CN104582929A - 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 - Google Patents
适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 Download PDFInfo
- Publication number
- CN104582929A CN104582929A CN201380042916.7A CN201380042916A CN104582929A CN 104582929 A CN104582929 A CN 104582929A CN 201380042916 A CN201380042916 A CN 201380042916A CN 104582929 A CN104582929 A CN 104582929A
- Authority
- CN
- China
- Prior art keywords
- weight
- polyethylene
- film
- blend compositions
- low density
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 113
- -1 polyethylene Polymers 0.000 title claims abstract description 57
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 56
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 29
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 29
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 23
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 23
- 230000002902 bimodal effect Effects 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 6
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 45
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 27
- 239000004711 α-olefin Substances 0.000 description 14
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QPFMBZIOSGYJDE-MICDWDOJSA-N 1,1,2,2-tetrachloro-1-deuterioethane Chemical compound [2H]C(Cl)(Cl)C(Cl)Cl QPFMBZIOSGYJDE-MICDWDOJSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003938 response to stress Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9115—Cooling of hollow articles
- B29C48/912—Cooling of hollow articles of tubular films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B32B1/00—Layered products having a non-planar shape
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- 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
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92714—Degree of crosslinking, solidification, crystallinity or homogeneity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9115—Cooling of hollow articles
- B29C48/912—Cooling of hollow articles of tubular films
- B29C48/913—Cooling of hollow articles of tubular films externally
-
- 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
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2439/00—Containers; Receptacles
-
- 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
- C08J2423/06—Polyethene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
本发明提供了一种适合用于吹塑膜的聚乙烯共混物组合物以及由此制备的膜。适合用于吹塑膜的聚乙烯共混物组合物,其包括以下物质的熔融共混产物:(a)0.5重量%至6重量%的双峰线性低密度聚乙烯,其密度为0.935至0.970g/cm3,且熔体指数(I2)为0.3至5g/10分钟;(b)90重量%或更高的单峰线性低密度聚乙烯,其密度为0.910至0.950g/cm3,熔体指数(I2)为0.1至小于或等于5g/10分钟;(c)任选的0.5重量%至4重量%的低密度聚乙烯,其密度为0.915至0.935g/cm3,熔体指数(I2)为大于0.8至小于或等于5g/10分钟,且分子量分布(Mw/Mn)为6至10;(d)任选的基于水滑石的中和剂;(e)任选的一种或多种成核剂;和(f)任选的一种或多种抗氧化剂。
Description
相关申请的参考
本申请要求2012年6月26日提交的美国临时专利申请No.61/664,301的权益。
技术领域
本发明涉及适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜。
背景技术
挤出吹塑膜方法中使用聚合物材料如基于乙烯的组合物是广为人知的。挤出吹塑膜方法使用挤出机,其加热、熔融和传递熔体聚合物材料并迫使其通过环形模头。该基于乙烯的膜由模头牵拉并形成为管形,最终通过一对牵引辊或者夹辊。然后将内部压缩空气从心轴压入,导致该管直径增加,形成为期望尺寸的气泡(bubble)。由此将吹塑膜沿两个方向拉伸,即在轴向,也就是通过使用使该气泡的直径膨胀的强迫空气(forced air),和在该气泡的长度方向上,也就是通过绕组单元(winding element)的作用,该绕组单元将气泡拉伸通过该机器。也将外部空气引入到该气泡圆周的周围,从而在当熔体离开模头时,将熔体冷却。通过向该气泡中引入或多或少的内部空气来改变该膜的宽度由此增加或者减少气泡尺寸。膜的厚度主要通过增加或者降低该牵引辊或者夹辊的速度来控制牵引速率(draw-down rate)而得到控制。
然后气泡在通过该牵引辊或者夹辊之后立即塌陷成膜的两个层。然后可通过切割或者密封进一步加工冷却的膜,从而生产各种消费品。
尽管在生产适合用于吹塑膜的聚合材料方面进行了研究努力,但是仍然需要适合用于吹塑膜的聚乙烯共混物组合物,提供改善的输出速率。此外,仍然需要生产适合用于吹塑膜的聚乙烯共混物组合物,提供改善的输出速率的方法。
发明内容
本发明提供适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜。
在一个实施方案中,本发明提供适合用于吹塑膜的聚乙烯共混物组合物,其包括以下物质的熔融共混产物:(a)0.5重量%至6重量%的双峰线性低密度聚乙烯,其密度为0.935至0.970g/cm3,且熔体指数(I2)为0.3至5g/10分钟;(b)90重量%或更高的单峰线性低密度聚乙烯,其密度为0.910至0.950g/cm3,熔体指数(I2)为0.1至小于或等于5g/10分钟;(c)任选的0.5重量%至4重量%的低密度聚乙烯,其密度为0.915至0.935g/cm3,熔体指数(I2)为大于0.8至小于或等于5g/10分钟,且分子量分布(Mw/Mn)为6至10;(d)任选的基于水滑石的中和剂;(e)任选的一种或多种成核剂;和(f)任选的一种或多种抗氧化剂。
在可供选择的实施方式中,本发明提供包括如上所述的聚乙烯共混物组合物的吹塑膜。
在另一可供选择的实施方式中,本发明还提供一种制品,所述制品包括一个或多个含有如上所述的聚乙烯共混物的吹塑膜。
在另一可供选择的实施方式中,本发明还提供容器装置,所述容器装置含有:(a)一个或多个基板;和(b)一个或多个层,所述层包括一个或多个含有如上所述的聚乙烯共混物组合物的吹塑膜。
在可供选择的实施方式中,本发明提供了一种根据前述实施方式中任一项的适合用于吹塑膜的聚乙烯共混物组合物、吹塑膜、制品和/或容器装置,不同之处在于当所述聚乙烯共混物组合物经由吹塑膜工艺成膜时,输出速率相对于类似线性低密度聚乙烯至少改进5%。
附图的简要说明
出于解释本发明的目的,在附图中显示了一种示例性的形式,但是其应当理解为对所示出的精确设置和手段没有限制。
图1报道了低密度聚乙烯在32.6和32.9ppm之间的13C NMR图谱。
发明详述
本发明提供了适合用于吹塑膜应用的聚乙烯共混物组合物和由其制备的膜。本文所使用的术语“聚乙烯共混物组合物”是指至少本文所述的双峰线性低密度聚乙烯和单峰线性线性低密度聚乙烯和任选的低密度聚乙烯的物理共混物。
根据本发明的适合用于吹塑膜的聚乙烯共混物组合物,其包括以下物质的熔融共混产物:(a)0.5重量%至6重量%的双峰线性低密度聚乙烯,其密度为0.935至0.970g/cm3,且熔体指数(I2)为0.3至5g/10分钟;(b)90重量%或更高的单峰线性低密度聚乙烯,其密度为0.910至0.950g/cm3,熔体指数(I2)为0.1至小于或等于5g/10分钟;(c)任选的0.5重量%至4重量%的低密度聚乙烯,其密度为0.915至0.935g/cm3,熔体指数(I2)为大于0.8至小于或等于5g/10分钟,且分子量分布(Mw/Mn)为6至10;(d)任选的基于水滑石的中和剂;(e)任选的一种或多种成核剂;和(f)任选的一种或多种抗氧化剂。
聚乙烯共混物组合物的密度为0.910至0.955g/cm3。从0.910至0.955g/cm3的所有单个数值和子集范围都包含在此并且公开在此;例如,密度可以从作为下限的0.910、0915g/cm3至作为上限的0.925、0.930、0.940、0.945或0.955g/cm3。例如,聚乙烯共混物组合物可以具有以下密度:0.917至0.935g/cm3;或在备选方案中,0.918至0.925g/cm3;或在备选方案中,0.919至0.923g/cm3。
聚乙烯共混物组合物的熔体指数(I2)为0.1至5g/10分钟。从0.1至5g/10分钟的所有单个数值和子集范围都包含在此并且公开在此;例如,熔体指数(I2)可以从作为下限的0.1、0.2、0.5或0.8g/10分钟至作为上限的1、2、3、4或5g/10分钟。例如,聚乙烯共混物组合物可以具有的熔体指数(I2)为0.2至5g/10分钟;或者,在备选方案中,0.2至3g/10分钟;或者在备选方案中,0.5至2g/10分钟。
本发明的聚乙烯共混物组合物可以提供更高的熔体强度、更高的气泡稳定性和更高的输出速率以及改善的光学性能。
在另一实施方案中,当所述聚乙烯共混物组合物经由吹塑膜工艺成膜时,输出速率相对于类似单峰线性低密度聚乙烯至少改进5%,例如5至20%。
双峰线性低密度聚乙烯(BLLDPE)组分
根据本发明的适合用于吹塑膜的聚乙烯共混物组合物包括0.5至6重量%的双峰线性低密度聚乙烯(BLLDPE)。双峰线性低密度聚乙烯在凝胶渗透色谱确定的GPC曲线上具有2个峰。所述双峰线性低密度聚乙烯包括(a)小于或等于100重量%,例如至少80重量%、或至少90重量%、或至少95重量%的衍生自乙烯的单元;和(b)小于20重量%、或小于10重量%、或小于5重量%的衍生自一种或多种非乙烯的α-烯烃共聚单体的单元。
α-烯烃共聚单体通常具有不大于20个碳原子。例如,该α-烯烃共聚单体可优选具有3至10个碳原子,和更优选3至8个碳原子。示例性的α-烯烃共聚单体包括但不限于丙烯,1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯和4-甲基-1-戊烯。所述一种或多种α-烯烃共聚单体可例如选自丙烯、1-丁烯、1-己烯和1-辛烯;或者在备选实施方案中,选自1-己烯和1-辛烯。
双峰线性低密度聚乙烯的密度为0.935至0.970g/cm3。例如,密度可以为从作为下限的0.935、0.940或0.950g/cm3至作为上限的0.965、0.968或0.970g/cm3。
双峰线性低密度聚乙烯的分子量分布(Mw/Mn)为2至20。例如,分子量分布(Mw/Mn)可以为从作为下限的2、3或4至作为上限的10、15或20。
双峰线性低密度聚乙烯的熔体指数(I2)为0.3至5g/10分钟,例如,0.5至2。
可以使用任何常规的乙烯(共)聚合反应制备双峰线性低密度聚乙烯。该常规乙烯(共)聚合反应方法包括,但不限于,以并联、串联和/或它们的任何组合的方式使用至少两个常规反应器(例如流化床气相反应器、环管反应器、搅拌釜式反应器、间歇反应器)在一种或多种催化剂体系(包括但不限于齐格勒-纳塔催化剂体系、金属茂催化剂体系和/或后金属茂催化剂体系)的存在下进行的气相聚合法、淤浆相聚合法、液相聚合法和它们的组合。在一个实施方案中,在串联的双元反应器构造中制备的双峰线性低密度聚乙烯具有在一个反应器中制备的高分子量组分和在另一个反应器中制备的低分子量组分,其中所述高分子量组分的熔体指数(I2)为小于0.3g/10分钟,例如0.01至0.3g/10分钟。
这样的双峰线性低密度聚乙烯可以商品名ELITETM从The DowChemical Company购得。
单峰线性低密度聚乙烯(LLDPE)组分
根据本发明的适合用于吹塑膜的聚乙烯共混物组合物包括90重量%或更高的单峰线性低密度聚乙烯(MLLDPE);例如,90至99重量%;或者在备选方案中,95至99重量%;或者在备选方案中,97至99重量%。单峰线性低密度聚乙烯在凝胶渗透色谱确定的GPC曲线上具有仅1个峰。
MLLDPE的密度为0.910至0.950g/cm3。从0.910至0.950g/cm3的所有单个数值和子集范围都包含在此并且公开在此;例如,密度可以从作为下限的0.910、0915、0.917、0.918或0.919g/cm3至作为上限的0.930、0.941、0.947或0.950g/cm3。例如,MLLDPE可以具有以下密度:0.915至0.950g/cm3;或者在备选方案中,0.917至0.950g/cm3;或在备选方案中,0.918至0.925g/cm3;或在备选方案中,0.918至0.922g/cm3。
MLLDPE的分子量分布(Mw/Mn)为2至5,例如,3.5至5。
MLLDPE的熔体指数(I2)为0.1至5g/10分钟。从0.1至5g/10分钟的所有单个数值和子集范围都包含在此并且公开在此;例如,熔体指数(I2)可以从作为下限的0.1、0.2、0.5或0.8g/10分钟至作为上限的1、2、3、4或5g/10分钟。例如,MLLDPE以具有的熔体指数(I2)为0.2至5g/10分钟;或者,在备选方案中,0.2至3g/10分钟;或者在备选方案中,0.5至2g/10分钟。
MLLDPE的熔体流动比(I10/I2)可以为6至10。6至10的的所有单个数值和子集范围都包含在此并且公开在此。例如,MLLDPE的熔体流动比(I10/I2)可以为7至10;或者在备选方案中,7至9。
在一个实施方案中,MLLDPE在差示扫描量热法(DSC)加热曲线上具有2或更多个峰,根据差示扫描量热法(DSC)方法测量。
MLLDPE可以包含小于35重量%的衍生自一种或多种α-烯烃共聚单体的单元。小于35重量%的所有单个数值和子集范围都包含在此并且公开在此;例如,MLLDPE可以包含小于25重量%的衍生自一种或多种α-烯烃共聚单体的单元;或者在备选方案中,小于20重量%的衍生自一种或多种α-烯烃共聚单体的单元;或者在备选方案中,小于15重量%的衍生自一种或多种α-烯烃共聚单体的单元;或者在备选方案中,小于10重量%的衍生自一种或多种α-烯烃共聚单体的单元。
α-烯烃共聚单体通常具有不大于20个碳原子。例如,该α-烯烃共聚单体可优选具有3至10个碳原子,和更优选3至8个碳原子。示例性的α-烯烃共聚单体包括但不限于丙烯,1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯和4-甲基-1-戊烯。所述一种或多种α-烯烃共聚单体可例如选自丙烯、1-丁烯、1-己烯和1-辛烯;或者在备选实施方案中,选自1-己烯和1-辛烯。
MLLDPE可以包括至少65重量%的衍生自乙烯的单元。从至少65重量%的所有单个数值和子范围都包括在本文中并公开在本文中;例如,MLLDPE可以包括至少75重量%的衍生自乙烯的单元;或者在备选方案中,至少85重量%的衍生子乙烯的单元;或者在备选方案中,至少90重量%的衍生自乙烯的单元。
MLLDPE可以进一步与一种或多种额外的组分例如其他聚合物和/或添加剂混配。这样的添加剂包括但不限于一种或多种基于水滑石的中和剂、一种或多种成核剂、防静电剂、颜色增强剂、染料、润滑剂、填料、颜料、主抗氧化剂、辅助抗氧化剂、加工助剂、UV稳定剂、成核剂,和/或其组合。MLLDPE可含有任何量的添加剂。MLLDPE可包括合并重量为约0至约10重量%的这些添加剂,基于MLLDPE和这些添加剂的总重量。
可以使用任何常规的乙烯(共)聚合反应制备MLLDPE。该常规乙烯(共)聚合反应方法包括,但不限于,以并联、串联和/或它们的任何组合的方式使用一个或多个常规反应器(例如流化床气相反应器、环管反应器、搅拌釜式反应器、间歇反应器)在一种或多种催化剂体系(包括但不限于齐格勒-纳塔催化剂体系、金属茂催化剂体系和/或后金属茂催化剂体系)的存在下进行的气相聚合法、淤浆相聚合法、液相聚合法和它们的组合。
这样的MLLDPE可以商品名DOWLEXTM从The Dow Chemical Company购得。
低密度聚乙烯(LDPE)组分
根据本发明适合用于吹塑膜的聚乙烯共混物组合物包括小于或等于4重量%的低密度聚乙烯(LDPE);例如,0.5至4重量%;或者在备选方案中,0.5至3重量%;或者在备选方案中,1至3.5重量%。低密度聚乙烯的密度为0.915至0.935g/cm3;例如,0.915至0.925g/cm3;或者在备选方案中,0.918至0.922g/cm3。低密度聚乙烯的熔体指数(I2)为大于0.8至小于或等于5g/10分钟;例如,1至3g/10分钟;或者在备选方案中,1.5至2.5g/10分钟。低密度聚乙烯的分子量分布(Mw/Mn)为6至10;例如,6至9.5;或者在备选方案中,6至9;或者在备选方案中,6至8.5;或者在备选方案中,7.5至9。这样的低密度聚乙烯组合物可从例如The Dow Chemical Company购得。
LDPE的长链支链为至少2/1000个碳和/或最大4/1000个碳。
这样的LDPE可从The Dow Chemical Company够得。
添加剂
该聚乙烯共混物组合物还可包括一种或多种另外的添加剂。这些添加剂包括但不限于一种或多种基于水滑石的中和剂,一种或多种成核剂,一种或多种防静电剂,一种或多种颜色增强剂,一种或多种染料,一种或多种润滑剂,一种或多种填料,一种或多种颜料,一种或多种主抗氧化剂,一种或多种辅助抗氧化剂,一种或多种加工助剂,一种或多种紫外线稳定剂,和/或其组合。该聚乙烯共混物组合物可包括任何量的这些添加剂。该聚乙烯共混物组合物可包括总重量为约0至约10重量%的这些添加剂,基于聚乙烯共混物组合物的总重量。
生产
该聚乙烯共混物组合物通过任何常规的熔融共混方法如通过挤出机如单螺杆或双螺杆挤出机挤出而制备。可将该BLLDPE、MLLDPE、任选的LDPE和任选的一种或多种添加剂以任何顺序通过一个或多个挤出机进行熔融共混,从而形成均匀的聚乙烯共混物组合物。
应用
可将该聚乙烯共混物组合物通过例如吹塑膜方法形成为膜。在一个实施方案中,当将该聚乙烯共混物组合物经由吹塑膜工艺形成为膜时,该输出速率相对于类似单峰线性低密度聚乙烯改善至少5%。在一个实施方案中,该聚乙烯共混物组合物可形成为多层吹塑膜结构。在另一实施方式中,该聚乙烯共混物组合物可形成为与一个或多个基板相连的单层或多层吹塑膜结构。根据本发明制备的该吹塑膜可用作层压膜,其中该吹塑的聚乙烯膜粘性层合至基板如双轴取向的聚丙烯(BOPP)膜或者双轴取向的聚对苯二甲酸乙二醇酯(BOPET)膜,衬垫膜,密封平幅,收缩膜,拉伸膜,等。根据本发明的吹塑膜的厚度为0.3至5密耳,如0.5至5密耳。
实施例
以下实施例说明本发明,但不意图限制本发明的范围。本发明的实施例证实当所述聚乙烯共混物组合物经由吹塑膜工艺成膜时,输出速率相对于类似单峰线性低密度聚乙烯至少改进5%。
聚乙烯共混物组合物的组分:
BLLDPE为在串联的双元反应器构造中经由溶液聚合方法制备的双峰线性低密度聚乙烯,熔体指数(I2)为约0.83g/10分钟且密度为约0.961g/cm3,其可以商品名ELITETM5960G从The Dow Chemical Company购得。测量BLLDPE的性质并报道在表1中。
MLLDPE为在存在有基于齐格勒-纳塔的催化剂体系的单一反应器中经由溶液聚合方法制备的线性低密度聚乙烯,熔体指数(I2)为约0.96g/10分钟且密度为约0.920g/cm3,其可以商品名DOWLEX 2045G从The DowChemical Company购得。测量MLLDPE的性质并报道在表1中。
LDPE为经由高压聚合方法制备的低密度聚乙烯,熔体指数(I2)为约1.85g/10分钟且密度为0.919g/cm3,由The Dow Chemical Company提供。
本发明的组合物1
本发明组合物1为聚乙烯共混物组合物,其包括以下物质的熔融共混产物:(a)3重量%的BLLDPE;和(b)97重量%的MLLDPE。测量本发明组合物1的性质并报道在表2中。
本发明组合物2
本发明组合物2为聚乙烯共混物组合物,其包括以下物质的熔融共混产物(a)3重量%的BLLDPE;(b)94重量%的MLLDPE(包括900份的DHT-4A每百万份的MLLDPE);和(c)3重量%of LDPE。测量本发明组合物2的性质并报道在表2中。
对比组合物A
对比组合物A为聚乙烯共混物组合物,其包含100重量%的MLLDPE。测量对比组合物A的性质并报道在表2中。
本发明的膜1
经由吹塑膜工艺基于在表3中报道的工艺条件将本发明的组合物1成形为本发明的膜1。测量本发明的膜1(单层膜)的性质,并且结果报道在表4中。在表4中报道的膜性质针对的是在最大速率(约14.9lb/hr/in或375lb/hr)制备的膜。
本发明的膜2
经由吹塑膜工艺基于在表3中报道的工艺条件将本发明的组合物2成形为本发明的膜2。测量本发明的膜2(单层膜)的性质,并且结果报道在表4中。在表4中报道的膜性质针对的是在最大速率(约15.6lb/hr/in或392lb/hr)制备的膜。
对比膜A
经由吹塑膜工艺基于在表3中报道的工艺条件将对比组合物A成形为对比膜A。测量对比膜A(单层膜)的性质,并且结果报道在表4中。在表4中报道的膜性质针对的是在最大速率(约13.9lb/hr/in或349lb/hr)制备的膜。
表1
单位 | BLLDPE | MLLDPE | LDPE | |
密度 | g/cm3 | 0.961 | 0.920 | 0.919 |
I2 | g/10min | 0.83 | 0.96 | 1.85 |
I10/I2 | 10.6 | 7.9 | 14.3 | |
粘度(0.1rad/s) | Pa.s | 17,602 | 8,636 | 8,863 |
粘度(1.0rad/s) | Pa.s | 8,230 | 7,021 | 4,639 |
粘度(10rad/s) | Pa.s | 3,746 | 4,260 | 1,658 |
粘度(100rad/s) | Pa.s | 1347 | 1,677 | 464 |
TanΔ(0.1rad/s) | 2.1 | 10.4 | 3.1 | |
熔体强度 | cN | 3.9 | 3.0 | 9.2 |
Mn | g/mol | 19,470 | 28,750 | 11,628 |
Mw | g/mol | 101,410 | 115,650 | 94,485 |
Mz | g/mol | 280,100 | 386,194 | 321,061 |
Mw/Mn | 5.21 | 4.02 | 8.13 | |
Tm1(DSC) | ℃ | 134.4 | 122.3 | 109.2 |
Tm2(DSC) | ℃ | 110.4 | ||
Tc1(DSC) | ℃ | 119.1 | 105.0 | 95.6 |
融化热 | J/g | 217.1 | 140.5 | 136.8 |
表2
表3
表3续表
膜的制备 | 单位 | 本发明的膜1 | 本发明的膜2 | 对比膜A |
熔点 | °F | 453 | 452 | 444 |
温度性能(°F) | ||||
桶T1 | °F | 350 | 350 | 350 |
桶T2 | °F | 425 | 425 | 425 |
桶T3 | °F | 380 | 380 | 380 |
桶T4 | °F | 325 | 325 | 325 |
桶T5 | °F | 345 | 345 | 345 |
筛T | °F | 430 | 430 | 430 |
适配器T | °F | 445 | 445 | 445 |
拦网T | °F | 430 | 430 | 430 |
下模T | °F | 440 | 440 | 440 |
内模T | °F | 440 | 440 | 440 |
上模T | °F | 440 | 440 | 440 |
表4
膜的性质 | 单位 | 本发明的膜1 | 本发明的膜2 | 对比膜A |
膜的厚度 | 密耳 | 2.0 | 2.0 | 2.0 |
落镖冲击耐性-(方法A) | g | 283 | 273 | 424 |
撕裂:Elmendorf-MD | g/密耳 | 441 | 415 | 452 |
撕裂:Elmendorf-CD | g/密耳 | 585 | 605 | 514 |
击穿强度 | ft*1bf/in3 | 216 | 186 | 321 |
总雾度 | % | 36.4 | 16.5 | 21.5 |
内部雾度 | % | 5.4 | 4.1 | 4.5 |
光泽度 | % | 15.8 | 41.4 | 33.6 |
割线模量-CD(1%) | psi | 46513 | 43005 | 44333 |
割线模量-MD(1%) | psi | 38847 | 40387 | 38174 |
试验方法
试验方法包括以下:
熔体指数
熔体指数(I2和I10)根据ASTM D-1238在190℃和分别在2.16kg和10kg载荷测得。它们的值以g/10min给出。
密度
用于测量密度的样品根据ASTM D4703制备。测量在使用ASTM D792,方法B进行样品压制的1小时内进行。
动态剪切流变
将样品在177℃在10MPa压力下在空气中压缩模塑成3mm厚x 25mm直径圆片,保持5分钟。然后从压机中取出样品,并将其置于操作台上冷却。
恒温扫频测量(constant temperature frequency sweep measurements)在ARES应变控制的流变仪(TA Instruments)(安装有25mm平行板)上在氮气吹洗下进行。对于每个测量,在将间隙调零之前将该流变仪热平衡至少30分钟。将样品置于板上,并使其在190℃熔融5分钟。然后使该板闭合至2mm,修剪样品,然后开始试验。该方法另外设置5分钟延迟,从而容许温度平衡。将该实验在190℃在0.1-100rad/s的频率范围每10个时间间隔里在5个点进行。应变幅度恒定为10%。根据振幅和相位分析应力响应,从中计算存储模量(G’),损耗模量(G”),复数模量(G*),动态粘度(η*),和tan(δ)或tanΔ。
熔体强度
熔体强度测量在附接至Gottfert Rheotester 2000毛细管流变仪的GottfertRheotens 71.97(Inc.;Rock Hill,SC)上进行。以平的进入角(180度)将聚合物熔体挤出通过毛细管模头,其中毛细管直径为2.0mm和长径比(毛细管长度/毛细管直径)为15。
在将该样品在190℃平衡10分钟之后,活塞以恒定的0.265mm/秒的活塞速率运行。该标准试验温度为190℃。将该样品以2.4mm/秒2的加速度单轴拉伸至位于该模头下方100mm的一组加速夹辊。记录拉伸力随着夹辊的卷带速度的变化。熔体强度记录为线料断裂之前平稳状态的力(plateau force,cN)。以下条件用于熔体强度测量:活塞速度=0.265mm/秒;轮加速度=2.4mm/s2;毛细管直径=2.0mm;毛细管长度=30mm;和机筒直径=12mm。
DSC结晶度测定
差示扫描量热法(DSC)可用于在宽范围的温度测量样品在给定温度的结晶度。对于实施例,安装有RCS(Refrigerated Cooling System)冷却附件和自动进样器模块的TA型Q1000DSC(TA Instruments;New Castle,DE)用来进行该试验。在试验过程中,使用50ml/分钟的氮气吹洗气体流速。将每个样品压成薄膜,并在压机中在175℃熔融;然后将熔融的样品空气冷却至室温(~25℃)。将3-10mg冷却物的样品切成6mm直径的圆盘,称重,置于轻的铝盘(约50mg)中,并卷曲包封。然后测试样品的热性质。
样品的热性质通过将样品的温度向上和向下改变从而建立响应和温度分布的关系曲线来确定。首先将样品快速加热至180℃,并保持等温状态三分钟从而除去任何前面的热历史。接着,将样品以10℃/分钟的冷却速率冷却至-40℃,并在-40℃保持3分钟。然后将样品以10℃/分钟的加热速率加热至150℃。记录冷却曲线和第二次加热曲线。确定的值是聚乙烯样品的峰值熔融温度(Tm),峰值结晶温度(Tc),熔化热(Hf),和使用方程1计算的%结晶度:
%结晶度=[(Hf(J/g))/(292J/g)]x 100 (方程1)
熔化热(Hf)和峰值熔融温度由第二次加热曲线给出。峰值结晶温度由冷却曲线确定。
高温凝胶渗透色谱
凝胶渗透色谱(GPC)***由安装有板载差示折射仪(on-board differentialrefractometer,RI)(其它合适的浓度探测器可包括IR4红外探测器,来自Polymer ChAR(Valencia,Spain))的Waters(Milford,Mass)150C高温色谱仪(其它合适的高温GPC装置包括Polymer Laboratories(Shropshire,UK)型号210和型号220)组成。数据采集使用Viscotek TriSEC软件,版本3,和4-通道Viscotek Data Manager DM400进行。该***也安装有来自于PolymerLaboratories(Shropshire,United Kingdom)的在线溶剂脱气装置。
可使用合适的高温GPC柱例如四个30cm长的Shodex HT80313微米柱或四个具有20-微米混合-孔-尺寸填充物的30cm Polymer Labs柱(MixA LS,Polymer Labs)。样品的传送隔间(sample carousel compartment)在140℃操作,并且该柱隔间在150℃操作。样品以“0.1克聚合物在50毫升溶剂中”的浓度制备。色谱溶剂和样品制备溶剂含有200ppm三氯苯(TCB)。两种溶剂都用氮气吹扫。将聚乙烯样品在160℃下温和地搅拌4小时。进样体积为200微升。将通过GPC的流速设定为1ml/分钟。
通过运行21个窄分子量分布聚苯乙烯标样来校准GPC柱组。该标样的分子量(MW)范围为580至8,400,000,并且该标样含在6种“鸡尾酒”混合物中。各标样混合物的各分子量间具有至少10倍间隔。标样混合物购自PolymerLaboratories。分子量等于或大于1,000,000g/摩尔的聚苯乙烯标样以“0.025g在50mL溶剂中”的形式制备,分子量小于1,000,000g/摩尔的聚苯乙烯标样以“0.05g在50mL溶剂中”的形式制备。在温和的搅拌下将聚苯乙烯标样在80℃下溶解,持续30分钟。首先运行窄标样混合物,且按照最高分子量组分依次递减的顺序,以使得降解最小化。使用方程2(如Williams和Ward,J.Polym.Sci.,Polym.Letters,6,621(1968)中所述),将聚苯乙烯标样的峰值分子量转化为聚乙烯分子量:
M聚乙烯=A x(M聚苯乙烯)B, (方程2)
其中M是聚乙烯或者聚苯乙烯的分子量(如所标记的),且B等于1.0。本领域技术人员知道,A可以在约0.38-约0.44的范围内,并且在使用宽的聚乙烯标样校准时确定。使用此聚乙烯校准方法获得分子量值例如分子量分布(MWD或Mw/Mn)以及相关的数据(通常称为常规GPC或者cc-GPC结果),在此处定义为Williams和Ward的改进方法。
13C NMR
通过如下步骤制备样品:添加约2.7g含有0.025M Cr(AcAc)3的50/50四氯乙烷-d2/邻二氯苯的混合物至在Norell 1001-710mm NMR管中的0.4g样品中,并且然后在N2箱中吹洗2小时。通过使用加热段(heating block)和加热枪将该管和它的内容物加热至150℃将样品溶解并且匀化。视觉检查每个样品以确保均匀性。使用安装有Bruker Dual DUL高温CryoProbe的Bruker 400MHz光谱分析仪收集数据。该数据以57-80小时每个数据文件来获取,其中使用7.3秒的脉冲重复延迟(sec pulse repetition delay)(6秒延迟+1.3秒获取时间),90度倾倒角(flip angles),反向门控去耦(inverse gateddecoupling)和120℃的样品温度。所有的测量都在非旋转样品上以锁定的模式完成。在***到该加热的(125℃)NMR样品变换器(Sample changer)之前立即将样品匀化,并在数据获取之前使其在探针中热平衡7分钟。从在32.7ppm的峰区域的积分和它的净LDPE的峰的相对比例计算分支数。
膜试验条件
在产生的膜上测得以下物理性质:
·总雾度和内部雾度:用于测量内部雾度和总雾度的样品根据ASTM D1746取样和制备。内部雾度通过在膜的两侧使用矿物油进行折射指数匹配获得。Hazegard Plus(BYK-Gardner USA;Columbia,MD)用于试验。
·45°光泽度:ASTM D-2457.
·1%割线模量-MD(纵向)和CD(横向):ASTM D-882.
·MD和CD Elmendorf撕裂强度:ASTM D-1922
·MD和CD拉伸强度:ASTM D-882
·落镖冲击强度:ASTM D-1709,方法A
·击穿强度:击穿强度在Instron Model 4201上使用Sintech Testworks软件版本3.10测得。该样品的尺寸为6”x 6”,和进行四次测量以测定平均击穿值。将该膜在膜生产之后调节40小时,和在ASTM控制的实验室中调节至少24小时。使用100lb测力计,其具有圆形样品托盘12.56平方英寸(”square)。击穿探针是1/2”直径的抛光不锈钢球,具有7.5”的最大行进长度。没有标尺长度(gauge length);该探针尽可能接近于,但不接触,样品。使用的十字头速度为10”/分钟。在样品的中间测量厚度。通过软件使用膜的厚度,十字头行进的距离,和峰值载荷来确定击穿。在每个样品之后使用“Kim-擦拭(Kim-wipe)”清洁该击穿探针。
确定吹塑膜的最大输出速率
以控制的速率和最大速率收集膜样品。控制的速率为250lb/hr,其等于模头圆周的10lb/小时/英寸(lb/hr/inch)的输出速率。注意,用于该最大输出实验的模头直径是8”模头,从而对于该控制的速率,作为实例,lb/hr和模头圆周lb/小时/英寸之间的转化示于方程3中。类似地,这种方程可用于其它速率,例如该最大速率,通过在方程3中用最大速率代替250lb/hr的标准速率来确定模头圆周的lb/小时/英寸。
模头圆周的Lb/Hr/Inch=(250Lb/Hr)/(8*π)=10 (方程3)
对于给定样品,最大速率通过增加输出速率至当气泡稳定性是限制因素时的点来确定。对于两个样品(标准速率和最大速率),保持挤出机条件(profile),但是对于最大速率样品,熔体温度由于增加的剪切速率而较高。最大速率通过用空气环使内部起泡冷却和外部冷却最大化来确定。最大的气泡稳定性通过气泡呈现出观察到的以下任一项现象时来确定:(a)该气泡不保持固定在该空气环中,(b)该气泡开始失去它的形状,(c)该气泡开始忽大忽小(breathe in and out),或者(d)霜白线高度变得不稳定。在此点,速率降低至气泡再次固定在该空气环中,同时保持气泡的形状和稳定的霜白线高度,然后收集样品。在该气泡上的冷却通过调节空气环并保持该气泡而调节。将这个作为最大输出速率同时保持气泡的稳定性。
产生单层膜。该模头直径为8英寸,模头间隙为70密耳,吹塑比为2.5,和使用内部气泡冷却。
本发明可以以其它形式体现,而不偏离本发明的精神和重要性质,因此,应该参考表示本发明的范围的权利要求,而不是前述的说明书。
Claims (6)
1.适合用于吹塑膜的聚乙烯共混物组合物,其包含以下物质的熔融共混产物:
0.5重量%至6重量%的双峰线性低密度聚乙烯,其密度为0.935至0.970g/cm3,且熔体指数(I2)为0.3至5g/10分钟;
90重量%或更高的单峰线性低密度聚乙烯,其密度为0.910至0.950g/cm3,熔体指数(I2)为0.1至小于或等于5g/10分钟;
任选的0.5重量%至4重量%的低密度聚乙烯,其密度为0.915至0.935g/cm3,熔体指数(I2)为大于0.8至小于或等于5g/10分钟,且分子量分布(Mw/Mn)为6至10;
任选的基于水滑石的中和剂;
任选的一种或多种成核剂;
和任选的一种或多种抗氧化剂。
2.权利要求1的聚乙烯共混物组合物,其中当所述聚乙烯共混物组合物经由吹塑膜方法形成为膜时,输出速率相对于类似线性低密度聚乙烯改善至少5%。
3.吹塑膜,其包括权利要求1的聚乙烯共混物组合物。
4.制品,其包括一个或多个含有权利要求1的聚乙烯共混物组合物的吹塑膜。
5.容器装置,其含有:
(a)一个或多个基板;和
(b)一个或多个层,所述层包括一个或多个含有权利要求1的聚乙烯共混物组合物的吹塑膜。
6.前述权利要求中的任一项,其中所述聚乙烯共混物组合物具有通过13C NMR测量的在32.7ppm的峰,表示在LDPE组分中存在C5支链的C3碳。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261664301P | 2012-06-26 | 2012-06-26 | |
US61/664,301 | 2012-06-26 | ||
PCT/US2013/042139 WO2014003925A1 (en) | 2012-06-26 | 2013-05-22 | A polyethylene blend-composition suitable for blown films, and films made therefrom |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104582929A true CN104582929A (zh) | 2015-04-29 |
CN104582929B CN104582929B (zh) | 2017-03-08 |
Family
ID=48576571
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380042916.7A Active CN104582929B (zh) | 2012-06-26 | 2013-05-22 | 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9371441B2 (zh) |
EP (1) | EP2864102B1 (zh) |
JP (1) | JP6426086B2 (zh) |
CN (1) | CN104582929B (zh) |
AR (1) | AR091553A1 (zh) |
BR (1) | BR112014025322B1 (zh) |
ES (1) | ES2702716T3 (zh) |
MX (1) | MX353971B (zh) |
WO (1) | WO2014003925A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106633325A (zh) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | 一种聚乙烯组合物以及耐久性薄膜 |
CN106633330A (zh) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | 一种聚乙烯组合物及其薄膜 |
CN110154477A (zh) * | 2019-06-11 | 2019-08-23 | 福建富一锦科技有限公司 | 一种pe盒中袋膜及其制备方法 |
CN111621080A (zh) * | 2017-05-31 | 2020-09-04 | 尤尼威蒂恩技术有限责任公司 | 线性低密度聚乙烯的共混物 |
CN115380070A (zh) * | 2020-03-31 | 2022-11-22 | 普瑞曼聚合物株式会社 | 乙烯系树脂组合物和膜 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103881212B (zh) * | 2014-03-25 | 2016-06-08 | 上海海洋大学 | 食品保鲜膜及其制备方法 |
CN106554541B (zh) * | 2015-09-28 | 2019-11-12 | 中国石油化工股份有限公司 | 一种聚乙烯组合物和抗静电薄膜 |
CN106674701A (zh) * | 2015-11-06 | 2017-05-17 | 中国石油化工股份有限公司 | 一种抗菌组合物及其薄膜 |
WO2018106388A1 (en) | 2016-12-05 | 2018-06-14 | Exxonmobil Chemical Patents Inc. | Broad orthogonal distribution metallocene polyethylenes for films |
WO2018226311A1 (en) * | 2017-06-08 | 2018-12-13 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and extrudates and methods of making the same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999055775A1 (en) * | 1998-04-23 | 1999-11-04 | Crc For Polymers Pty. Ltd. | Low density polyethylene polymer blend and stretch wrap film application |
CN1608841A (zh) * | 2003-09-24 | 2005-04-27 | 埃克森美孚化学专利公司 | 整理收缩 |
CN1890315A (zh) * | 2003-12-01 | 2007-01-03 | 尤尼威蒂恩技术有限责任公司 | 低浊度、高强度的聚乙烯组合物 |
CN101052522A (zh) * | 2004-10-04 | 2007-10-10 | 保瑞利斯技术公司 | 膜 |
US20080038533A1 (en) * | 2006-05-31 | 2008-02-14 | Best Steven A | Linear polymers, polymer blends, and articles made therefrom |
US20090192270A1 (en) * | 2008-01-28 | 2009-07-30 | Malakoff Alan M | Ethylene-Based Polymers And Articles Made Therefrom |
WO2010144784A1 (en) * | 2009-06-11 | 2010-12-16 | Dow Global Technologies Inc. | Novel ldpe enabling high output and good optics when blended with other polymers |
WO2011109563A2 (en) * | 2010-03-02 | 2011-09-09 | Dow Global Technologies Llc | Ethylene-based polymer compositions |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2838120B2 (ja) * | 1988-11-30 | 1998-12-16 | 住友化学工業株式会社 | ポリエチレン樹脂組成物およびその積層フィルム |
US7422786B2 (en) * | 2003-09-24 | 2008-09-09 | Exxonmobil Chemical Patents Inc. | Collation shrink |
WO2007082817A1 (en) * | 2006-01-19 | 2007-07-26 | Basell Polyolefine Gmbh | Polyethylene composition for stretched tape products |
DE602007004315D1 (de) * | 2006-04-07 | 2010-03-04 | Dow Global Technologies Inc | L und herstellungsverfahren dafür |
EP1854841A1 (en) * | 2006-05-08 | 2007-11-14 | Borealis Technology Oy | Film |
JP5244311B2 (ja) * | 2006-12-27 | 2013-07-24 | 日本ポリエチレン株式会社 | バッグインボックス用内袋 |
CN102656229A (zh) * | 2010-10-19 | 2012-09-05 | 陶氏环球技术有限责任公司 | 具有减少的淀积量的聚乙烯组合物、以及由该聚乙烯组合物制备的具有减少的起霜量的膜 |
-
2013
- 2013-05-22 EP EP13726979.1A patent/EP2864102B1/en active Active
- 2013-05-22 BR BR112014025322-6A patent/BR112014025322B1/pt active IP Right Grant
- 2013-05-22 US US14/388,644 patent/US9371441B2/en active Active
- 2013-05-22 JP JP2015520191A patent/JP6426086B2/ja active Active
- 2013-05-22 CN CN201380042916.7A patent/CN104582929B/zh active Active
- 2013-05-22 ES ES13726979T patent/ES2702716T3/es active Active
- 2013-05-22 MX MX2014015724A patent/MX353971B/es active IP Right Grant
- 2013-05-22 WO PCT/US2013/042139 patent/WO2014003925A1/en active Application Filing
- 2013-06-25 AR ARP130102239 patent/AR091553A1/es active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999055775A1 (en) * | 1998-04-23 | 1999-11-04 | Crc For Polymers Pty. Ltd. | Low density polyethylene polymer blend and stretch wrap film application |
CN1608841A (zh) * | 2003-09-24 | 2005-04-27 | 埃克森美孚化学专利公司 | 整理收缩 |
CN1890315A (zh) * | 2003-12-01 | 2007-01-03 | 尤尼威蒂恩技术有限责任公司 | 低浊度、高强度的聚乙烯组合物 |
CN101052522A (zh) * | 2004-10-04 | 2007-10-10 | 保瑞利斯技术公司 | 膜 |
US20080038533A1 (en) * | 2006-05-31 | 2008-02-14 | Best Steven A | Linear polymers, polymer blends, and articles made therefrom |
US20090192270A1 (en) * | 2008-01-28 | 2009-07-30 | Malakoff Alan M | Ethylene-Based Polymers And Articles Made Therefrom |
WO2010144784A1 (en) * | 2009-06-11 | 2010-12-16 | Dow Global Technologies Inc. | Novel ldpe enabling high output and good optics when blended with other polymers |
WO2011109563A2 (en) * | 2010-03-02 | 2011-09-09 | Dow Global Technologies Llc | Ethylene-based polymer compositions |
Non-Patent Citations (1)
Title |
---|
周殿明: "《塑料薄膜挤出成型》", 30 April 2012, 机械工业出版社 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106633325A (zh) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | 一种聚乙烯组合物以及耐久性薄膜 |
CN106633325B (zh) * | 2015-10-28 | 2019-04-16 | 中国石油化工股份有限公司 | 一种聚乙烯组合物以及耐久性薄膜 |
CN106633330A (zh) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | 一种聚乙烯组合物及其薄膜 |
CN111621080A (zh) * | 2017-05-31 | 2020-09-04 | 尤尼威蒂恩技术有限责任公司 | 线性低密度聚乙烯的共混物 |
CN111621080B (zh) * | 2017-05-31 | 2023-05-05 | 尤尼威蒂恩技术有限责任公司 | 线性低密度聚乙烯的共混物 |
CN110154477A (zh) * | 2019-06-11 | 2019-08-23 | 福建富一锦科技有限公司 | 一种pe盒中袋膜及其制备方法 |
CN110154477B (zh) * | 2019-06-11 | 2022-01-18 | 福建富一锦科技有限公司 | 一种pe盒中袋膜及其制备方法 |
CN115380070A (zh) * | 2020-03-31 | 2022-11-22 | 普瑞曼聚合物株式会社 | 乙烯系树脂组合物和膜 |
Also Published As
Publication number | Publication date |
---|---|
US9371441B2 (en) | 2016-06-21 |
WO2014003925A1 (en) | 2014-01-03 |
CN104582929B (zh) | 2017-03-08 |
EP2864102B1 (en) | 2018-10-10 |
EP2864102A1 (en) | 2015-04-29 |
AR091553A1 (es) | 2015-02-11 |
JP6426086B2 (ja) | 2018-11-21 |
JP2015521688A (ja) | 2015-07-30 |
US20150291783A1 (en) | 2015-10-15 |
MX353971B (es) | 2018-02-07 |
MX2014015724A (es) | 2015-04-10 |
BR112014025322B1 (pt) | 2021-06-01 |
ES2702716T3 (es) | 2019-03-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104582929B (zh) | 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 | |
CN103649205B (zh) | 适合用于吹塑膜的聚乙烯共混物组合物,生产它的方法,和由其制备的膜 | |
CN104582931B (zh) | 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 | |
CN104540657B (zh) | 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 | |
CN103635525B (zh) | 适合用于吹塑膜的聚乙烯共混物组合物,生产它的方法,和由其制备的膜 | |
CN104582930A (zh) | 适合用于吹塑膜的聚乙烯共混物组合物和由其制备的膜 | |
CN104684990A (zh) | 聚烯烃共混物组合物及由其制备的薄膜 | |
US20240017535A1 (en) | Multilayer structures that include biaxially oriented films and sealant layers and methods for making the same | |
US20240025164A1 (en) | Multilayer structures that include oriented films and sealant layers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |