CN115477803A - Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure - Google Patents
Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure Download PDFInfo
- Publication number
- CN115477803A CN115477803A CN202210691641.0A CN202210691641A CN115477803A CN 115477803 A CN115477803 A CN 115477803A CN 202210691641 A CN202210691641 A CN 202210691641A CN 115477803 A CN115477803 A CN 115477803A
- Authority
- CN
- China
- Prior art keywords
- evoh resin
- evoh
- ethylene
- resin particle
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 372
- 229920005989 resin Polymers 0.000 title claims abstract description 285
- 239000011347 resin Substances 0.000 title claims abstract description 285
- 239000002245 particle Substances 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 350
- 239000008188 pellet Substances 0.000 claims abstract description 203
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 42
- 239000005977 Ethylene Substances 0.000 claims description 42
- 239000010410 layer Substances 0.000 claims description 38
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000012790 adhesive layer Substances 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000009891 weiqi Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 9
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 304
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 126
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 105
- 238000005406 washing Methods 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 47
- 239000010408 film Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 27
- 238000005119 centrifugation Methods 0.000 description 22
- 239000008187 granular material Substances 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007863 gel particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 235000010338 boric acid Nutrition 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000004291 polyenes Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 101000767534 Arabidopsis thaliana Chorismate mutase 2 Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 101000986989 Naja kaouthia Acidic phospholipase A2 CM-II Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XLLZUKPXODPNPP-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] XLLZUKPXODPNPP-UHFFFAOYSA-N 0.000 description 1
- BUWURQPWRDROFU-UHFFFAOYSA-N [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] BUWURQPWRDROFU-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910001730 borate mineral Inorganic materials 0.000 description 1
- 239000010429 borate mineral Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- BMQVDVJKPMGHDO-UHFFFAOYSA-K magnesium;potassium;chloride;sulfate;trihydrate Chemical compound O.O.O.[Mg+2].[Cl-].[K+].[O-]S([O-])(=O)=O BMQVDVJKPMGHDO-UHFFFAOYSA-K 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- VPOLVWCUBVJURT-UHFFFAOYSA-N pentadecasodium;pentaborate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] VPOLVWCUBVJURT-UHFFFAOYSA-N 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DPUZPWAFXJXHBN-UHFFFAOYSA-N tetrasodium dioxidoboranyloxy(dioxido)borane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]B([O-])OB([O-])[O-] DPUZPWAFXJXHBN-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to an ethylene-vinyl alcohol copolymer (EVOH) resin pellet composition, an ethylene-vinyl alcohol copolymer film formed therefrom, and a multilayer structure comprising the same. The EVOH resin particle composition includes first EVOH resin particles having a crest physical volume (Vmp) of 0.00001-6 um 3 /um 2 (ii) a And second EVOH resin particles having a surface wave peak solid volume (Vmp) of 0.00015 to 20um 3 /um 2 . The invention can improve the processing performance and mechanical property of EVOH composition when being made into film.
Description
Technical Field
The present invention relates to an ethylene-vinyl alcohol (EVOH) composition; in particular, it relates to an ethylene-vinyl alcohol copolymer resin pellet composition, a film and a multilayer structure formed from the EVOH resin pellet composition.
Background
EVOH resins are widely used in multilayer bodies for preserving perishable goods. For example, EVOH resins and multilayer bodies made therefrom are commonly used in the food packaging industry, medical equipment and consumable industry, pharmaceutical industry, electronics industry, and agrochemical industry. Specifically, EVOH resin is generally used in the form of a film; for example: it can be used to incorporate into a multilayer body as a distinct layer to act as an oxygen barrier.
In practice, the film made of EVOH material is required to have various properties such as processability, mechanical properties, and heat resistance. For example: when the EVOH thin film is formed, a large amount of Gel particles (Gel, also called fish eyes) are not formed on the surface, which means that the EVOH thin film has excellent processability; furthermore, when the EVOH film is stretched under a specific tension, it has good elongation, which means that it has desirable mechanical properties.
Disclosure of Invention
However, a concept or means for effectively satisfying the above requirements has not been proposed in the prior art. In view of the above problems, the present inventors have found that when two kinds of EVOH resin particles contained in an EVOH resin particle composition have a specific value range of the peak physical volume (Vmp) of the surface wave, the film formed from the EVOH resin particle composition can have good processability and mechanical properties.
Accordingly, in one aspect, the present invention provides an ethylene vinyl alcohol copolymer (EVOH) resin particle composition comprising: first EVOH resin particles having a surface wave peak solid volume (Vmp) of 0.00001 to 6um 3 /um 2 And second EVOH resin particles having a surface wave peak physical volume (Vmp) of 0.00015 to 20 μm 3 /um 2 。
According to some embodiments of the invention, the Vmp of the second EVOH resin pellet is greater than the Vmp of the first EVOH resin pellet.
According to some embodiments of the present invention, the melting point of the first EVOH resin particle is 135 to 179 ℃ and wherein the melting point of the second EVOH resin particle is 180 to 198 ℃.
According to some embodiments of the invention, the ethylene content of the first EVOH resin particles is 36 to 50mole percent.
According to some embodiments of the invention, the second EVOH resin particle has an ethylene content of 20 to 35mole percent.
According to some embodiments of the present invention, the EVOH resin pellet has a cylindrical, elliptic cylindrical, prismatic, spherical, elliptic spherical, or Weiqi shape, and has a major diameter/height of 1 to 5mm and a minor diameter of 1 to 5mm.
According to some embodiments of the invention, the weight percentage of the first EVOH resin particles to the second EVOH resin particles is 5:95 to 75:25.
according to some embodiments of the present invention, the EVOH resin pellet composition has a boron content of 5 to 550ppm.
According to some embodiments of the present invention, the EVOH resin pellet composition has an alkali metal content of 10 to 550ppm.
According to some embodiments of the invention, the first EVOH resin particle has a kurtosis (Sku) surface parameter of 0.0020 to 25; and the second EVOH resin particles have a kurtosis (Sku) surface parameter of 0.0070-111.
According to some embodiments of the present invention, the first EVOH resin particle has a surface parameter of a maximum peak height (Sp) of 0.0005 to 29 um; and the second EVOH resin pellet has a surface parameter of a maximum surface peak height (Sp) of 0.0020 to 63 um.
According to some embodiments of the present invention, the first EVOH resin particle has a protruding peak height (Spk) surface parameter of 0.001 to 2 um; and the second EVOH resin pellet has a protruding peak height (Spk) surface parameter of 0.003-22 um.
According to some embodiments of the invention, the first EVOH resin particle has a pole height (Sxp) surface parameter of 0.001 to 12 um; and the second EVOH resin pellet has a pole height (Sxp) surface parameter of 0.002-48 um.
According to some embodiments of the invention, the first EVOH resin particle has a linear average height (Ra) surface parameter of 0.001 to 0.990 um; and the second EVOH resin particles have a linear average height (Ra) surface parameter of 0.001-0.990 um.
According to some embodiments of the invention, the first EVOH resin particle has a line maximum height (Rz) surface parameter of 0.001 to 9.900 um; and the second EVOH resin particle has a linear maximum height (Rz) surface parameter of 0.001-9.900 um.
In another aspect of the present invention, an ethylene-vinyl alcohol copolymer film is formed from the EVOH resin pellet composition.
Yet another aspect of the present invention provides a multilayer structure comprising: (a) At least one ethylene-vinyl alcohol copolymer film formed of the EVOH resin pellet composition; (b) at least one polymer layer; and (c) at least one adhesive layer.
According to some embodiments of the present invention, the polymer layer is selected from the group consisting of a low density polyethylene layer, a polyethylene-grafted maleic anhydride (plma) layer, a polypropylene layer, and a nylon layer, and the adhesive layer is a tie layer.
According to some embodiments of the invention, the multilayer structure is a polymer layer/a bonding layer/an ethylene-vinyl alcohol copolymer film/a bonding layer/a polymer layer.
The invention provides an ethylene vinyl alcohol copolymer (EVOH) resin particle composition, an ethylene vinyl alcohol copolymer film formed by the EVOH resin particle composition and a multilayer structure comprising the EVOH resin particle composition, and a film formed by the EVOH resin particle composition has good processing performance and mechanical property without being limited by a specific theory.
Drawings
Embodiments of the present technology will now be described, by way of example only, with reference to the accompanying drawings, in which:
fig. 1 is a schematic illustration of a physical volume of a peak of a surface wave applied in accordance with the present invention.
It should be understood that aspects of the present invention are not limited to the configurations, instrumentalities, and characteristics shown in the attached drawings.
Detailed Description
In one aspect, the present invention relates to an ethylene vinyl alcohol copolymer (EVOH) resin particle composition comprising: first EVOH resin particles having a surface wave peak physical volume (Vmp) of 0.00001 to 6um 3 /um 2 And second EVOH resin particles having a surface wave peak physical volume (Vmp) of 0.00015 to 20 μm 3 /um 2 。
As used herein, the term "physical volume at the peak of a surface wave (Vmp) refers to the physical volume at a load area rate of p%, and its specific definition can be referred to ISO 25178. In addition, the sizes of the core, the protruding crest and the protruding trough can be quantified by volume parameters. As shown in fig. 1, vmp represents the volume of the protruding crest, vmc represents the volume of the core, vvc represents the volume of the core space, vvv represents the negative load area ratio of the protruding trough, and a section of 10% to 80% is designated as the core in the example preset of fig. 1. The Vmp of the first EVOH resin particle is 0.00001-6 um 3 /um 2 For example: 0.00001, 0.00005, 0.00100, 0.00200, 0.00500, 0.01000, and,0.05000, 0.10000, 0.50000, 1, 2, 3, 4, 5, or 6um 3 /um 2 . The second EVOH resin particle has a Vmp of 0.00015-20 um 3 /um 2 For example: 0.00015, 0.00050, 0.01000, 0.05000, 0.10000, 0.50000, 1, 5, 10, 15 or 20um 3 /um 2 . According to a preferred embodiment of the present invention, the Vmp of the second EVOH resin pellet is greater than the Vmp of the first EVOH resin pellet.
According to some embodiments of the invention, the melting point of the first EVOH resin particles is 135 to 179 ℃, for example: 135. 140, 145, 150, 155, 160, 165, 170, 175, or 179 ℃. On the other hand, the melting point of the second EVOH resin pellet is 180 to 198 ℃, for example: 180. 182, 184, 186, 188, 190, 192, 194, 196 or 198 ℃.
According to some embodiments of the invention, the ethylene content of the first EVOH resin particles may be about 36 to 50mole percent (mole%), for example: 36. 38, 40, 42, 44, 46, 48 or 50mole%. On the other hand, the ethylene content of the second EVOH resin pellet is 20 to 35mole%, for example: 20. 21, 23, 25, 27, 29, 31, 33 or 35 mol%.
Additionally or alternatively, the EVOH may have a degree of saponification of 90mole% or more, preferably 95 mole% or more, preferably 97mole% or more, preferably 99.5mole% or more.
EVOH pellets as used herein refers to the form and/or shape of the EVOH resin pelletized to form one or more pellets, which, although described throughout the present disclosure as being pelletized to form one or more EVOH pellets, may be processed into beads, cubes, chips, shavings, and the like; according to some embodiments of the present invention, the EVOH resin pellet has a cylindrical, elliptic cylindrical, prismatic, spherical, elliptic spherical, or go-chess shape, and has a major diameter or height of 1 to 5mm, for example: 1. 2, 3, 4 or 5mm; and a short diameter of 1 to 5mm, for example: 1. 2, 3, 4 or 5mm. As used herein, the term "major diameter/height" refers to the longest outer diameter of an object having a surface formed by a closed curve; the term "minor diameter" refers to the smallest diameter in a cross section perpendicular to the major diameter or height and having the largest area. As used herein, the term "object having a surface formed of a closed curved surface" is understood to mean an object having a surface formed of a curved surface as a whole; an object formed by a plurality of intersecting surfaces without edges and corners; or an object with a cross section which is not rectangular at any position.
Specifically, when the EVOH resin pellet is cylindrical or elliptic, its high range is between 1 and 5mm, for example: 1.5-5.0 mm, 1.7-5.0 mm, 2.2-5.0 mm, 2.4-5.0 mm, 2.6-5.0 mm, 2.8-5.0 mm, 3.0-5.0 mm, 3.2-5.0 mm, 3.4-5.0 mm, 3.6-5.0 mm, 3.8-5.0 mm, 4.0-5.0 mm, 1.7-4.5 mm, 1.7-4.4 mm, 1.7-4.2 mm, 1.7-4.0 mm, 1.7-3.8 mm, 1.7-3.6 mm, 1.7-3.4 mm, 1.7-3.2 mm, 1.7-3.0 mm; the minor diameter ranges from 1 to 5mm, for example: 1.5-5.0 mm, 1.7-5.0 mm, 2.2-5.0 mm, 2.4-5.0 mm, 2.6-5.0 mm, 2.8-5.0 mm, 3.0-5.0 mm, 3.2-5.0 mm, 3.4-5.0 mm, 3.6-5.0 mm, 3.8-5.0 mm, 4.0-5.0 mm, 1.7-4.5 mm, 1.7-4.4 mm, 1.7-4.2 mm, 1.7-4.0 mm, 1.7-3.8 mm, 1.7-3.6 mm, 1.7-3.4 mm, 1.7-3.2 mm, 1.7-3.0 mm.
When the EVOH pellets are round pellets, such as round pellets, oval pellets or go-chess pellets, the major diameter ranges from 1 to 5mm, for example: 1.5-5.0 mm, 2.2-5.0 mm, 2.4-5.0 mm, 2.6-5.0 mm, 2.8-5.0 mm, 3.0-5.0 mm, 3.2-5.0 mm, 3.4-5.0 mm, 3.6-5.0 mm, 3.8-5.0 mm, 4.0-5.0 mm, 2.0-4.5 mm, 2.0-4.4 mm, 2.0-4.2 mm, 2.0-4.0 mm, 2.0-3.8 mm, 2.0-3.6 mm, 2.0-3.4 mm, 2.0-3.2 mm, 2.0-3.0 mm; the minor axis is in the range of 1 to 5mm, for example: 1.5-5.0 mm, 1.8-4.6 mm, 2.4-4.6 mm, 2.6-4.6 mm, 2.8-4.6 mm, 3.0-4.6 mm, 3.2-4.6 mm, 3.4-4.6 mm, 3.6-4.6 mm, 3.8-4.6 mm, 4.0-4.6 mm, 1.6-4.5 mm, 1.6-4.4 mm, 1.6-4.2 mm, 1.6-4.0 mm, 1.6-3.8 mm, 1.6-3.6 mm, 1.6-3.4 mm, 1.6-3.2 mm, 1.6-3.0 mm, when the pill is shaped, the long diameter and the short diameter are equal.
According to some embodiments of the invention, the weight percentage of the first EVOH resin particles to the second EVOH resin particles is 5:95 to 75:25, for example: 5: 95. 15: 85. 25: 75. 35: 65. 45, and (2) 45: 55. 55: 45. 65:35 or 75:25.
according to some embodiments of the present invention, the EVOH resin particle composition may in some cases comprise a boron compound and/or boric acid and/or cinnamic acid and/or an alkali metal and/or a conjugated polyene and/or a lubricant and/or an alkaline earth metal. The above-mentioned substances can impart better properties to the EVOH resin pellet composition.
According to some embodiments of the present invention, the EVOH resin pellet composition may comprise a boron compound, wherein the boron content is 5 to 550ppm. In some cases of the above-described method, the boron content of the EVOH resin particulate composition may be 10 to 450ppm, 10 to about 400ppm, 10 to about 350ppm, 10 to about 300ppm, 10 to about 275ppm, 10 to about 250ppm, 10 to about 225ppm, 10 to about 200ppm, 10 to about 175ppm, about 20 to 450ppm, about 20 to about 400ppm, about 20 to about 350ppm, about 20 to about 300ppm, about 20 to about 275ppm, about 20 to about 250ppm, about 20 to about 225ppm, about 20 to about 200ppm, about 20 to about 175ppm, about 60 to 450ppm, about 60 to about 400ppm, about 60 to about 350ppm, about 60 to about 300ppm, about 60 to about 275ppm, about 60 to about 250ppm, about 60 to about 225ppm, about 60 to about 200ppm, about 60 to about 175ppm, about 175 to about about 100 to 450ppm, about 100 to about 400ppm, about 100 to about 350ppm, about 100 to about 300ppm, about 100 to about 275ppm, about 100 to about 250ppm, about 100 to about 225ppm, about 100 to about 200ppm, about 100 to about 175ppm, about 140 to 450ppm, about 140 to about 400ppm, about 140 to about 350ppm, about 140 to about 300ppm, about 140 to about 275ppm, about 140 to about 250ppm, about 140 to about 225ppm, about 140 to about 200ppm, about 180 to about 450ppm, about 180 to about 400ppm, about 180 to about 350ppm, about 180 to about 300ppm, about 180 to about 275ppm, about 180 to about 250ppm, about 180 to about 225ppm, about 220 to about 450ppm, about 220 to about 400ppm, about 220 to about 350ppm, about 220 to about 300ppm, about 220 to about 275ppm. When the boron content of the EVOH resin pellet composition is in a certain range, the viscosity of the EVOH resin pellet composition can be increased, the opportunity for the EVOH resin pellet composition to adhere to a screw is reduced, or EVOH on the screw is removed, so that the material has a self-cleaning function, and the uniformity of the film thickness can be further improved. According to a preferred embodiment of the present invention, the EVOH resin particle composition may further contain cinnamic acid, an alkali metal, a conjugated polyene, an alkaline earth metal, a salt thereof and/or a mixture thereof, in addition to the boron compound; these are common materials usually present in EVOH resin pellet compositions, giving them better properties. When the content of the compound having a conjugated polyene structure is 1 to 30000ppm per unit weight of the EVOH resin pellet composition, the coloring after heating can be further suppressed, and the thermal stability is further improved. When the content of the alkali metal compound or alkaline earth metal compound is 10 to 550ppm in terms of metal in the EVOH resin composition per unit weight, the long run moldability is further improved; the content may be, for example, according to circumstances: between 10-550ppm, between about 10-500ppm, between about 10-450ppm, between about 10-400ppm, between about 10-350ppm, between about 10-300ppm, between about 10-250ppm, between about 10-200ppm, between about 10-150ppm, between about 10-100ppm, between about 10-50ppm, between about 50-550ppm, between about 50-500ppm, between about 50-450ppm, between about 50-400ppm, between about 50-350ppm, between about 50-300ppm, between about 50-250ppm, between about 50-200ppm, between about 50-150ppm, between about 50-100ppm, between about 100-550ppm, between about 100-500ppm, between about 100-450ppm, between about 100-400ppm, between about 100-350ppm, between about 100-300 ppm, between about 100-250ppm, between about 100-200ppm, between about 100-150ppm, between about 200-550ppm, between about 200-200 ppm, between about 200-300ppm and about 300ppm, between about 400-300 ppm and about 300 ppm.
According to some embodiments of the invention, the boron compound may comprise boric acid or a metal salt thereof. <xnotran> , , ( , ), , ( , , , ), ( , ), ( , , , , ), ( , ), ( (II), , ), ( , , , , , ), ( , ), ( , , , ), ( , , , ), , ( , , , , ), ( (I), , ), ( , , ), . </xnotran> Borate minerals such as borax, kainite, boronite, periclase/gangalite (suanite), and boromagnesite (szaibelyite) may be included. Among them, borax, boric acid and sodium borate (e.g., sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate and sodium octaborate) are preferably used.
According to some embodiments of the invention, the first EVOH resin particle has a kurtosis (Sku) surface parameter of 0.0020 to 25, such as: from about 0.0100 to 25, from about 0.1000 to 25, from about 1 to 23.3000, from about 1 to 20, from about 1 to 15, from about 5 to 15, or from about 7 to 10. In another aspect, the second EVOH resin particle has a kurtosis (Sku) surface parameter of 0.0070 to 111, such as: from about 0.0100 to 111, from 0.0200 to 100, from about 0.2000 to 65, from about 2 to 50, from about 2 to 40, from about 10 to 40, or from about 20 to 40.
As used herein, the definition of the so-called "kurtosis (Sku) surface parameter" refers to ISO 25178; it can be understood that the height distribution of the contour surface within a sampling range is a parameter for determining the sharpness of the surface shape.
According to some embodiments of the present invention, the first EVOH resin particle has a surface parameter of a maximum peak height (Sp) of 0.0005 to 29um, for example: between about 0.0005 and 28um, between about 0.0010 and 25um, between about 0.0100 and 25um, between about 0.1000 and 25um, between about 1 and 20um, between about 1 and 15um, between about 5 and 15um, or between about 7 and 10um. On the other hand, the second EVOH resin pellet has a surface parameter of maximum surface peak height (Sp) of 0.0020 to 63um, such as: between about 0.0020 and 60um, between about 0.0200 and 60um, between about 0.2000 and 60um, between about 2 and 60um, between about 10 and 60um, between about 20 and 50um, between about 25 and 40um, between about 30 and 40um, or between about 30 and 36um.
As used herein, the definition of the so-called "maximum peak height (Sp) surface parameter" refers to ISO 25178.
According to some embodiments of the present invention, the first EVOH resin particle has a protruding peak height (Spk) surface parameter of 0.001 to 2um, for example: between about 0.001-2 um, between about 0.005-2 um, between about 0.010-2 um, between about 0.050-2 um, between about 0.100-1 um, or between about 0.500-1 um. On the other hand, the second EVOH resin pellet has a surface parameter of the protruding peak height (Spk) of 0.003 to 22um, for example: between about 0.003 and 20um, between about 0.030 and 20um, between about 0.300 and 20um, between about 1 and 20um, between about 5 and 15um, or between about 5 and 10um.
As used herein, the definition of the so-called "protruding peak height (Spk) surface parameter" refers to ISO 25178; in particular, it refers to the average height of the peak of the protruding wave.
According to some embodiments of the invention, the first EVOH resin particle has a pole height (Sxp) surface parameter of 0.001 to 12um, for example: between about 0.001 to 11um, between about 0.005 to 10um, between about 0.010 to 2um, between about 0.050 to 2um, between about 0.100 to 1um, or between about 0.500 to 1um. In another aspect, the second EVOH resin particle has a pole height of 0.002 to 48um (Sxp surface parameter, e.g., between about 0.003 to 48um, between about 0.030 to 30um, between about 0.300 to 20um, between about 1 to 20um, between about 5 to 15um, or between about 5 to 10 um).
As used herein, the definition of the so-called "pole height (Sxp) surface parameter" refers to ISO 25178; specifically, it means a height difference between the surface average surface and the surface wave peak after removing the peak having a particularly high height in the surface, and it means a height difference between 2.5% and 50% of the load area ratio by default.
According to some embodiments of the invention, the first EVOH resin particle has a linear average height (Ra) surface parameter of 0.001 to 0.990um, such as: between about 0.001 and 0.990um, between about 0.001 and 0.700um, between about 0.001 and 0.500um, between about 0.001 and 0.300um, between about 0.001 and 0.100um, between about 0.050 and 0.990um, between about 0.050 and 0.700um, between about 0.050 and 0.500um, between about 0.050 and 0.300um, or between about 0.050 and 0.100um. On the other hand, the second EVOH resin particles have a linear average height (Ra) surface parameter of 0.001 to 0.990um, such as: between about 0.001-0.990 um, between about 0.001-0.700 um, between about 0.001-0.500 um, between about 0.010-0.300 um, between about 0.010-0.100 um, between about 0.050-0.990 um, between about 0.050-0.700 um, between about 0.050-0.500 um, between about 0.050-0.300 um, or between about 0.050-0.100 um.
As used herein, the term "line arithmetic mean height (Ra) surface parameter" is a parameter defining surface roughness, and is defined in accordance with JIS B0601, specifically, it can be understood as an average absolute value of a profile curve over a reference length.
According to some embodiments of the invention, the first EVOH resin particles have a maximum height of line (Rz) surface parameter of 0.0010 to 9.9000um, such as: between about 0.0010 and 9um, between about 0.0010 and 7um, between about 0.0010 and 5um, between about 0.0100 and 3um, between about 0.0500 and 5um, between about 0.0500 and 3um, between about 0.0500 and 1um, or between about 0.0500 and 0.0800um. On the other hand, the second EVOH resin particles have a maximum height of line (Rz) surface parameter of 0.0010 to 9.9000um, such as: between about 0.0800-9 um, between about 0.1000-9 um, between about 0.1500-7 um, between about 0.5000-5 um, between about 0.5000-2.5000 um, or between about 1-2.5000 um. As used herein, the "line maximum height (Rz) surface parameter" is a parameter defining the surface roughness, which is defined with reference to JIS B0601, and specifically, it can be understood as the distance of a profile curve from the highest peak and the lowest valley on a reference length.
In another aspect, the present invention provides an ethylene-vinyl alcohol copolymer film formed from the EVOH resin pellet composition. Specifically, the ethylene-vinyl alcohol copolymer film is a single layer film.
In yet another aspect, the present invention provides a multilayer structure comprising: (a) At least one ethylene-vinyl alcohol copolymer film formed of the EVOH resin pellet composition; (b) at least one polymer layer; and (c) at least one adhesive layer.
According to some embodiments of the present invention, the polymer layer is selected from the group consisting of a low density polyethylene layer, a polyethylene grafted maleic anhydride (pe-grafted maleic anhydride) layer, a polypropylene layer, and a nylon layer, and the adhesive layer is an adhesive layer (tie layer), such as ARKEMA OREVAC 18729 from ARKEMA. Specifically, the laminated structure of the multi-layer structure is a polymer layer, an adhesive layer, an ethylene-vinyl alcohol copolymer film, an adhesive layer and a polymer layer in sequence. According to some embodiments of the present invention, the polymer layer has a thickness of 100 to 500um, preferably 200 to 400um, and more preferably 300um; the thickness of the bonding layer is 10-40 um, preferably 20-30 um, more preferably 25um; the thickness of the ethylene-vinyl alcohol copolymer film is 20-80 um, preferably 40-60 um, and more preferably 50um.
Without being bound by any theory, it is believed that the physical volume of the peak of the surface wave (Vmp) is the main factor affecting the tip heat conduction, and therefore, in relation to the melting condition during the processing of the material, it further affects the uniformity of the heat conduction during the processing of the first EVOH resin particle and the second EVOH resin particle. Therefore, when the Vmp values of the first EVOH resin pellet and the second EVOH resin pellet in the EVOH resin pellet composition are in a specific range and the surface roughness of EVOH peaks with high melting points is large, the peak parts are preferentially melted during processing, so that the plastic pellets can conduct heat uniformly and the temperature of the melting area is advanced; when the surface roughness of the EVOH wave crest with low melting point is small, the local overheating of the wave crest part during processing can be reduced; therefore, the solid volume (Vmp) of the peak part of the surface wave of the two EVOH resin particles is controlled to regulate and control the heat conduction state after melt mixing, so that the EVOH resin particles can be uniformly melted, and an EVOH film with good processing performance and mechanical properties is obtained subsequently.
Examples
The following non-limiting examples of various aspects of the invention are provided primarily to illustrate various aspects of the invention and the benefits achieved thereby. The EVOH formulations of each of the examples and comparative examples were prepared from at least two ingredients. More specifically, the two components of the EVOH resin pellet compositions of the examples and comparative examples are two kinds of EVOH resin pellets.
Preparation of EVOH resin pellet composition
The following provides a non-limiting method for preparing the EVOH resin pellet composition. 5 non-limiting example EVOH resin pellet compositions (example EVOH 1-5) and 6 comparative example EVOH resin pellet compositions (comparative example EVOH 1-6) were prepared according to a method similar to that disclosed below. However, the specific methods of preparing the example EVOH 1-5 and the comparative example EVOH 1-6 generally differ from the methods disclosed below in one or more respects.
First EVOH resin pellets of example 1
A polymerization reactor equipped with a cooling coil was charged with 500kg of vinyl acetate, 100kg of methanol, 0.0585kg of acetyl peroxide and 0.015kg of citric acid, the inside of the polymerization reactor was once replaced with nitrogen, and then replaced with ethylene and pressurized until the ethylene pressure became 45kg/cm 2 . The temperature was raised to 67 ℃ under an ethylene pressurized atmosphere while stirring to start the polymerization. After 6 hours from the start of the polymerization, 0.0525kg of a sorbic acid-conjugated polyene was added as a polymerization inhibitor at a point at which the polymerization rate reached 60%. Thus, an ethylene-vinyl acetate copolymer having an ethylene structural unit content of 44mole% was obtained. Then, the mixture containing ethylene-vinyl acetate copolymerThe reaction solution was supplied to a distillation column, and methanol vapor was introduced from the bottom of the column to remove unreacted vinyl acetate, thereby obtaining a methanol solution of an ethylene-vinyl acetate copolymer.
In this example, a component (ethylene-vinyl acetate copolymer, hereinafter referred to as "EVAC" polymer) formed by polymerizing ethylene monomer and vinyl acetate monomer was saponified to form EVOH at a degree of saponification of 99.5%. Subsequently, EVOH was dissolved in an aqueous alcohol solution having a methanol to water ratio of 70. The EVOH/methanol/water solution was left at 60 ℃ for 1 hour to facilitate the dissolution of EVOH in the EVOH/methanol/water solution. The solid content of the EVOH/methanol/water solution was 41 wt.%.
Subsequently, the solution of methanol, water and EVOH was pelletized by strand cutting (Strip cut). Specifically, the above-mentioned solution of methanol, water and EVOH was pumped into a feed pipe at a flow rate of 120L/min using a pump, then fed into a circular opening die having a diameter of 0.5mm, the EVOH solution was extruded into a water/methanol mixed solution (water/methanol mass ratio = 9/1) at 5 ℃ to precipitate a strand-like shape, and cut with a rotary knife rotating at 500rpm to obtain pellets of EVOH. Subsequently, the EVOH pellets were centrifuged to separate EVOH particles, and the separated EVOH particles were washed with water; performing the centrifugal dehydration step for the second time, then immersing the EVOH particles into a boric acid/sodium acetate solution, performing a drying step and adding calcium stearate to obtain an EVOH resin particle final product, wherein the drying step is three-stage drying, and the first stage drying is performed by using a belt dryer and drying at 80 ℃ for 2 hours; the second stage drying is carried out by using a belt dryer at 100 ℃ for 20 hours; the third stage of drying was carried out using a flow type dryer at 120 ℃ for 20 hours and finally the pellets were conveyed, in the following cases: the delivery mode was air delivery, the pipeline diameter was 6 inches, the number of bends was 4, the pipeline length was 30 meters, and the delivery speed was 40m/min. The first EVOH resin particles of this example were cylindrical in shape, with a height of 5mm and a short diameter of 1mm.
In the centrifugation and washing steps, the rotating speed of the first dehydrator is 5000rpm; the water/wet particle ratio during transportation is 10; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 3000rpm; the weight ratio of water to wet granules is 5 during water washing; the water flow speed is 2m/min during water washing; the second dehydration machine rotation speed is 2000rpm.
Second EVOH resin pellets of example 1
Second EVOH resin pellets of example 1 were prepared herein using a method similar to that described above. Except that here, an ethylene-vinyl acetate copolymer (hereinafter, referred to as "EVAC") having an ethylene content of 32mole% was saponified to prepare an EVOH polymer having a saponification degree of 99.5%. And the diameter of the opening die for strip cutting is 2mm, and the rotating speed of the rotating knife is 2000rpm.
In the centrifugation and washing steps employed in the second EVOH resin pellet of the present embodiment, the first dehydrator rotation speed was 3000rpm; the water/wet particle ratio during transportation is 3; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 2000rpm; the weight ratio of water to wet granules is 3 during water washing; the water flow speed is 2.5m/min during water washing; the second spin-drier speed was 3000rpm. The final product of the second EVOH resin pellet of this example was cylindrical in shape, with a height of 2mm and a short diameter of 3mm.
For the subsequent further processing, the above-mentioned first EVOH resin pellet and second EVOH resin pellet were further mixed in proportions of 25 and 75wt%, respectively, into the EVOH resin pellet composition of example 1, and the mixture was mixed by means of a conical screw mixer (model: CM-2, available from Acciaumite industries, ltd.) at 10rpm for 5 minutes.
First and second EVOH resin pellets of example 2
First and second EVOH methanol aqueous solutions used in example 2 were prepared using a procedure (preparation process) similar to that of the EVOH resin pellet of example 1. However, when the first EVOH aqueous methanol solution of example 2 was prepared, its ethylene content was 48mole%; and the granulating step of granulating the aforementioned solution of methanol, water and EVOH by underwater pelletizing. Specifically, the aforementioned solution of methanol, water and EVOH was pumped into a feed tube at a flow rate of 120L/min using a pump, then fed into an input tube having a diameter of 1mm, and cut at 1500rpm using a rotary knife to obtain pellets of EVOH. While circulating condensed water at 5 ℃ was used to cool the EVOH pellets. Subsequently, the EVOH pellets were centrifuged to separate EVOH particles, and the separated EVOH particles were washed with water; the above-mentioned centrifugal dehydration step is again carried out a second time, followed by dipping the EVOH particles into a boric acid/sodium acetate solution, followed by a drying step and addition of calcium stearate to obtain the EVOH resin pellet end product. The first EVOH resin pellet of this example had an elliptical shape with a major axis of 3mm and a minor axis of 2mm.
In the centrifugation and washing steps, the rotating speed of the primary dehydrator is 3000rpm; the water/wet particle ratio during transportation is 10; the type of centrifugal pump (pump) for conveying is a semi-open type; the rotational speed of a delivery pump (pump) is 4000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 2m/min during water washing; the rotating speed of the second dehydrator is 1000rpm; finally, the first EVOH resin pellet had an ellipsoidal shape with a major axis of 3mm and a minor axis of 2mm.
On the other hand, when the second EVOH aqueous methanol solution of example 2 was prepared, its ethylene content was 27mole%; and a similar procedure to that used for the first EVOH resin pellets of example 2; and the diameter of the input tube is 2mm: in the centrifugation and washing steps, the rotating speed of the first dehydrator is 2000rpm; the water/wet particle ratio is 5 when the feed is carried; the type of the centrifugal pump (pump) for conveying is closed; the rotational speed of a delivery pump (pump) is 1000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 5m/min during water washing; the rotating speed of the second dehydrator is 3000rpm; finally, the product of the second EVOH resin pellet was spherical and had a minor axis of 3mm. Further, the EVOH resin pellet composition of example 2 was further blended with the first EVOH resin pellet and the second EVOH resin pellet in proportions of 10 wt% and 90wt%, respectively.
First and second EVOH resin pellets of example 3
A first aqueous methanol EVOH solution for use in example 3 was prepared using a procedure similar to that of the EVOH resin pellets of example 2. However, the first EVOH aqueous methanol solution of example 3 was prepared with an ethylene content of 38mole%; and a similar process to that of the first EVOH resin pellets of example 2 was used, the diameter of the input tube was 0.5mm, and the rotational speed of the rotary cutter was 3000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 2500rpm; the water/wet pellet ratio during transportation is 8; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 5000rpm; the weight ratio of water to wet granules is 8 during water washing; the water flow speed is 2.5m/min during water washing; the rotating speed of the second dehydrator is 3000rpm; finally, the product of the first EVOH resin particles is spherical, and the short diameter of the product is 1mm.
On the other hand, when the second EVOH aqueous methanol solution of example 3 was prepared using a similar procedure to that of the EVOH resin pellets of example 1, its ethylene content was 29mole%; the diameter of an opening die for strip cutting is 4mm, and the rotating speed of a rotating knife is 3000rpm; in the centrifugation and washing steps, the rotation speed of the primary dehydrator is 1000rpm; the water/wet particle ratio during transportation is 5; the type of the centrifugal pump (pump) for conveying is a semi-open type; the rotational speed of a delivery pump (pump) is 5000rpm; the weight ratio of water to wet granules is 5 during water washing; the water flow speed is 5m/min during washing; the rotating speed of the second dehydrator is 4000rpm; finally, the second EVOH resin pellet had a cylindrical shape with a height of 1mm and a minor axis of 5mm. Further, the first EVOH resin pellet and the second EVOH resin pellet were further mixed in proportions of 50wt% and 50wt%, respectively, to obtain the EVOH resin pellet composition of example 3.
First and second EVOH resin pellets of example 4
First EVOH resin pellets used in example 4 were prepared using a similar procedure to the EVOH resin pellets of example 2. However, when the first EVOH aqueous methanol solution of example 4 was prepared, its ethylene content was 48 mol%; the diameter of the input pipe is 0.5mm, and the rotating speed of the rotary knife is 500rpm; in the steps of centrifuging and washing, the rotating speed of the first dehydrator is 2500rpm; the water/wet particle ratio during transportation is 6; the type of centrifugal pump (pump) for conveying is a semi-open type; the rotational speed of a delivery pump (pump) is 5000rpm; the weight ratio of water to wet granules is 7 during water washing; the water flow speed is 2m/min during water washing; the rotating speed of the second dehydrator is 4000rpm; finally, the first EVOH resin pellet was formed into an oval sphere shape having a major axis of 5mm and a minor axis of 1mm.
On the other hand, when the second EVOH aqueous methanol solution of example 4 was prepared using a similar procedure to that for the EVOH resin pellets of example 1, its ethylene content was 32 mol%; the diameter of an opening die for strip cutting is 2mm, and the rotating speed of a rotating knife is 1500rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 3000rpm; the water/wet particle ratio during transportation is 9; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 4000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 5m/min during washing; the rotating speed of the second dehydrator is 4000rpm; finally, the second EVOH resin pellet had a cylindrical shape with a height of 3mm and a short diameter of 3mm. Further, the EVOH resin pellet composition of example 4 was further mixed with the first EVOH resin pellet and the second EVOH resin pellet in proportions of 15 wt% and 85wt%, respectively.
First and second EVOH resin pellets of example 5
First and second EVOH resin pellets used in example 5 were prepared using a similar procedure to the EVOH resin pellets of example 2. However, when the first EVOH aqueous methanol solution of example 5 was prepared, its ethylene content was 38 mol%; the diameter of the input pipe is 1mm, and the rotating speed of the rotary knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 4000rpm; the water/wet particle ratio during transportation is 7; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 3000rpm; the weight ratio of water to wet granules is 8 during water washing; the water flow speed is 7m/min during water washing; the rotating speed of the second dehydrator is 2000rpm; finally, the first EVOH resin pellet had an ellipsoidal shape with a major axis of 4mm and a minor axis of 2mm.
On the other hand, when the second EVOH aqueous methanol solution of example 5 was prepared, its ethylene content was 24 mol%; the diameter of the input pipe is 0.5mm, and the rotating speed of the rotating knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 5000rpm; the water/wet pellet ratio during transportation is 9; the type of a centrifugal pump (pump) for conveying is a semi-open type; the rotational speed of a delivery pump (pump) is 3000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 6m/min during water washing; the rotating speed of the second dehydrator is 1000rpm; finally, the product of the second EVOH resin pellets had an ellipsoidal shape with a major diameter of 4mm and a minor diameter of 1mm. Further, the EVOH resin pellet composition of example 5 was further blended with the first EVOH resin pellet and the second EVOH resin pellet at a ratio of 35 wt% and 65wt%, respectively.
First and second EVOH resin pellets of comparative example 1
First EVOH resin pellets used in comparative example 1 were prepared using a similar procedure to the EVOH resin pellets of example 2. However, when the first EVOH aqueous methanol solution of comparative example 1 was prepared, its ethylene content was 44 mol%; the diameter of the input pipe is 2.5mm, and the rotating speed of the rotary knife is 1200rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 2000rpm; the water/wet pellet ratio during transportation is 10; the type of centrifugal pump (pump) for transportation is open type; the rotational speed of a delivery pump (pump) is 1000rpm; the weight ratio of water/wet granules is 15 during water washing; the water flow speed is 2m/min during water washing; the rotating speed of the second dehydrator is 1000rpm; finally, the product of the first EVOH resin pellet was in the form of a sphere having a minor axis of 3.5mm.
On the other hand, when the second EVOH aqueous methanol solution of comparative example 1 was prepared using a similar procedure to that for the EVOH resin pellets of example 1, its ethylene content was 29 mol%; the diameter of the opening die for strip cutting is 3.5mm, and the rotating speed of the rotary knife is 500rpm; in the centrifugation and washing steps, the rotation speed of the primary dehydrator is 1000rpm; the water/wet pellet ratio during delivery is 15; the type of a centrifugal pump (pump) for conveying is an open type; the rotational speed of a delivery pump (pump) is 2000rpm; the weight ratio of water to wet granules is 20 when washing; the water flow speed is 1m/min during water washing; the rotating speed of the second dehydrator is 1000rpm; finally, the second EVOH resin particle was cylindrical in shape, with a height of 5mm and a minor axis of 4.5mm. Further, the EVOH resin pellet composition of comparative example 1 was further blended with the first EVOH resin pellet and the second EVOH resin pellet at a ratio of 5wt% and 95wt%, respectively.
First and second EVOH resin pellets of comparative example 2
First EVOH resin pellets for comparative example 2 were prepared using a similar procedure to the EVOH resin pellets of example 2. However, when the first EVOH aqueous methanol solution of comparative example 2 was prepared, its ethylene content was 35 mol%; the diameter of the input pipe is 1mm, and the rotating speed of the rotating knife is 1500rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 3000rpm; the water/wet pellet ratio was 20 during delivery; the type of centrifugal pump (pump) for conveying is open type; the rotational speed of a delivery pump (pump) is 1000rpm; the weight ratio of water/wet granules is 15 during water washing; the water flow speed is 1.5m/min during water washing; the rotating speed of the second dehydrator is 2000rpm; finally, the first EVOH resin pellet had an ellipsoidal shape with a major axis of 3mm and a minor axis of 2mm.
On the other hand, the second EVOH resin pellet of comparative example 2 was prepared using a similar procedure to that of the EVOH resin pellet of example 1, however, when the second EVOH aqueous methanol solution of comparative example 2 was prepared, its ethylene content was 24 mol%; the diameter of an opening die for strip cutting is 1mm, and the rotating speed of a rotating knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 8000rpm; the water/wet particle ratio is 1 during conveying; the type of the centrifugal pump (pump) for conveying is closed; the rotating speed of a delivery pump (pump) is 8000rpm; the weight ratio of water to wet granules is 1 during water washing; the water flow speed is 8m/min during water washing; the rotating speed of the second dehydrator is 5000rpm; finally, the second EVOH resin pellet had a cylindrical shape with a height of 4mm and a minor axis of 2mm. Further, the EVOH resin pellet composition of comparative example 2 was further blended with the first EVOH resin pellet and the second EVOH resin pellet at a ratio of 75wt% and 25wt%, respectively.
First and second EVOH resin pellets of comparative example 3
First and second EVOH resin pellets for comparative example 3 were prepared using a similar process to the EVOH resin pellets of example 1. However, when the first EVOH aqueous methanol solution of comparative example 3 was prepared, its ethylene content was 48 mol%; the diameter of an opening die for strip cutting is 3mm, and the rotating speed of a rotating knife is 1700rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 7000rpm; the water/wet pellet ratio during transportation is 3; the type of the centrifugal pump (pump) for conveying is closed; the rotational speed of a delivery pump (pump) is 7000rpm; the weight ratio of water to wet granules is 1 during water washing; the water flow speed is 7m/min during water washing; the rotating speed of the second dehydrator is 6000rpm; finally, the first EVOH resin pellet had a cylindrical shape with a height of 2.5mm and a short diameter of 4mm. On the other hand, the second aqueous methanol solution of comparative example 3 was prepared, and its ethylene content was 32 mol%; the diameter of an opening die for strip cutting is 2mm, and the rotating speed of a rotating knife is 1200rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 6000rpm; the water/wet particle ratio is 1 during conveying; the type of the centrifugal pump (pump) for conveying is closed; the rotational speed of the delivery pump (pump) is 6000rpm; the weight ratio of water to wet granules is 3 during water washing; the water flow speed is 6m/min during water washing; the rotating speed of the second dehydrator is 5000rpm; finally, the second EVOH resin pellet was cylindrical in shape, with a height of 3.5mm and a short diameter of 3mm. Further, the EVOH resin pellet composition of comparative example 3 was further blended with the first EVOH resin pellet and the second EVOH resin pellet in proportions of 15 wt% and 85wt%, respectively.
First and second EVOH resin pellets of comparative example 4
First and second EVOH resin pellets for comparative example 4 were prepared using a similar process to the EVOH resin pellets of example 2. However, when the first EVOH aqueous methanol solution of comparative example 4 was prepared, its ethylene content was 38 mol%; the diameter of the input pipe is 0.5mm, and the rotating speed of the rotary knife is 3000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 3000rpm; the water/wet-pellet ratio at the time of delivery was 8; the type of centrifugal pump (pump) for transportation is open type; the rotational speed of a delivery pump (pump) is 4000rpm; the weight ratio of water to wet granules is 8 during water washing; the water flow speed is 2.5m/min during water washing; the rotating speed of the second dehydrator is 3000rpm; finally, the product of the first EVOH resin pellets was spherical with a minor axis of 1mm. On the other hand, when the second EVOH aqueous methanol solution of comparative example 4 was prepared, its ethylene content was 27 mol%; the diameter of the input pipe is 3mm, and the rotating speed of the rotating knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 8000rpm; the water/wet pellet ratio during transportation is 1; the type of the centrifugal pump (pump) for conveying is closed; the rotational speed of a delivery pump (pump) is 8000rpm; the weight ratio of water to wet granules is 3 during water washing; the water flow speed is 6m/min during water washing; the rotating speed of the second dehydrator is 6000rpm; finally, the product of the second EVOH resin pellet was in the form of a sphere having a minor axis of 4mm. Further, the first EVOH resin pellet and the second EVOH resin pellet were further blended in a proportion of 10 wt% and 90wt%, respectively, to obtain an EVOH resin pellet composition of comparative example 4.
First and second EVOH resin pellets of comparative example 5
First and second EVOH resin pellets for comparative example 5 were prepared using a similar process to the EVOH resin pellets of example 2. However, the first EVOH aqueous methanol solution of comparative example 5 was prepared to have an ethylene content of 44 mol%; the diameter of the input pipe is 2.5mm, and the rotating speed of the rotating knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 1000rpm; the water/wet particle ratio during transportation is 10; the type of centrifugal pump (pump) for transportation is open type; the rotational speed of a delivery pump (pump) is 3000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 1m/min during water washing; the rotating speed of the second dehydrator is 1000rpm; finally, the first EVOH resin pellet had an oval spherical shape with a major axis of 4mm and a minor axis of 3.5mm. On the other hand, when the second EVOH aqueous methanol solution of comparative example 5 was prepared, its ethylene content was 29 mol%; the diameter of the input pipe is 0.5mm, and the rotating speed of the rotating knife is 1700rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 3000rpm; the water/wet particle ratio during transportation is 5; the type of the centrifugal pump (pump) for conveying is closed; the rotational speed of a delivery pump (pump) is 2000rpm; the weight ratio of water to wet granules is 10 during water washing; the water flow speed is 5m/min during water washing; the rotating speed of the second dehydrator is 3000rpm; finally, the second EVOH resin pellet had an oval spherical shape with a major axis of 2.5mm and a minor axis of 1mm. Further, the EVOH resin pellet composition of comparative example 5 was prepared by blending the first EVOH resin pellets and the second EVOH resin pellets in proportions of 20 wt% and 80wt%, respectively.
First and second EVOH resin pellets of comparative example 6
First and second EVOH resin pellets for comparative example 6 were prepared using a similar process to the EVOH resin pellets of example 2. However, the first EVOH aqueous methanol solution of comparative example 6 was prepared to have an ethylene content of 38 mol%; the diameter of the input pipe is 1.5mm, and the rotating speed of the rotary knife is 1700rpm; in the centrifugation and washing steps, the rotating speed of the primary dehydrator is 7000rpm; the water/wet particle ratio during transportation is 2; the type of the centrifugal pump (pump) for conveying is closed; the rotating speed of a delivery pump (pump) is 8000rpm; the weight ratio of water to wet granules is 3 during water washing; the water flow speed is 10m/min during water washing; the rotating speed of the second dehydrator is 6000rpm; finally, the product of the first EVOH resin pellets was spherical and had a minor axis of 2.5mm. On the other hand, when the second EVOH aqueous methanol solution of comparative example 6 was prepared, its ethylene content was 32 mol%; the diameter of the input pipe is 0.5mm, and the rotating speed of the rotary knife is 1000rpm; in the centrifugation and washing steps, the rotating speed of the first dehydrator is 1000rpm; the water/wet particle ratio during transportation is 3; the type of centrifugal pump (pump) for conveying is a semi-open type; the rotational speed of a delivery pump (pump) is 3000rpm; the weight ratio of water to wet granules is 5 during water washing; the water flow speed is 3m/min during water washing; the rotating speed of the second dehydrator is 4000rpm; finally, the second EVOH resin pellet had an oval spherical shape with a major axis of 4mm and a minor axis of 1mm. Further, the EVOH resin pellet composition of comparative example 6 was further blended with the first EVOH resin pellet and the second EVOH resin pellet at a ratio of 35 wt% and 65wt%, respectively.
Parameters of EVOH resin pellets
The following provides parameters of the EVOH resin pellets of the present invention and methods for evaluating/analyzing the same.
Roughness of the surface of the particles
In order to evaluate/analyze the surface roughness of the EVOH resin pellets of the examples, measurement of the surface roughness of the pellets was performed with the EVOH resin pellets being laid on top of a plate; the measurement is performed by excluding the part of the data with a tilt greater than 0.5 to ensure that the scan plane is relatively horizontal (tilt = maximum height Sz of the plane/side length 129 μm of the analysis range). A laser microscope was used LEXT OLS5000-SAF manufactured by Olympus, and images were made at an air temperature of 24 + -3 ℃ and a relative humidity of 63 + -3%. The filter is set to no filtering. The light source is a 405nm wavelength light source. The objective lens is 100x magnification (MPLAPON-100 xLEXT). The optical zoom is set to 1.0x. The image area was set to 129 μm x 129 μm (when Rz was measured, the center line of the image area was taken). The resolution is set to 1024 pixels x1024 pixels. The values of 100 particles were measured and averaged. Wherein Vmp, sku, sp, spk and Sxp are measured using ISO 25178; ra and Rz are measured by the method of JIS B0601 (2001).
Ethylene content analysis
In order to evaluate/analyze the ethylene content of the EVOH resin particles of the examples, the present inventors employed a Raman spectrometer manufactured by UniDRON and measured the ethylene content of 5 sites at random for each EVOH resin particle with a laser source having a wavelength of 473nm, and the average value was taken as the ethylene content value of a sample of the EVOH resin particle.
Melting point analysis
Herein, the melting point temperature of EVOH resin pellets was measured by a DSC Q200 apparatus (Tzero TECHNOLOGIES, INC., tzero (TM) lid) TA instruments T170607 and bottom (Tzero pan) TA instruments T170620) according to ISO 11357-3-2011.
Practically speaking, without being limited by a particular theory, when there are a large number of EVOH resin pellets, 100 EVOH resin pellets may be taken first and their individual ethylene contents obtained by the above-mentioned ethylene content analysis method. Then, for the ethylene content of 35 to 48 mol%, it is classified in advance as low-melting EVOH resin pellets having a melting point of about 135 to 179 ℃; whereas those having an ethylene content of 24 to 34 mol% are classified beforehand as high-melting EVOH resin pellets having a melting point of about 180 to 198 ℃. Further, 10 EVOH resin pellets were randomly picked out of the groups of low-melting EVOH resin pellets and high-melting EVOH resin pellets, surface roughness was obtained by the above-described surface parameter measurement method, and the melting points of the EVOH resin pellets were determined by the above-described melting point measurement method.
Preparation and analysis of EVOH Single-layer film
The EVOH resin pellet compositions of examples 1 to 5 and comparative examples 1 to 6 were each formed into films according to the following method. The EVOH resin pellet compositions of examples 1-5 and comparative examples 1-6 were fed into a single-screw extruder (model ME25/5800V4, trade name OCS) to extrude to prepare monolayer films. The thickness of each film formed from the EVOH resin particle compositions of examples 1 to 5 and comparative examples 1 to 6 was 20um. Setting the temperature of the extruder to 220 ℃; and the rotational frequency of the screw was set to 7rpm (rotations/minutes).
Analysis of processability of EVOH film: measurement and evaluation of Gel particles (Gel)
Here, the gel particles of the EVOH film were measured and analyzed using a Charged Coupled Device (CCD) sensor and FSA-100 designed by FSA-100V.8 software. The evaluation method is as follows: if the gel particle size is <100 μm, the amount is <450, which is best represented by "O"; the number of the compounds is 450 to 1000, namely the number is expressed by 'delta'; while those with a number >1000 are not preferred as represented by "X". If the gel particle size is 100-200 μm, the amount is <50, which is best represented by "O"; the number of the compounds is 50 to 100, namely the number is expressed by 'delta'; while those with a number >100 are indicated as "X" to be less preferred. If the gel particle size is greater than 200 μm, the amount is less than 10, which is best represented by "O"; the number of the compounds is 10 to 20, namely the number is expressed by 'delta'; and those with a number >20 are not preferred as represented by "X".
Mechanical property analysis of EVOH film: measurement and evaluation of film elongation
Herein, a single-layer film with the thickness of 180um is formed by the single-screw extruder and is cut into the size of MD 30mm TD 90mm (TD, or width Direction; MD means Machine Direction, namely the mechanical Direction or the longitudinal Direction and the length Direction); then, after being left in an environment at a temperature of 130 ℃ for 30 minutes, the tensile strength was measured in the MD and TD directions at a tensile rate of 1000mm/min by ASTM D882. As used herein, "percent elongation (%)" is defined as [ (post-stretched length-pre-stretched length)/pre-stretched length ]. 100%; the evaluation method is as follows: the film samples exhibited film elongation values greater than 1000% as best represented by "O"; the film samples may exhibit film stretch values of between 800 and 1000% expressed as "Δ"; on the other hand, the film sample having a film elongation value of less than 800% is not preferable in terms of "X".
Preparation of multilayer structures
Here, the EVOH resin pellet compositions of examples 1 to 5 and comparative examples 1 to 6, polypropylene and adhesive layers (for example)
18729, arkema ltd) to form individual multilayer films of examples 1 to 5 and comparative examples 1 to 6. The multilayer film had 5 layers, and specifically, EVOH particles (i), polypropylene (ii), and a binder resin (iii) were fed separately to a five-layer coextrusion film former to prepare a multilayer sheet having the following structure: (II)/(III)/(I)/(III)/(II) and the thicknesses were 300/25/50/25/300 (um), respectively.
Analysis of results of examples and comparative examples
In this section, the results of gel particle and elongation analysis of the EVOH resin particle compositions of examples 1 to 5 and comparative examples 1 to 6, respectively, and the films produced therefrom are compared. Specific data are shown in tables 1 and 2, respectively.
TABLE 1
TABLE 2
As is clear from tables 1 and 2, the first EVOH resin pellets contained in the EVOH resin pellet compositions of examples 1 to 5The peak physical volume (Vmp) of the surface wave is 0.00001 to 6um 3 /um 2 And the second EVOH resin particle has a volume (Vmp) of 0.00015 to 20um in a peak physical volume (Vmp) of a surface wave 3 /um 2 (ii) a So that the prepared film has good performances on gel particles and stretching rate; in other words, the film has substantially excellent processability and mechanical properties. In contrast, the EVOH resin pellet compositions of comparative examples 1 to 6 do not satisfy the numerical range of the solid volume (Vmp) of the peak portion of the surface wave of the first and second EVOH resin pellets; resulting in the film made therefrom having unsatisfactory processability and mechanical properties. Preferably, the second EVOH resin pellet of the present invention has a larger Vmp than that of the first EVOH resin pellet. Preferably, the melting point of the first EVOH resin particles is 135-179 ℃, and the melting point of the second EVOH resin particles is 180-198 ℃. Preferably, the ethylene content of the first EVOH resin particle is 36 to 50 mol%, and the ethylene content of the second EVOH resin particle is 20 to 35 mol%.
Further, as can be seen from comparison of tables 1 and 2, although the first EVOH resin pellet contained in the EVOH resin pellet composition of comparative example 4, the second EVOH resin pellet contained in the EVOH resin pellet composition of comparative example 5, and the second EVOH resin pellet contained in the EVOH resin pellet composition of comparative example 6 fall within the Vmp value ranges of the first/second EVOH resin pellets defined in the present invention, respectively, none of the other EVOH resin pellets contained in these EVOH resin pellet compositions falls within the corresponding Vmp value ranges. It can be understood that, only when the EVOH resin pellet composition contains two EVOH resin pellets each having a Vmp value within the range defined in the present application, the two EVOH resins can be blended and formed into a film having more desirable processability and mechanical properties.
In addition, the inventors have found that the solid volume (Vmp) of the peak of the surface wave desired in the present invention can be further controlled and obtained by controlling the process variables of the centrifugation and washing processes in the processing of EVOH resin pellets; specifically, the method comprises the following steps: without being limited by any theory, the solid volume of the peak part of the surface wave of the EVOH resin particles is increased to a certain extent due to overhigh rotating speed of a dehydrator, overlow water/wet particle ratio during conveying and washing, overhigh rotating speed of a conveying pump when a centrifugal pump is used in a closed type during conveying, overhigh water flow speed and the like; conversely, the solid volume of the surface wave peak of EVOH resin particles is reduced to some extent by the excessively low rotation speed of the dehydrator, the excessively high water/wet particle ratio during transportation and washing, the excessively low rotation speed of the delivery pump when the centrifugal pump is open during transportation, the excessively low water flow rate, and the like; in an embodiment, the rotation speed of the dehydrator is preferably controlled to 1000 to 5000rpm, the water/wet pellet ratio during transportation and washing is preferably controlled to 3 to 10, the rotation speed of the delivery pump is preferably not more than 5000rpm when the centrifugal pump is used in a closed state during transportation, the rotation speed of the delivery pump is preferably not less than 1000rpm when the centrifugal pump is used in an open state during transportation, the water flow speed during washing is 2 to 7m/min, and the rotation speed of the second dehydrator is preferably controlled to 1000 to 4000rpm, whereby the desired solid volume of the surface wave peak of the EVOH resin pellets can be obtained.
All ranges provided herein are intended to include each specific range within the given range as well as combinations of sub-ranges between the given ranges. Moreover, unless otherwise indicated, all ranges provided herein are inclusive of the endpoints of the ranges. Thus, a range of 1-5 specifically includes 1, 2, 3, 4, and 5, as well as sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and so forth.
All publications and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, each individual publication or patent application is specifically and individually indicated to be incorporated by reference. In the event of a discrepancy between this document and any publication or patent application incorporated by reference herein, this document controls.
The terms "comprising," "having," and "including," as used herein, have an open, non-limiting meaning. The terms "a" and "an" and "the" are to be understood to cover the plural as well as the singular. The term "one or more" means "at least one" and thus may include a single feature or a mixture/combination of features. The term "between" includes both of its endpoints.
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be modified in all instances by the term "about" meaning within ± 5% of the number indicated. As used herein, the term "substantially free" or "substantially free" refers to less than about 2% of a particular feature. All elements or features positively set forth herein are negatively excluded from the claimed scope.
[ notation ] none.
[ deposit of biological Material ] No.
Claims (19)
1. An ethylene vinyl alcohol copolymer (EVOH) resin particle composition comprising:
first EVOH resin pellets having a peak physical volume (Vmp) of 0.00001 to 6um 3 /um 2 And are and
second EVOH resin particles having a surface wave peak physical volume (Vmp) of 0.00015-20 um 3 /um 2 。
2. The EVOH resin pellet composition of claim 1, wherein the Vmp of the second EVOH resin pellet is greater than the Vmp of the first EVOH resin pellet.
3. The EVOH resin particle composition of claim 1, wherein the melting point of the first EVOH resin particles is 135-179 ℃, and wherein the melting point of the second EVOH resin particles is 180-198 ℃.
4. The EVOH resin particle composition of any of claims 1 to 3, wherein the ethylene content of the first EVOH resin particles is 36 to 50 mol%.
5. The EVOH resin particle composition of any of claims 1 to 3, wherein the ethylene content of the second EVOH resin particles is 20-35 mol%.
6. The EVOH resin pellet composition of any one of claims 1 to 3, wherein the EVOH resin pellets have a cylindrical, elliptic, prismatic, spherical, elliptic, or Weiqi shape, and have a major axis/height of 1 to 5mm and a minor axis of 1 to 5mm.
7. The EVOH resin particle composition of any one of claims 1 to 3, wherein the weight percentage of the first EVOH resin particles to the second EVOH resin particles is 5:95 to 75:25.
8. EVOH resin pellet composition according to any of claims 1 to 3, having a boron content of 5 to 550ppm.
9. EVOH resin pellet composition according to any of claims 1 to 3, having an alkali metal content of 10 to 550ppm.
10. The EVOH resin particle composition of any one of claims 1 to 3, wherein:
the first EVOH resin particles having a kurtosis (Sku) surface parameter of from 0.0020 to 25; and is
The second EVOH resin particles have a kurtosis (Sku) surface parameter of 0.0070-111.
11. The EVOH resin particle composition of any one of claims 1 to 3, wherein:
the first EVOH resin particle has a surface parameter of maximum surface peak height (Sp) of 0.0005-29 um; and is
The second EVOH resin particle has a surface parameter of a maximum surface peak height (Sp) of 0.0020 to 63 um.
12. The EVOH resin particle composition of any one of claims 1 to 3, wherein:
the first EVOH resin particle has a projected peak height (Spk) surface parameter of 0.001-2 um; and is provided with
The second EVOH resin particle has a protruding peak height (Spk) surface parameter of 0.003-22 um.
13. The EVOH resin particle composition of any one of claims 1 to 3, wherein:
the first EVOH resin pellet has a pole height (Sxp) surface parameter of 0.001-12 um; and is
The second EVOH resin pellet has a pole height (Sxp) surface parameter of 0.002-48 um.
14. The EVOH resin particle composition of any one of claims 1 to 3, wherein:
the first EVOH resin particles having a surface parameter of linear average height (Ra) of 0.001-0.990 um; and is provided with
The second EVOH resin particles have a linear average height (Ra) surface parameter of 0.001-0.990 um.
15. The EVOH resin pellet composition of any of claims 1 to 3, wherein:
the first EVOH resin particles having a maximum height-from-line (Rz) surface parameter of 0.0010 to 9.9000 um; and is provided with
The second EVOH resin particles have a maximum height-from-line (Rz) surface parameter of 0.0010 to 9.9000 um.
16. An ethylene-vinyl alcohol copolymer film formed from the EVOH resin particle composition of any one of claims 1 to 15.
17. A multilayer structure comprising:
(a) At least one ethylene-vinyl alcohol copolymer film formed of an EVOH resin pellet composition as claimed in any one of claims 1 to 15;
(b) At least one polymer layer; and
(c) At least one adhesive layer.
18. The multi-layer structure of claim 17, wherein the polymer layer is selected from the group consisting of a low density polyethylene layer, a polyethylene-grafted maleic anhydride (pe-maleic anhydride) layer, a polypropylene layer, and a nylon layer, and the adhesive layer is a tie layer.
19. The multilayer structure of claim 17 or 18, wherein the multilayer structure is a polymer layer/a bonding layer/an ethylene vinyl alcohol copolymer film/a bonding layer/a polymer layer.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110121911 | 2021-06-16 | ||
| TW110121920 | 2021-06-16 | ||
| TW110121918A TWI767756B (en) | 2021-06-16 | 2021-06-16 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, as well as multilayer structure containing the same |
| TW110121911A TWI765750B (en) | 2021-06-16 | 2021-06-16 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, as well as multilayer structure containing the same |
| TW110121913A TWI772064B (en) | 2021-06-16 | 2021-06-16 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, as well as multilayer structure containing the same |
| TW110121920A TWI761235B (en) | 2021-06-16 | 2021-06-16 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, as well as multilayer structure containing the same |
| TW110121916A TWI772065B (en) | 2021-06-16 | 2021-06-16 | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, as well as multilayer structure containing the same |
| TW110121918 | 2021-06-16 | ||
| TW110121913 | 2021-06-16 | ||
| TW110121916 | 2021-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115477803A true CN115477803A (en) | 2022-12-16 |
Family
ID=84420835
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210692339.7A Pending CN115477805A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| CN202210691644.4A Pending CN115477804A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| CN202210691641.0A Pending CN115477803A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210692339.7A Pending CN115477805A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
| CN202210691644.4A Pending CN115477804A (en) | 2021-06-16 | 2022-06-16 | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN115477805A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1337233C (en) * | 1987-09-07 | 1995-10-10 | Kiyoshi Yonezu | Multilayered structure utilizing an ethylene-vinyl alcohol copolymer composition |
| JPH11294947A (en) * | 1998-04-10 | 1999-10-29 | Nippon Synthetic Chem Ind Co Ltd:The | Method for drying saponified pellet of ethylene-vinyl acetate copolymer |
| JP2002293948A (en) * | 2001-01-22 | 2002-10-09 | Kuraray Co Ltd | Method for producing ethylene-vinyl alcohol copolymer resin composition |
| JP2005068324A (en) * | 2003-08-26 | 2005-03-17 | Nippon Synthetic Chem Ind Co Ltd:The | Saponified ethylene-vinyl acetate copolymer composition |
| CN111944262A (en) * | 2019-12-24 | 2020-11-17 | 长春石油化学股份有限公司 | Ethylene-vinyl alcohol copolymer resin particles, method for forming same, film formed therefrom, and multilayer structure |
| US11021599B1 (en) * | 2019-12-24 | 2021-06-01 | Chang Chun Petrochemical Co., Ltd | Ethylene-vinyl alcohol copolymer resin composition, film, and multi-layer structure comprising the same, as well as methods thereof |
| JP2021084855A (en) * | 2019-11-29 | 2021-06-03 | チャン チュン ペトロケミカル カンパニー リミテッド | Polymer film and uses of the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4107446B2 (en) * | 1998-04-10 | 2008-06-25 | 日本合成化学工業株式会社 | Method for drying saponified pellets of ethylene-vinyl acetate copolymer |
-
2022
- 2022-06-16 CN CN202210692339.7A patent/CN115477805A/en active Pending
- 2022-06-16 CN CN202210691644.4A patent/CN115477804A/en active Pending
- 2022-06-16 CN CN202210691641.0A patent/CN115477803A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1337233C (en) * | 1987-09-07 | 1995-10-10 | Kiyoshi Yonezu | Multilayered structure utilizing an ethylene-vinyl alcohol copolymer composition |
| JPH11294947A (en) * | 1998-04-10 | 1999-10-29 | Nippon Synthetic Chem Ind Co Ltd:The | Method for drying saponified pellet of ethylene-vinyl acetate copolymer |
| JP2002293948A (en) * | 2001-01-22 | 2002-10-09 | Kuraray Co Ltd | Method for producing ethylene-vinyl alcohol copolymer resin composition |
| JP2005068324A (en) * | 2003-08-26 | 2005-03-17 | Nippon Synthetic Chem Ind Co Ltd:The | Saponified ethylene-vinyl acetate copolymer composition |
| JP2021084855A (en) * | 2019-11-29 | 2021-06-03 | チャン チュン ペトロケミカル カンパニー リミテッド | Polymer film and uses of the same |
| CN111944262A (en) * | 2019-12-24 | 2020-11-17 | 长春石油化学股份有限公司 | Ethylene-vinyl alcohol copolymer resin particles, method for forming same, film formed therefrom, and multilayer structure |
| US11021599B1 (en) * | 2019-12-24 | 2021-06-01 | Chang Chun Petrochemical Co., Ltd | Ethylene-vinyl alcohol copolymer resin composition, film, and multi-layer structure comprising the same, as well as methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115477805A (en) | 2022-12-16 |
| CN115477804A (en) | 2022-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7372902B2 (en) | Ethylene-vinyl alcohol copolymer resin, film and multilayer structure containing the same, and method for forming the ethylene-vinyl alcohol copolymer resin | |
| WO2016088862A1 (en) | Ethylene - vinyl ester-based copolymer saponification product composition and production method therefor | |
| TWI741853B (en) | Ethylene vinyl alcohol copolymer resin composition as well as films and multi-layer structures thereof | |
| CN115477803A (en) | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure | |
| JP3137930B2 (en) | Saponified ethylene-vinyl acetate copolymer composition and multilayer structure using the same | |
| WO2022262806A1 (en) | Ethylene-vinyl alcohol copolymer resin particle composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure | |
| EP0982352B1 (en) | Unstretched polypropylene molding | |
| JPWO2009044925A1 (en) | Anti-blocking agent master batch and polyolefin resin film using the same | |
| JP4704708B2 (en) | Resin composition and method for producing the same | |
| CN115477801B (en) | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure comprising the same | |
| EP4105022A1 (en) | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same | |
| US11566091B2 (en) | Ethylene vinyl alcohol copolymer resin composition, ethylene vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same | |
| US11746170B2 (en) | Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same | |
| JP2024117372A (en) | Method for producing stretched film | |
| JP2024117370A (en) | Method for producing stretched film | |
| JP2024117371A (en) | Method for producing stretched film | |
| JP2024117369A (en) | Method for producing stretched film | |
| JP2023084758A (en) | Resin composition including ethylene vinyl alcohol copolymer, production method of the same, and pellet composed of the same | |
| JP4156138B2 (en) | Ethylene-vinyl acetate copolymer saponified film and method for producing the same | |
| JPH11291341A (en) | Manufacture of ethylene-vinyl acetate copolymer saponified compound film | |
| JPH11291342A (en) | Manufacture of ethylene-vinyl acetate copolymer saponified compound film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |