CN109467895A - A kind of high-barrier PET material and preparation method thereof - Google Patents
A kind of high-barrier PET material and preparation method thereof Download PDFInfo
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- CN109467895A CN109467895A CN201811480336.7A CN201811480336A CN109467895A CN 109467895 A CN109467895 A CN 109467895A CN 201811480336 A CN201811480336 A CN 201811480336A CN 109467895 A CN109467895 A CN 109467895A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The present invention relates to technical field of polymer materials, and in particular to a kind of high-barrier PET material and preparation method thereof.Component includes: PET resin 65-80%, PEN resin 5-20%, HDPE resin 5-15%, modified barrier filler 0.1-5%, nano inorganic filler 0.1-5%, antioxidant 0.3-1%, dispersing agent 1-2% and compatilizer 2-6% by weight.Preparation method includes: (1) raw material preparation；(2) mixing；(3) melting extrusion is granulated.While high-barrier PET material prepared by the present invention has preferable resistance oxygen ability and gas barrier property, balance barrier property and mechanical property are taken into account；Preparation process is simple, is suitable for actual use, is easy to be mass produced.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of high-barrier PET material and preparation method thereof.
Background technique
Polyethylene terephthalate (poly (ethylene terephthalate)), abbreviation PET are thermoplasticity half
Crystalline plastics material.With high-fire resistance, high transparency, high gas-obstructing character, good resistance to chemical reagents and insulating properties, quilt
It is widely used for fiber, biaxially oriented film and polyester bottles and various packing containers etc..Current engineering plastics in the market,
PET is due to excellent cost performance, the greatly trend of substituted PBT, in packaging material field, especially packaging for bottle Material Field, PET
Even more development is swift and violent.
PET inherently has good characteristic: such as crystal property, intensity and rigidity, barrier property is also very high, especially
To non-polar gas, and its creep resistance and dimensional stability, linear expansion coefficient is also small, and this characteristic makes
It is very suitable to make packaging material.
Chinese patent CN106883565A discloses a kind of high-barrier composite film, wherein barrier layer using PET 30~
60%, PEN 8~18%, nano modification montmorillonite 30~80% are blended to improve the barrier property of PET, but PET and
The compatibility of PEN is poor, cannot preferably make up PET to the barrier property of vapor, there is its limitation.
As the continuous improvement of Chemical Engineering Technology and people's lives level constantly improve, barrier property general for PET,
Be no longer satisfied demand, for example, flexible package punch, solar cell backboard film, in terms of, therefore develop high
Barrier property PET material is market urgent need, and the trend of development.
Summary of the invention
The defect that it is an object of the invention to overcome PET barrier property of the existing technology bad, provides a kind of high-barrier
PET material and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of high-barrier PET material, percentage, including following components:
Preferably, including following components:
Preferably, the modified barrier filler is the mixture of one or both of modified montmorillonoid, modified galapectite.
Preferably, the modified montmorillonoid is to obtain montmorillonite by para-aminobenzoate is sulfonate modified；It is described to change
Property galapectite be by galapectite by aluminate coupling agent modification obtain.
Further, the method for modified montmorillonoid are as follows:
(1) montmorillonite that will have been dried, is heated to 60-80 DEG C, and at revolving speed 400-1000rpm, constant temperature stirs 1~2h；
It is preferred that revolving speed is 500rpm；
(2) para-aminobenzoate hydrochlorate is added, continues 15~18h of stirring；
(3) not chloride ion-containing is washed with water in washing water；It washed, dried with dehydrated alcohol again, obtain modified montmorillonoid.
The method of modified galapectite are as follows:
(1) galapectite dried is stirred to 5~10min at 100~110 DEG C；
(2) aluminate coupling agent is added, maintains 100~110 DEG C of temperature or so, continues 20~60min of stirring.
Preferably, the nano inorganic filler is Nano-meter SiO_22, Nano titanium nitride, one of nano aluminium oxide or at least
Two kinds of mixture, partial size is between 50~500nm.
It is highly preferred that the nano inorganic filler is Nano-meter SiO_22, Nano titanium nitride and nano aluminium oxide mixture；Its
Middle Nano-meter SiO_22, Nano titanium nitride, nano aluminium oxide weight ratio be 25~50:1:25~50.
Preferably, the antioxidant is the mixing of one or both of antioxidant 1010 and irgasfos 168.
It is further preferred that the antioxidant is the mixture of antioxidant 1010 and irgasfos 168；Wherein antioxidant 1010 with
The weight ratio of irgasfos 168 is 1:1.
Preferably, the dispersing agent is the mixture of one or both of polyethylene wax or polypropylene wax.
Preferably, the compatilizer is SEBS.
A kind of preparation method of high-barrier PET material, comprising the following steps:
(1) raw material preparation: PET resin 65-80%, PEN resin 5-20%, HDPE resin 5-15%, modified barrier filler
0.1-5%, nano inorganic filler 0.1-5%, antioxidant 0.3-1%, dispersing agent 1-2%, compatilizer 2-6%；
(2) mixing: antioxidant and dispersing agent are uniformly mixed according to the above ratio, obtain mixed powder；Modified barrier is filled out
Material, nano inorganic filler are uniformly mixed according to the above ratio；PET resin, PEN resin, HDPE resin, compatilizer is added and obtains
Mixed powder is mixed by said ratio；
(3) melting extrusion is granulated.
Preferably, modified barrier filler, nano inorganic filler described in step (2) be blended in revolving speed be 1200~
1300rpm, temperature are uniformly mixed under conditions of being 80~110 DEG C.
The utility model has the advantages that
(1) PET is blended the present invention with naphthalene-ring containing PEN, nonpolar HDPE, in optimization non-polar gas transmission coefficient
While, material can also be effectively improved to the obstructing capacity of steam, and can greatly slow down hydrone pair in high humidity environment
The broken ring of material structure, is conducive to keeping for a long time for barrier property.
(2) the barrier filler of PET material of the invention addition is can to greatly improve material resistance made of Recompounded multielement
Oxygen ability, and improve the big disadvantage of PET water imbibition, it prevents a large number of water molecules from permeating, weakens hydrone in process of osmosis to PET
The loosening of polar molecule chain and plasticization, to guarantee material barrier property more permanent in high humidity environment.Polynary selection
Barrier filler can also reduce amount of filler, take into account balance barrier property and mechanical property, expand its answering in some special dimensions
With.
(3) modified montmorillonoid of high-barrier PET material of the invention addition or/and modified galapectite, can effectively improve
The compatibility of filler and resin, to guarantee the excellent barrier property and mechanical property of material.
(4) high-barrier PET material of the invention can largely reduce other barriers and fill out when Nano titanium nitride is added
The additional amount of material plays better barriering effect.
(5) preparation process of high-barrier PET material of the invention is simple, is suitable for actual use, is easy to be mass produced.
Specific embodiment
In order to be more readily understood technical solution of the present invention and technical effect, the present invention is carried out below with reference to embodiment detailed
Explanation.
Term is explained:
PET: polyethylene terephthalate；
PEN: polyethylene naphthalate；
SEBS: being middle spring with the ethylene-butene copolymer that polybutadiene plus hydrogen obtain using polystyrene as end segment
The linear tri-block copolymer of block.
Dispersing agent is polyethylene wax in following embodiments, and the compatilizer is SEBS.
Embodiment 1
A kind of high-barrier PET material, including following compositions: PET resin 74.5%, PEN resin 10%, HDPE resin 7%,
Modified galapectite 1%, nano silica 1%, nano aluminium oxide 0.98%, Nano titanium nitride 0.02%, antioxidant 0.5%,
Dispersing agent 1%, compatilizer 4%.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, and specific modification procedure is that will do
Dry galapectite stirs 5min under 100 DEG C, 500rpm revolving speed；Aluminate coupling agent is slowly added into again (to dilute using ether
Agent), 110 DEG C of temperature are maintained, continues to stir 30min.
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 150nm, the nano aluminium oxide of 150nm, 150nm Nano titanium nitride with it is upper
Modified galapectite is stated to be uniformly mixed under 100 DEG C, 1200rpm speed conditions；PET resin, PEN resin, HDPE tree is added
Rouge, compatilizer and obtained mixed powder mix according to the ratio；Melting extrusion is granulated.
Embodiment 2
A kind of high-barrier PET material, including following compositions: PET resin 74.5%, PEN resin 10%, HDPE resin 7%,
Modified montmorillonite used 1%, nano silica 1%, nano aluminium oxide 0.98%, Nano titanium nitride 0.02%, antioxidant 0.5%,
Dispersing agent 1%, compatilizer 4%.
Modified montmorillonoid is to obtain montmorillonite by para-aminobenzoate is sulfonate modified in the present embodiment, specific to walk
The rapid montmorillonite will to have dried, is heated to 60 DEG C, stirs 2h under 500rpm revolving speed；Para-aminobenzoate hydrochlorate, dimension is added
60 DEG C of temperature are held to continue to stir 16h；Not chloride ion-containing is washed with water in washing water；It washed, dried with dehydrated alcohol again.
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 150nm, the nano aluminium oxide of 150nm, 150nm Nano titanium nitride with it is upper
Modified montmorillonoid is stated to be uniformly mixed under the conditions of 100 DEG C, 1200rpm；PET resin, PEN resin, HDPE resin, phase is added
The mixed powder for holding agent and obtaining mixes according to the ratio；Melting extrusion is granulated.
Embodiment 3
A kind of high-barrier PET material, including following compositions: PET resin 80%, PEN resin 7%, HDPE resin 5% change
Property montmorillonite 2 %, modified galapectite 2%, nano silica 0.98%, Nano titanium nitride 0.02%, antioxidant 0.5%, point
Powder 1%, compatilizer 1.5%.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, and the specific steps are the same as those in embodiment 1.
Modified montmorillonoid is to obtain montmorillonite by para-aminobenzoate is sulfonate modified in the present embodiment, specific to walk
Suddenly with embodiment 2.
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By the Nano titanium nitride of nano silica, 150nm that above-mentioned partial size is 150nm and above-mentioned modified montmorillonoid, modified angstrom
Lip river stone is uniformly mixed under 80 DEG C, 1300rpm speed conditions；PET resin, PEN resin, HDPE resin, compatilizer is added
It is mixed according to the ratio with obtained mixed powder；Melting extrusion is granulated.
Embodiment 4
A kind of high-barrier PET material, including following compositions: PET resin 65%, PEN resin 5%, HDPE resin 15% change
Property galapectite 5%, nano silica 2.45%, nano aluminium oxide 2.5%, Nano titanium nitride 0.05%, antioxidant 1%, point
Powder 2%, compatilizer 2%.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, and the specific steps are the same as those in embodiment 1.
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 50nm, the nano aluminium oxide of 500nm, 200nm Nano titanium nitride with it is above-mentioned
Modified galapectite is uniformly mixed under the conditions of 100 DEG C, 1200rpm；PET resin, PEN resin, HDPE resin, compatible is added
Agent and obtained mixed powder mix according to the ratio；Melting extrusion is granulated.
Embodiment 5
A kind of high-barrier PET material, including following compositions: PET resin 65%, PEN resin 20%, HDPE resin 5% change
Property montmorillonite 0.1%, nano silica 1%, nano aluminium oxide 1.06%, Nano titanium nitride 0.04%, antioxidant 0.3%,
Dispersing agent 1.5%, compatilizer 6%.
Modified montmorillonoid is obtained by aluminate coupling agent modification in the present embodiment, and the specific steps are the same as those in embodiment 1.
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 250nm, the nano aluminium oxide of 300nm, 50nm Nano titanium nitride with it is above-mentioned
Modified montmorillonoid is uniformly mixed under the conditions of 110 DEG C, 1200rpm；PET resin, PEN resin, HDPE resin, compatible is added
Agent and obtained mixed powder mix according to the ratio；Melting extrusion is granulated.
Comparative example 1
A kind of high-barrier PET material, ingredient be embodiment 1 formula in be not added HDPE resin, and other components and its
Between relative scale it is constant.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, the specific same embodiment of modification procedure
1。
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 150nm, the nano aluminium oxide of 150nm, 150nm Nano titanium nitride with it is upper
Modified galapectite is stated to be uniformly mixed under 100 DEG C, 1200rpm speed conditions；PET resin, PEN resin, compatilizer is added
It is mixed according to the ratio with obtained mixed powder；Melting extrusion is granulated.
Comparative example 2
A kind of high-barrier PET material, ingredient be embodiment 1 formula in be not added PEN resin, and other components and its it
Between relative scale it is constant.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, the specific same embodiment of modification procedure
1。
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；By above-mentioned partial size be the nano silica of 150nm, the nano aluminium oxide of 150nm, 150nm Nano titanium nitride with it is upper
Modified galapectite is stated to be uniformly mixed under 100 DEG C, 1200rpm speed conditions；PET resin, HDPE resin, compatilizer is added
It is mixed according to the ratio with obtained mixed powder；Melting extrusion is granulated.
Comparative example 3
A kind of high-barrier PET material, ingredient be embodiment 1 formula in nano inorganic filler, and other components are not added
Relative scale between and its is constant.
Modified galapectite is obtained by aluminate coupling agent modification in the present embodiment, the specific same embodiment of modification procedure
1。
The preparation method of the high-barrier PET material is to mix in proportion antioxidant and dispersing agent, is mixed
Powder；Above-mentioned modified galapectite stirs evenly under 100 DEG C, 1200rpm speed conditions；PET resin, PEN resin, HDPE is added
Resin, compatilizer and obtained mixed powder and the modification galapectite stirred evenly mix according to the ratio；Melting extrusion is granulated.
Comparative example 4
100% pure PET material.
Embodiment and comparative example the performance test results are shown in Table 1:
Table 1
As can be seen from Table 1, high-barrier PET material prepared by the present invention has good barrier property and mechanical property.From
The comparison of embodiment 1 and comparative example 1~2 can be seen that PET is blended with PEN, HDPE can penetrate system in optimization non-polar gas
While number, material can also be effectively improved to the obstructing capacity of steam, its compatibility can be improved；From embodiment 1 and comparison
Example 1 can be seen that the Recompounded multielement in the present invention and obstruct filler, can greatly improve material resistance oxygen ability, and improve PET suction
Aqueous big disadvantage.
In addition, PET and PEN do one layer therein respectively in multilayer material in the report for preparing high barrier material
Report more, but this compatibility between layers is poor, also will affect the barrier property of material.
The foregoing is only a preferred embodiment of the present invention, according to the disclosure and teachings of the above specification, the present invention
Those skilled in the art can also change and modify the above embodiment.Therefore, the invention is not limited to upper
Face is disclosed and the specific embodiment of description, should also be as falling into claim of the invention to some modifications and changes of the invention
Protection scope in.In addition, these terms are intended merely to facilitate although using some specific terms in this specification
It is bright, it does not limit the present invention in any way.
Claims (10)
1. a kind of high-barrier PET material, which is characterized in that percentage includes following components:
2. high-barrier PET material according to claim 1, which is characterized in that the component are as follows:
3. high-barrier PET material according to claim 1, which is characterized in that the modified barrier filler is that modified illiteracy is de-
The mixture of one or both of soil, modified galapectite；Wherein modified montmorillonoid is by montmorillonite by p-aminobenzoic acid
Hydrochloride modification obtains, and modified galapectite is to obtain galapectite by aluminate coupling agent modification.
4. high-barrier PET material according to claim 1, which is characterized in that the nano inorganic filler is Nano-meter SiO_22、
One of Nano titanium nitride, nano aluminium oxide or at least two mixture, partial size is between 50~500nm.
5. high-barrier PET material according to claim 1, which is characterized in that the nano inorganic filler is Nano-meter SiO_22、
The mixture of Nano titanium nitride and nano aluminium oxide；Wherein Nano-meter SiO_22, Nano titanium nitride, nano aluminium oxide weight ratio be 25
~50:1:25~50.
6. high-barrier PET material according to claim 1, which is characterized in that the antioxidant is antioxidant 1010 and resists
The mixture of one or both of oxygen agent 168.
7. high-barrier PET material according to claim 1, which is characterized in that the antioxidant is antioxidant 1010 and resists
The mixture of oxygen agent 168；The weight ratio of the antioxidant 1010 and irgasfos 168 is 1:1.
8. high-barrier PET material according to claim 1, which is characterized in that the dispersing agent is polyethylene wax or poly- third
The mixture of one or both of alkene wax；The compatilizer is SEBS.
9. a kind of preparation method of high-barrier PET material according to claim 1-8, which is characterized in that including
Following steps:
(1) raw material preparation: PET resin 65-80%, PEN resin 5-20%, HDPE resin 5-15%, modified barrier filler 0.1-
5%, nano inorganic filler 0.1-5%, antioxidant 0.3-1%, dispersing agent 1-2%, compatilizer 2-6%；
(2) mixing: antioxidant and dispersing agent are uniformly mixed according to the above ratio, obtain mixed powder；By modified barrier filler, receive
Rice inorganic filler is uniformly mixed according to the above ratio；PET resin, PEN resin, HDPE resin, compatilizer and obtained mixing is added
Powder is mixed by said ratio；
(3) melting extrusion is granulated.
10. preparation method according to claim 9, it is characterised in that: modified barrier filler, nanometer described in step (2)
The temperature of inorganic filler mixing is 80~110 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110843297A (en) * | 2019-11-13 | 2020-02-28 | 嘉兴鹏翔包装材料有限公司 | High-barrier VMPET film and preparation method thereof |
| CN112226052A (en) * | 2020-10-14 | 2021-01-15 | 中瀚新材料科技有限公司 | High-barrier modified polyester and preparation method thereof |
| CN112277417A (en) * | 2020-10-29 | 2021-01-29 | 广东宝佳利绿印股份有限公司 | Three-layer co-extrusion high-transparency high-barrier BOPET film |
| CN113103708A (en) * | 2021-05-21 | 2021-07-13 | 浙江晟祺实业有限公司 | High-molecular moisture-proof composite material and preparation method thereof |
| CN115028916A (en) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | High-barrier light plastic for plastic packaging container and preparation method thereof |
| CN115093681A (en) * | 2022-07-11 | 2022-09-23 | 西华大学 | High-barrier PET material and preparation method thereof |
| CN115536997A (en) * | 2022-10-17 | 2022-12-30 | 杭州恒峰塑料制品有限公司 | Blending type barrier plastic packaging container |
| CN115975355A (en) * | 2022-12-29 | 2023-04-18 | 广州市信联包装容器实业有限公司 | High-barrier-toughness PET (polyethylene terephthalate) -based composite film and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110843297A (en) * | 2019-11-13 | 2020-02-28 | 嘉兴鹏翔包装材料有限公司 | High-barrier VMPET film and preparation method thereof |
| CN112226052A (en) * | 2020-10-14 | 2021-01-15 | 中瀚新材料科技有限公司 | High-barrier modified polyester and preparation method thereof |
| CN112277417A (en) * | 2020-10-29 | 2021-01-29 | 广东宝佳利绿印股份有限公司 | Three-layer co-extrusion high-transparency high-barrier BOPET film |
| CN113103708A (en) * | 2021-05-21 | 2021-07-13 | 浙江晟祺实业有限公司 | High-molecular moisture-proof composite material and preparation method thereof |
| CN115028916A (en) * | 2022-06-08 | 2022-09-09 | 广州丽盈塑料有限公司 | High-barrier light plastic for plastic packaging container and preparation method thereof |
| CN115093681A (en) * | 2022-07-11 | 2022-09-23 | 西华大学 | High-barrier PET material and preparation method thereof |
| CN115093681B (en) * | 2022-07-11 | 2023-06-13 | 成都瑞琦医疗科技有限责任公司 | High-barrier PET material and preparation method thereof |
| CN115536997A (en) * | 2022-10-17 | 2022-12-30 | 杭州恒峰塑料制品有限公司 | Blending type barrier plastic packaging container |
| CN115536997B (en) * | 2022-10-17 | 2023-12-01 | 杭州恒峰塑料制品有限公司 | Blending type barrier plastic packaging container |
| CN115975355A (en) * | 2022-12-29 | 2023-04-18 | 广州市信联包装容器实业有限公司 | High-barrier-toughness PET (polyethylene terephthalate) -based composite film and preparation method and application thereof |
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