CN115093681B - High-barrier PET material and preparation method thereof - Google Patents
High-barrier PET material and preparation method thereof Download PDFInfo
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- CN115093681B CN115093681B CN202210808994.4A CN202210808994A CN115093681B CN 115093681 B CN115093681 B CN 115093681B CN 202210808994 A CN202210808994 A CN 202210808994A CN 115093681 B CN115093681 B CN 115093681B
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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 high-barrier PET material comprises, by weight, 100 parts of PET resin and C 3 N 4 ‑SC CO 2 0.1 to 1.5 parts of antioxidant and 0.3 to 1 part of antioxidant; c (C) 3 N 4 ‑SC CO 2 Is g-C 3 N 4 Blending with the mixed solution, and passing through supercritical CO 2 The treated product, the mixed solution contains deionized water, ethanol and silane coupling agent; the preparation method comprises the following steps: c (C) 3 N 4 ‑SC CO 2 Blending with PET resin, and then carrying out melt extrusion granulation to obtain the high-barrier PET material. The high-barrier PET material prepared by the invention has better gas barrier property and simultaneously has balanced barrier property and mechanical property; the preparation process is simple, is suitable for use and is easy for mass 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 with excellent properties such as good mechanical properties, CO 2 、O 2 The composite material has good barrier property, high tensile strength and the like, is an environment-friendly material, is widely applied to various packaging materials and film materials, and has gradually increased proportion in recent years and rapid development.
Common high barrier resins such as EVOH (ethylene vinyl alcohol copolymer) and PEN (polyethylene naphthalate) are expensive and cannot be used on a large scale. PVDC (polyvinylidene chloride) has been widely used, but it is inferior in impact resistance and the like because it contains chlorine elements and decomposes HCl gas when heated and burned, limiting its use. Compared with PET, the PET material 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 modes for improving the barrier property of PET gas mainly comprise a surface coating method, a multilayer compounding method, a blending or copolymerization method and the like, but the processes of the other methods are more complicated except the blending method. Polyethylene terephthalate (PET) nanocomposites of varying graphene (RGO) content were prepared by melt blending and micro injection molding methods as Guo Shaoyun et al. The gas barrier property of the PET/RGO nanocomposite under different injection molding pressure conditions is researched, and the result shows that compared with pure PET, the oxygen permeability of the composite 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 adopting the method, the processing technology is complex, the product is difficult to recycle, the cost is relatively high, and the PET bottle becomes a bottleneck for large-scale application and popularization.
Disclosure of Invention
< technical problem to be solved by the invention >
The current PET has insufficient gas barrier property.
< technical scheme adopted by the invention >
Aiming at the technical problems, the invention aims to provide a high-barrier PET material and a preparation method thereof.
The specific contents are as follows:
first, the invention provides a high-barrier PET material, which comprises, by weight, 100 parts of PET resin and C 3 N 4 -SC CO 2 0.1 to 1.5 parts0.3-1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Blending with the mixed solution, and passing through supercritical CO 2 The treated product, the mixed solution 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 carrying out melt extrusion granulation to obtain the high-barrier PET material.
< technical mechanism adopted by the invention >
By reacting the prepared g-C 3 N 4 Supercritical CO 2 The treatment has the following functions: using SC CO 2 High permeability, high solubility and high diffusivity of molecules, enabling g-C 3 N 4 Peeling into two-dimensional sheets and reducing agglomeration; the second action is that: using SC CO 2 The nonpolar 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 When the pressure is increased, micro-region shearing force exists at the boundary of the two-phase interface, and g-C is generated under the action of the shearing force 3 N 4 Stripping to form a laminated structure; meanwhile, the silane coupling agent is easy to dissolve in water and absolute ethyl alcohol, and is used in SC CO 2 Under the molecular action, ethanol molecules and silane coupling agent molecules can be infiltrated into g-C 3 N 4 Interlayer and intra-layer defect holes, thereby increasing the compatibility of inorganic phase and organic phase in subsequent reaction;
< beneficial effects achieved by the invention >
The high-barrier PET material prepared by the invention has better gas barrier property and simultaneously has balanced barrier property and mechanical property; the preparation process is simple, is suitable for use and is easy for mass production.
Drawings
FIG. 1 is supercritical CO 2 The connection structure of the equipment is schematically shown.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
First, the invention provides a high-barrier PET material, which comprises, by weight, 100 parts of PET resin and C 3 N 4 -SC CO 2 0.1 to 1.5 parts of antioxidant and 0.3 to 1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Blending with the mixed solution, and passing through supercritical CO 2 The treated product, the mixed solution contains deionized water, ethanol and a silane coupling agent.
In the invention, C 3 N 4 -SC CO 2 The preparation method of (C) is g-C 3 N 4 Adding into the mixed solution, stirring while ultrasonic, and placing into supercritical CO 2 In the equipment, the treatment is carried out for 5 to 10 hours under 5 to 30MPa and 40 to 80 ℃, the pressure is slowly released to obtain the treatment liquid, the treatment liquid is centrifuged, the upper layer liquid is taken out, and the C is obtained after drying 3 N 4 -SC CO 2 。
Supercritical CO 2 The equipment is composed of CO 2 The device comprises a gas cylinder, a pressure controller, an air inlet connection system, a high-pressure reaction kettle, a pressure relief valve and a cooling frame; supercritical CO 2 A schematic diagram of the connection structure of the device is shown in fig. 1.
In the invention, the volume ratio of the ethanol to the deionized water is 1:1-4.
In the invention, the silane coupling agent occupies g-C 3 N 4 0.3 to 5 percent of the 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 a speed of 5-20 ℃/min, preserving heat for 2-4 h, cooling to room temperature at a 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 hr, and ultrasonic treatingDispersing for 20-50 min, repeatedly washing the soaked mixed solution with deionized water for multiple times to neutrality, 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 carrying out 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 conclusion, the method comprises the steps of,
(1) The invention utilizes a high-temperature polymerization method to synthesize the graphite-phase carbon nitride g-C with a two-dimensional lamellar structure by regulating and controlling the polymerization temperature, time and heating rate 3 N 4 。
(2) The invention utilizes supercritical CO 2 Process as nonpolar solvent, transfer of silane coupling agent to g-C 3 N 4 Is slowly decompressed in the inner hole and the interlayer. Using SC CO 2 The nonpolar nature of (2) makes the solubility of polar substances weaker, so that the polar substances can be mutually dissolved with ethanol and are insoluble in water, and the polar substances are mainly divided into two phases in a system: SC CO 2 Ethanol phase and water phase. g-C of the Block 3 N 4 Dispersed in SC CO 2 In water and ethanol systems, g-C in order to minimize interfacial free energy in the system 3 N 4 Will first be present in SC CO 2 At the interface of the ethanol phase and the water phase. With further increase in pressure, CO 2 Molecules can intercalate into g-C 3 N 4 Is expanded in volume, during which it dissolves in SC CO 2 The ethanol and the silane coupling agent molecules dissolved in the ethanol are also carried into g-C 3 N 4 Between the sheets, with the increase of pressure, the block g-C 3 N 4 The shear force is generated by extrusion at the interface of the two phases,let g-C 3 N 4 The sheeting layer was peeled off.
(3) The invention aims to improve the problems of insufficient barrier property, mechanical property, scratch resistance and the like of PET materials. By g-C 3 N 4 Amino and unsaturated amino groups exist in triazine ring and defect, and the triazine ring and defect are treated by supercritical CO 2 Processing to make g-C 3 N 4 The silane coupling agent is transferred into the inorganic phase layer and the defect hole when the interlayer spacing of the sheet layers is opened, and the PET terminal hydroxyl and the g-C can be made at the same time of reactive extrusion 3 N 4 The amino group reaction is carried out, and the silane coupling agent is used for connecting an organic phase and an inorganic phase, so that the interaction force of the organic phase and the inorganic phase is enhanced, the interlayer spacing of the inorganic phase is opened, and the g-C of PET molecular chains and lamellar layers is facilitated 3 N 4 The intercalation structure and the stripping structure are formed, and the compatibility of the intercalation structure 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 that the addition amount of the inorganic filler is low (less than 1%).
< example >
Example 1
(1)g-C 3 N 4 Is prepared from
Weighing 10g of melamine in a crucible;
placing the crucible in a muffle furnace, heating to 550 ℃ at a speed of 15 ℃/min, preserving heat for 3 hours, cooling to room temperature at a speed of 15 ℃/min, taking out the crucible, and grinding the obtained light yellow product into powder by an agate mortar;
soaking the pale yellow powder in 2-5 mol/L nitric acid solution for 3h, performing ultrasonic dispersion for 30min during the soaking process, repeatedly washing the soaked mixed solution with deionized water for multiple times to neutrality, and drying to obtain g-C 3 N 4 。
(2)C 3 N 4 -SC CO 2 Is prepared from
Will g-C 3 N 4 3 g is added into 40mL of mixed liquid, and the mixed liquid 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 addition amount of the silane coupling agent is g-C 3 N 4 Addition amount of2% (mass fraction). Adding, stirring while ultrasonic treating for 30min, and placing in supercritical CO 2 Treating at 15MPa and 60 ℃ for 7 hours, and slowly releasing pressure; after pressure relief, the treated mixture containing g-C is taken out 3 N 4 Ultrasonic dispersing, centrifuging for 15-40 min at 2000-4000 r/min, and removing supernatant to obtain g-C 3 N 4 Is a dispersion of (a); and then drying at 100 ℃ for 6-8 hours, and grinding for standby.
(3) Preparation of composite materials
1 part C 3 N 4 -SC CO 2 Blending with 100 parts of PET resin and 0.5 part of antioxidant, and then carrying out melt extrusion granulation, wherein the extrusion temperature is 260-300 ℃ and the rotating speed is 10-50 r/min, thus obtaining the high-barrier PET material.
Example 2
This example differs from example 1 in that in (2), ultra-high pressure CO 2 In the process, the mixture is treated for 7 hours at 25MPa and 70 ℃ and slowly depressurized.
Example 3
This example differs from example 1 in that in (2), ultra-high pressure CO 2 In the process, the mixture is treated for 7 hours at the temperature of 5MPa and 40 ℃ and slowly depressurized.
Example 4
This example differs from example 1 in that (2) the silane coupling agent is added in an amount of g-C 3 N 4 5% of the amount added (mass fraction).
Example 5
This example differs from example 1 in that (2) the silane coupling agent is added in an amount of g-C 3 N 4 0.5% of the amount added.
Example 6
This example differs from example 1 in that in (2), g-C is as follows 3 N 4 4, g is added 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 silane coupling agent is addedThe dosage is g-C 3 N 4 2% of the amount added (mass fraction).
Example 7
This example differs from example 1 in that in (2), g-C is as follows 3 N 4 2, g is added into 35mL 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 addition amount of the silane coupling agent is g-C 3 N 4 2% of the amount added (mass fraction).
Comparative example
Comparative example 1
The comparative example differs from example 1 in that in (2), the mixed solution is a blend of absolute ethanol and deionized water; wherein, the volume ratio of the absolute ethyl alcohol to the deionized water is 1:2.
< test example >
Experimental determination was performed using examples 1 to 5 as samples and comparative example 1 as a sample.
Measurement of mechanical properties is referred to GB/T1040-2006;
the barrier properties include a water vapor barrier test and an oxygen barrier test, the water vapor barrier test being referenced to GB1037-88, the oxygen barrier test being referenced to GB1038-2000.
Table 1 experimental determination results of samples
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A high-barrier PET material is characterized by comprising, by weight, 100 parts of PET resin and C 3 N 4 -SC CO 2 0.1 to 1.5 parts of antioxidant and 0.3 to 1 part of antioxidant;
C 3 N 4 -SC CO 2 is g-C 3 N 4 Blending with the mixed solution, and passing through supercritical CO 2 The treated product, the mixed solution contains deionized water, ethanol and a silane coupling agent.
2. The high barrier PET material of claim 1, wherein C 3 N 4 -SC CO 2 The preparation method of the (C) is that,
g-C 3 N 4 adding into the mixed solution, stirring while ultrasonic, and placing into supercritical CO 2 In the equipment, the treatment is carried out for 5 to 10 hours under 5 to 30MPa and 40 to 80 ℃, the pressure is slowly released to obtain the treatment liquid, the treatment liquid is centrifuged, the upper layer liquid is taken out, and the C is obtained after drying 3 N 4 -SC CO 2 。
3. The high barrier PET material of claim 1 or 2, wherein the volume ratio of ethanol to deionized water is 1:1-4.
4. The high barrier PET material of claim 1 or 2, wherein the silane coupling agent comprises g-C 3 N 4 0.3 to 5 percent of the mass.
5. The high barrier PET material of claim 1, wherein g-C 3 N 4 The preparation method of the (C) is that,
placing the nitrogen-containing precursor in a crucible, heating to 500-580 ℃ at a speed of 5-20 ℃/min, preserving heat for 2-4 h, cooling to room temperature at a 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 hr, ultrasonic dispersing for 20-50 min during soaking, and mixingRepeatedly washing the mixed solution with deionized water for several times to neutrality, and oven 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 of producing a high barrier PET material as claimed in any one of claims 1 to 7, comprising the steps of:
C 3 N 4 -SC CO 2 blending with PET resin, and then carrying out melt extrusion granulation to obtain the high-barrier PET material.
9. The method for producing high barrier PET material according to claim 8, wherein the extrusion temperature is 260 to 300 ℃ and the rotation speed is 10 to 50r/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277882A (en) * | 2003-02-28 | 2004-10-07 | Semiconductor Energy Lab Co Ltd | Carbon nitride composition, thin film transistor having the carbon nitride composition, display having the thin film transistor, and methods for producing them |
| CN105692573A (en) * | 2016-03-29 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of nano-structure carbon nitride |
| CN109467895A (en) * | 2018-12-05 | 2019-03-15 | 常州瑞杰新材料科技有限公司 | A kind of high-barrier PET material and preparation method thereof |
| CN110229475A (en) * | 2018-03-06 | 2019-09-13 | 中国科学院化学研究所 | A kind of PET nanocomposite and preparation method thereof |
| CN113337092A (en) * | 2021-06-16 | 2021-09-03 | 西华大学 | Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060099362A1 (en) * | 2004-11-05 | 2006-05-11 | Pepsico, Inc. | Enhanced barrier packaging for oxygen sensitive foods |
| CN109788760B (en) * | 2016-07-28 | 2021-12-14 | 艾克森实验室有限公司 | Antimicrobial photoreactive compositions comprising organic and inorganic multijunction composites |
-
2022
- 2022-07-11 CN CN202210808994.4A patent/CN115093681B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004277882A (en) * | 2003-02-28 | 2004-10-07 | Semiconductor Energy Lab Co Ltd | Carbon nitride composition, thin film transistor having the carbon nitride composition, display having the thin film transistor, and methods for producing them |
| CN105692573A (en) * | 2016-03-29 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of nano-structure carbon nitride |
| CN110229475A (en) * | 2018-03-06 | 2019-09-13 | 中国科学院化学研究所 | A kind of PET nanocomposite and preparation method thereof |
| CN109467895A (en) * | 2018-12-05 | 2019-03-15 | 常州瑞杰新材料科技有限公司 | A kind of high-barrier PET material and preparation method thereof |
| CN113337092A (en) * | 2021-06-16 | 2021-09-03 | 西华大学 | Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Atif Ayub，et al.."Gas barrier properties evaluation for boron nitride nanosheets-polymer (polyethylene-terephthalate) composites".《Applied Nanoscience》.2020,第11卷(第1期),第91-99页. * |
| 李明柳，等."质子化氮化碳整理涤纶织物工艺及其性能研究".《产业用纺织品》.2020,第38卷(第12期),第35-40,48页. * |
| 李正秋，等."PLA/R-TiO2复合材料的紫外光老化行为".《西华大学学报》.2019,第38卷(第5期),第55-63页. * |
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