subjected to ultrasonic dispersion, the mixture is centrifuged for 15-40 min at 2000-4000 r/min, and the supernatant is removed to obtain g-C 3 N 4 The dispersion of (1); and drying for 6-8 h at 100 ℃, and grinding for later use.
(3) Preparation of composite materials
1 part of C 3 N 4 -SC CO 2 And mixing the PET resin with 100 parts of PET resin and 0.5 part of antioxidant, and then performing melt extrusion granulation at the extrusion temperature of 260-300 ℃ and the rotation speed of 10-50 r/min to obtain the high-barrier PET material.
Example 2
This example differs from example 1 in that in (2), ultrahigh pressure CO 2 Treating at 25MPa and 70 deg.C for 7 hr, and slowly releasing pressure.
Example 3
This example differs from example 1 in that in (2), ultrahigh pressure CO 2 Treating at 5MPa and 40 deg.C for 7 hr, and slowly releasing pressure.
Example 4
This example is different from example 1 in that (2) the silane coupling agent is added in an amount of g to C 3 N 4 5 percent of the addition amount (mass fraction).
Example 5
This example is different from example 1 in that (2) the silane coupling agent is added in an amount of g to C 3 N 4 0.5 percent of the addition amount (mass fraction).
Practice ofExample 6
This example is different from example 1 in that in (2), g to C 3 N 4 Adding 4 g of the mixture into 20mL of mixed solution, wherein the mixed solution is a blend of absolute ethyl alcohol, deionized water and a silane coupling agent; wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1:4, and the adding amount of the silane coupling agent is g-C 3 N 4 2 percent of the addition amount (mass fraction).
Example 7
This example differs from example 1 in that in (2), g to C 3 N 4 2 g of the mixture is added into 35mL of mixed solution, and the mixed solution is a blend of absolute ethyl alcohol, deionized water and a silane coupling agent; wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1:4, and the adding amount of the silane coupling agent is g-C 3 N 4 2 percent of the added amount (mass fraction).
< comparative example >
Comparative example 1
The difference between the comparative example and the example 1 is that in (2), the mixed solution is a blend of absolute ethyl alcohol and deionized water; wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 2.
< test example >
The experimental measurements were carried out using examples 1-5 as samples and comparative example 1 as sample.
The determination of the mechanical property refers to GB/T1040-2006;
the barrier performance comprises a water vapor barrier test and an oxygen barrier test, wherein the water vapor barrier test refers to GB1037-88, and the oxygen barrier test refers to GB 1038-2000.
TABLE 1 Experimental results for the samples
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The high-barrier PET material is characterized by comprising 100 parts by weight of PET resin and C 3 N 4 -SC CO 2 0.1-1.5 parts of antioxidant and 0.3-1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Mixing with the mixed solution, and subjecting to supercritical CO 2 And (3) the treated product is prepared by mixing a mixed solution containing deionized water, ethanol and a silane coupling agent.
2. The high-barrier PET material as claimed in claim 1, wherein C is C 3 N 4 -SC CO 2 The preparation method of the compound comprises the following steps of,
g-C 3 N 4 adding into the mixed solution, stirring while ultrasonic treating, and placing in supercritical CO 2 In equipment, treating for 5-10 h at 5-30 MPa and 40-80 ℃, slowly releasing pressure to obtain a treatment solution, centrifuging the treatment solution, taking supernatant, and drying to obtain C 3 N 4 -SC CO 2 。
3. The high-barrier PET material according to claim 1 or 2, wherein the volume ratio of ethanol to deionized water is 1: 1-4.
4. The high barrier PET material according to claim 1 or 2, wherein the silane coupling agent is present in g-C 3 N 4 0.3 to 5% by mass.
5. The high-barrier PET material as claimed in claim 1, wherein g-C 3 N 4 The preparation method of the compound comprises the following steps of,
putting the nitrogen-containing precursor into a crucible, heating to 500-580 ℃ at the speed of 5-20 ℃/min, preserving heat for 2-4 h, cooling to room temperature at the speed of 5-20 ℃/min, and grinding to obtain an intermediate;
soaking the intermediate in 2-5 mol/L nitric acid solution for 2-4 h, ultrasonically dispersing for 20-50 min in the soaking process, repeatedly washing the soaked mixed solution with deionized water for many times until the mixed solution is neutral, and drying to obtain g-C 3 N 4 。
6. The high-barrier PET material of claim 5 wherein the nitrogen-containing precursor comprises at least one of urea, dicyandiamide, or melamine.
7. The high barrier PET material of claim 1, wherein the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, or antioxidant 618.
8. A method for preparing a high-barrier PET material as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
C 3 N 4 -SC CO 2 blending with PET resin, and then performing melt extrusion granulation to obtain the high-barrier PET material.
9. The method for preparing the high-barrier PET material according to claim 8, wherein the extrusion temperature is 260-300 ℃ and the rotation speed is 10-50 r/min.
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