CN103665848A - Polyethylene and nylon 6 blending modified barrier material - Google Patents
Polyethylene and nylon 6 blending modified barrier material Download PDFInfo
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- CN103665848A CN103665848A CN201310661418.2A CN201310661418A CN103665848A CN 103665848 A CN103665848 A CN 103665848A CN 201310661418 A CN201310661418 A CN 201310661418A CN 103665848 A CN103665848 A CN 103665848A
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- nylon
- polyethylene
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- polythene
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 35
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 30
- 230000004888 barrier function Effects 0.000 title claims abstract description 27
- -1 Polyethylene Polymers 0.000 title claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 19
- 238000002156 mixing Methods 0.000 title claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000004970 Chain extender Substances 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003017 thermal stabilizer Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001723 carbon free-radicals Chemical class 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 11
- 239000004033 plastic Substances 0.000 abstract description 11
- 238000001125 extrusion Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polyethylene and nylon 6 blending modified barrier material. The barrier material mainly comprises the following components in parts by weight: 40.0 to 60.0 parts of nylon 6, 30.0 to 40.0 parts of polyethylene, 10.0 to 20.0 parts of compatilizer, 0.3 to 1.0 part of lubricant, 0 to 20.0 parts of glass fiber, 0.3 to 2.0 parts of chain extender, and 0.3 to 1.0 part of composite heat stabilizer. The barrier material has the advantages of low melt flow index, high viscosity, high temperature resistance, and thermo-oxidative aging resistance; can be applied to extrusion and a blow moulding process so as to manufacture plastic products with a barrier property, improves the design freedom in choosing raw materials of barrier plastic products, and can be used to manufacture membrane plastic products at the same time.
Description
Technical field
The present invention relates to polymeric material field, in particular a kind of polythene/nylon 6 mixing modification barrier material.
Background technology
Polyethylene is a kind of general barrier material of high performance-price ratio, but for some, there is defect during the application of high-end or special dimension, such as under applied at elevated temperature environment, because polyethylene is as general-purpose plastics, its resistance toheat is not high, not strong to the osmotic-pressure-tolerant of hydrocarbon organic solvent, and there is polar group in nylon 6 molecules, intermolecular attraction increases, its barrier property is significantly better than polyethylene, to polyethylene with carry out Blending Modification of Nolyn 6 and can improve poly barrier property, simultaneously because nylon 6 is engineering plastics, its heat resistance is higher than polyethylene, therefore, prepare a kind of polythene/nylon 6 mixing modification blending and modifying barrier material, the material barrier property obtaining and heat resistance are between polyethylene and nylon 6 between the two, can be used as automobile, motorcycle fuel system fitment material.Plastics barrier material product mostly is blowing or squeeze technology for forming, first require material to there is higher melt strength, secondly owing to mostly being air cooling in molding process, therefore require material to there is good heatproof air aging performance, in order to avoid surface of plastic products yellowing.For polyethylene and nylon 6 mixing alloy material, because polyethylene and nylon 6 solubility parameters differ larger, both consistencies are poor, both there will be layering skin effect phenomenon at simple blend, properties is poor, first need to solve the problem of consistency, the common nylon 6 material viscosity of secondly selling is on the market 2.4~3.0, its melt strength is low, be unsuitable for blowing and extrusion molding processing, need to carry out tackify to common nylon 6, finally, in blowing or the extrusion molding course of processing, nylon 6 material is progressively cooled to room temperature from 200 ℃ in being exposed to air, product surface there will be very serious xanthochromia problem, therefore need to solve the heatproof air aging performance of material.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of polythene/nylon 6 mixing modification barrier material, mainly comprise following component and content:
Nylon 6:40.0~60.0 part
Polyethylene: 30.0~40.0 parts
Compatilizer: 10.0~20.0 parts
Lubricant: 0.3~1.0 part
Glass fibre: 0~20.0 part
Chainextender: 0.3~2.0 part
Composite thermal stabilizer: 0.3~1.0 part
Described nylon 6 viscosity 2.4-2.8;
Described polyethylene is high density polyethylene(HDPE) (Lanzhou Petrochemical 5000S);
Described compatilizer is maleic anhydride grafted polyethylene, and percentage of grafting is 0.8~1.2%, can solve the compatibility problem of polyethylene and nylon 6;
Described lubricant is at least one in calcium stearate, Zinic stearas, Magnesium Stearate, ethylene bis stearamide, polyester type lubricant (Honeywell AC540), and lubricant can improve the processing characteristics of nylon 6, reduces power consumption of polymer processing.
Described glass fibre is alkali-free glass fiber, and filament diameter is 12-15um, can further improve the resistance toheat of polyethylene/nylon 6 barrier material;
Described chainextender is at least one in Styrene And Chloroalkyl Acrylates glycidyl ester copolymer, Zelan 338, can reduce the melting index of material, increase the viscosity of nylon 6, improve the melt strength of polythene/nylon 6 mixing modification barrier material;
Described composite thermal stabilizer is Hinered phenols stablizer (as antioxidant 1010, oxidation inhibitor 1098), phosphorous acid esters stablizer (as irgasfos 168), azanol class carbon radicals trapping agent, bisphenolmonoacryates carbon radicals trapping agent, the phenols carbon radicals trapping agent of ortho position allyl group replacement, three kinds or the combination of Four types stablizer in Benzopyranone kind carbon radicals trapping agent, and composite thermal stabilizer can prevent nylon 6 oxidation flavescence in process of production;
By dried recovery nylon 6 and polyethylene, compatilizer, chainextender, composite thermal stabilizer, lubricant is put into together in proportion high-speed mixer high speed and is mixed after 1~5min, from the first feeder (main feeding), join extruding pelletization parallel equidirectional two-screw forcing machine, temperature by feed zone to head is followed successively by: 230~255 ℃, 230~255 ℃, 225~255 ℃, 220~245 ℃, 220~245 ℃, 210~230 ℃, 210~230 ℃, 220~240 ℃, the temperature of die head is 230~240 ℃, glass fibre adds from glass fiber opening in twin screw extrusion, after extruding through water-cooled, pelletizing, then pack, make polythene/nylon 6 mixing modification barrier material.
The polythene/nylon 6 mixing modification barrier material that the present invention makes can be used for extrusion molding, blowing processing, makes all kinds of containers, pipe, clavate obstruct plastics, also can make film class plastics.
Embodiment
The formula of embodiment 1~15 is as following table 1~2:
Table 1: embodiment 1~10 formula
Table 2: embodiment 11~15 formulas
Above-mentioned polythene/nylon 6 mixing modification barrier material is placed 3~4 hours in 120 ℃ in air dry oven, directly get dried pellet test melting index, adopt injection moulding machine to be injection molded into standard batten and colour table for testing heat-drawn wire and value of chromatism, during test color difference, the colour table being injection molded into is divided into two groups, one group of otherwise processed not wherein, another group is placed in air dry oven in 120 ℃ and takes out after placing 48 hours and test.Test result is as following table 3~4:
Table 3: embodiment 1~10 polythene/nylon 6 mixing modification barrier material performance measured value
Table 4: embodiment 11~15 polythene/nylon 6 mixing modification barrier material performance measured values
Polyethylene/nylon 6 barrier material after blending and modifying has that eutectic refers to, high viscosity, high temperature resistant, hot-air aging resistance feature, can be used for extruding and blow molding processing, manufacture has the plastics of barrier property, improve the design freedom that intercepts plastics selection, can be used for manufacturing film class plastics simultaneously.
Claims (3)
1. a polythene/nylon 6 mixing modification barrier material, mainly comprises following component and content:
Nylon 6:40.0~60.0 part
Polyethylene: 30.0~40.0 parts
Compatilizer: 10.0~20.0 parts
Lubricant: 0.3~1.0 part
Glass fibre: 0~20.0 part
Described nylon 6 viscosity 2.4-2.8, described polyethylene is high density polyethylene(HDPE), described compatilizer is maleic anhydride grafted polyethylene, percentage of grafting is 0.8~1.2%, described lubricant is calcium stearate, Zinic stearas, Magnesium Stearate, ethylene bis stearamide, at least one in polyester type lubricant, described glass fibre is alkali-free glass fiber, filament diameter is 12-15um, it is characterized in that described polythene/nylon 6 mixing modification barrier material also comprises 0.3~2.0 part of Styrene And Chloroalkyl Acrylates glycidyl ester copolymer, at least one chainextender in styrene-maleic anhydride copolymer.
2. polythene/nylon 6 mixing modification barrier material according to claim 1, characterized by further comprising 0.3~1.0 part of composite thermal stabilizer.
3. composite thermal stabilizer according to claim 2 is Hinered phenols stablizer, phosphorous acid esters stablizer, azanol class carbon radicals trapping agent, bisphenolmonoacryates carbon radicals trapping agent, the phenols carbon radicals trapping agent of ortho position allyl group replacement, three kinds or the combination of Four types stablizer in Benzopyranone kind carbon radicals trapping agent.
Priority Applications (1)
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CN201310661418.2A CN103665848B (en) | 2013-11-28 | 2013-11-28 | A kind of polythene/nylon 6 mixing modification barrier material |
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CN201310661418.2A CN103665848B (en) | 2013-11-28 | 2013-11-28 | A kind of polythene/nylon 6 mixing modification barrier material |
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Publication Number | Publication Date |
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CN103665848A true CN103665848A (en) | 2014-03-26 |
CN103665848B CN103665848B (en) | 2016-03-30 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106188458A (en) * | 2016-07-14 | 2016-12-07 | 山东省临沂市三丰化工有限公司 | A kind of stabiliser compositions of polyurethane curing agent |
CN107974075A (en) * | 2016-10-21 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | Nylon 6 material that a kind of proof stress turns white and preparation method thereof |
CN109988263A (en) * | 2019-04-02 | 2019-07-09 | 嘉兴华雯化工有限公司 | A kind of anhydride macromolecule chain extender and preparation method thereof |
CN111117216A (en) * | 2019-12-19 | 2020-05-08 | 金发科技股份有限公司 | Polyamide composition and preparation method thereof |
CN112898768A (en) * | 2019-11-19 | 2021-06-04 | 上海龙程塑料制品有限公司 | High-performance barrier material and multilayer composite barrier structure |
CN114085448A (en) * | 2021-12-23 | 2022-02-25 | 南通科顺建筑新材料有限公司 | High-temperature-resistant waterproof coiled material sizing material composition, high-temperature-resistant waterproof coiled material sizing material, and preparation method and application thereof |
CN114426696A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Polyurethane filler and preparation method and application thereof |
CN114773840A (en) * | 2022-04-20 | 2022-07-22 | 四川杨氏达防水材料有限公司 | High-temperature-resistant phthalic diamide high-molecular waterproof coiled material and preparation method thereof |
CN114806148A (en) * | 2022-05-25 | 2022-07-29 | 何平安 | Nylon co-extrusion film for wind power blade molding and production process thereof |
CN119078333A (en) * | 2024-11-06 | 2024-12-06 | 山东齐鲁乙烯化工股份有限公司 | High-barrier antibacterial food packaging film and preparation method thereof |
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CN106188458B (en) * | 2016-07-14 | 2019-06-11 | 山东省临沂市三丰化工有限公司 | A kind of stabiliser compositions of polyurethane curing agent |
CN107974075A (en) * | 2016-10-21 | 2018-05-01 | 合肥杰事杰新材料股份有限公司 | Nylon 6 material that a kind of proof stress turns white and preparation method thereof |
CN109988263A (en) * | 2019-04-02 | 2019-07-09 | 嘉兴华雯化工有限公司 | A kind of anhydride macromolecule chain extender and preparation method thereof |
CN109988263B (en) * | 2019-04-02 | 2021-12-28 | 嘉兴华雯化工股份有限公司 | Anhydride polymer chain extender and preparation method thereof |
CN112898768A (en) * | 2019-11-19 | 2021-06-04 | 上海龙程塑料制品有限公司 | High-performance barrier material and multilayer composite barrier structure |
CN111117216B (en) * | 2019-12-19 | 2021-09-17 | 金发科技股份有限公司 | Polyamide composition and preparation method thereof |
CN111117216A (en) * | 2019-12-19 | 2020-05-08 | 金发科技股份有限公司 | Polyamide composition and preparation method thereof |
CN114426696A (en) * | 2020-09-18 | 2022-05-03 | 中国石油化工股份有限公司 | Polyurethane filler and preparation method and application thereof |
CN114426696B (en) * | 2020-09-18 | 2023-05-12 | 中国石油化工股份有限公司 | Polyurethane filler and preparation method and application thereof |
CN114085448A (en) * | 2021-12-23 | 2022-02-25 | 南通科顺建筑新材料有限公司 | High-temperature-resistant waterproof coiled material sizing material composition, high-temperature-resistant waterproof coiled material sizing material, and preparation method and application thereof |
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CN114806148A (en) * | 2022-05-25 | 2022-07-29 | 何平安 | Nylon co-extrusion film for wind power blade molding and production process thereof |
CN119078333A (en) * | 2024-11-06 | 2024-12-06 | 山东齐鲁乙烯化工股份有限公司 | High-barrier antibacterial food packaging film and preparation method thereof |
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