CN1431954A - Improved barrier compsns. for multilayer extrusion and barrier performance - Google Patents
Improved barrier compsns. for multilayer extrusion and barrier performance Download PDFInfo
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- CN1431954A CN1431954A CN01810282A CN01810282A CN1431954A CN 1431954 A CN1431954 A CN 1431954A CN 01810282 A CN01810282 A CN 01810282A CN 01810282 A CN01810282 A CN 01810282A CN 1431954 A CN1431954 A CN 1431954A
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- molded article
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- 230000004888 barrier function Effects 0.000 title claims abstract description 56
- 230000001976 improved effect Effects 0.000 title claims abstract description 24
- 238000001125 extrusion Methods 0.000 title 1
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 45
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920000098 polyolefin Polymers 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 230000008093 supporting effect Effects 0.000 claims description 21
- 229920000728 polyester Polymers 0.000 claims description 20
- -1 polyethylene Polymers 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 12
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000006085 branching agent Substances 0.000 claims description 5
- 229920001230 polyarylate Polymers 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229920006039 crystalline polyamide Polymers 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 238000003856 thermoforming Methods 0.000 claims description 2
- 230000000295 complement effect Effects 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000002650 laminated plastic Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 10
- 238000000518 rheometry Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 101150015738 Fev gene Proteins 0.000 description 11
- 102100037681 Protein FEV Human genes 0.000 description 11
- 230000008595 infiltration Effects 0.000 description 10
- 238000001764 infiltration Methods 0.000 description 10
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 9
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003380 propellant Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0862—Crystallinity
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
-
- 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
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
Abstract
Improved multi-layer coextruded blow-molded objects (such as fuel containers) having at least a barrier layer and a support layer are disclosed together with improved methods for preparing such objects. The barrier layer includes an amount of modified polyolefin having approximately the same density as the support layer, wherein the modified polyolefin is prepared by grafting an unsaturated carboxylic acid or a derivative thereof to the polyolefin, the modified polyolefin being added in an amount such that the gas-barrier layer sufficiently adheres to the adjacent layer and such that the gas barrier properties of the fabricated article are still adequate. The present invention also relates to modification of the rheology of base resins, such as PET (a preferred material for the barrier layer), so that they more closely match the rheology of high density polyethylene (a preferred material for the support layer).
Description
Invention field
The present invention relates to improve the bonding force between the barrier layer and supporting layer in the coextrusion blow molding applications.More specifically, the present invention relates to add a kind of modified poly ethylene that bond properties is arranged at barrier layer or supporting layer, wherein said modified poly ethylene makes by a kind of unsaturated carboxylic acid or derivatives thereof is grafted on the high density polyethylene (HDPE).In addition, the present invention also relates to base resin, rheology modified as PET, the rheological property of they and high density polyethylene (HDPE) (in the coextrusion blow molding process, being used for a kind of preferred material of supporting layer) more closely mates like this.Better matching has promoted stratotype homogeneous in the parison on rheological property, and this brings consistent more final products.
Background of invention and general introduction
Because in light weight, the source is wide, production cost is relatively low and intensity is high, plastics (synthetic resin) are used to various container manufacturings for a long time.Vistanex is proved to be in this application and is particularly useful.Though vistanex has a lot of ideal performances, as chemicals, as the gas or the steam barrier layer of hydrocarbon, alcohols, ketone, ethers etc., they are not effective especially.Therefore, vistanex itself and not being suitable for because many application scenarios that environment or security reason must prevent the chemicals vapour leakage.These application scenarios comprise the container of molded article as storage or transportation usefulness, or container such as fuel tank, conduit or film.
Therefore, people have taked various means to improve the barrier property of polyolefin containers.One of them example is US-A-5,441,781, it proposes a kind of laminated vessel (fuel tank), like this one deck can play barrier layer for gases and another the layer (polyolefin layer) play the support effect.This list of references points out to have the 3rd layer (one " adhesive layer ") that the barrier layer can be adhered on the supporting layer.This list of references points out that adhesive layer comprises a kind of resin, and as a kind of modified poly ethylene, this modified poly ethylene is to make by a kind of unsaturated carboxylic acid or derivatives thereof is grafted on the high density polyethylene (HDPE) (HDPE).
Simplify and make and reduce cost if can eliminate this adhesive layer, but remaining a kind of is the container with abundant capacity for air resistance of substrate with the polyolefin, and this will be gratifying.
People are surprised to find now, when a small amount of certain jointing material (mentioning in ' 781 patents as those) is introduced in a kind of resin (PETG for example that fuel element is had the infiltration barrier property, PET), and particularly the sort of oxygenated fuel component such as methyl alcohol and ethanol are had in the resin of infiltration barrier property, the bond properties of this resin improves so, has but kept gas barrier property.
Therefore, one aspect of the present invention is about a kind of improved resin, it comprises PETG and maleic anhydride modified high density polyethylene (HDPE) (HDPE-g-MAH), wherein PETG accounts for 90% to 98% of said composition, modified poly ethylene accounts for 10% to 2% of said composition, and maleic anhydride accounts for the 0.5wt% of modified poly ethylene to 5.0wt%.
Also find, when certain other jointing material (for example LLDPE-g-MAH) to be added among the PET with above-mentioned HDPE-g-MAH same concentrations, the barrier property of mixture reduces.Therefore, though only by mixing a kind of and all chemical compatible material of two-phase just can obtain cohesive between PET and HDPE, distinctive feature of the present invention is to have obtained this bonding force under the condition of not damaging the barrier layer obstructing capacity.
Because allow cancellation adhesive layer or articulamentum, this new type resin can be effective to sandwich construction.The barrier layer that comprises resin of the present invention can be bonding with other layer better, comprises the polyolefin supporting layer, eliminated the necessity of adhesive layer or articulamentum.Therefore be not the described 3 or 5 layers of structure of ' 781 patents, the resin among the present invention allows is 2 or 3-tier architecture.In addition, even still use articulamentum, if PET is at first high-density polycthylene grafted maleic anhydride modified by introducing, the bonding force between PET and the articulamentum will improve.
Therefore, another aspect of the present invention is a kind of two-layer multilayer plastic container that comprises, first gas-barrier layer, one deck is the polyolefin supporting layer in addition, wherein barrier layer comprises a certain amount of modification high-density polyethylene, wherein modification high-density polyethylene is to make by a kind of unsaturated carboxylic acid or derivatives thereof is grafted on the high density polyethylene (HDPE), adds a certain amount of modification high-density polyethylene and makes gas-barrier layer adhere on the adjacent layer fully.
The bond properties that generally improves PET also is valuable, and PET will also can use in other purposes beyond the container like this.Therefore, another aspect of the present invention comprises that (they can be crystalline polyesters to a kind of raising barrier layer, crystalline polyamide, crystallization polyarylate and crystalline ethylene-vinyl alcohol copolymer resin) method of bond properties and between polyolefine material, comprise that introducing is a kind of by a kind of unsaturated carboxylic acid or derivatives thereof is grafted to the modification high-density polyethylene that makes on the high density polyethylene (HDPE), wherein modified poly ethylene is added in the PETG to the content of 10wt% to account for 2wt%, and preferred 3wt% is to 8wt%.As fuel tank the time, polythene material is high density polyethylene (HDPE) preferably, and modified poly ethylene is a modification high-density polyethylene.
At present, coextrusion blowing is the method for optimizing of making the multilevel shaping goods.This method needs one to mate with each layer of promotion in annular parison dyeing full and uniform in rheology fully between composition material.Traditional PET, with other traditional polyester, as poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(naphthalenedicarboxylic acid second diester), gather 2 hydroxy propanoic acid, contain the polyester copolymer of terephthalic acids ester moiety, and the liquid crystal polyarylate is the same, in molten condition, demonstrate tangible Newtonian behavior, yet the HDPE resin demonstrates clear and definite non-newtonian feature.Therefore, PET has brought so far with combining of HDPE and has had the edge until uniformity very poor coextrusion sheet material and blow-molded article.Therefore, another aspect of the present invention solves this problem by the long chain branching degree that improves in the polyester, and can not form a large amount of crosslinked or gels.Detailed Description Of The Invention
Improved barrier layer resins of the present invention comprises a base resin, and it can be a crystalline polyester, crystalline polyamide, crystallization polyarylate or crystalline ethylene-vinyl alcohol copolymer resin and a spot of modification high-density polyethylene (HDPE).HDPE preferably uses the modification of a kind of unsaturated carboxylic acid or derivatives thereof, for example maleic anhydride, acrylic acid etc.Improved barrier layer resins comprises 90% to 98% base resin, 10% to 2% modified poly ethylene.Modified poly ethylene comprises the unsaturated carboxylic acid or derivatives thereof of 0.5wt% to 5.0wt% (preferred 0.5wt% is to 1.4wt%).
Compare with unmodified PET, the resin among the present invention has shown improved bonding force, and has kept its barrier property.Therefore, the resin among the present invention can be effective in the two-layer at least multilayer plastic container, first gas-barrier layer, and another layer is the polyolefin supporting layer.Such container is at US-A-5, description arranged in 441,781.The polyolefine material that is suitable for is at US-A-5, and 380,810, U.S. patent application 08/857,817, or in the U.S. patent application 08/857,816 description is arranged.The preferred material that is used for supporting layer is HDPE.If melt strength needs to improve (for example when making such as the such heavy goods of automotive oil tank), so such as those at WO99/10393; WO99/10415; WO99/10421; WO99/10422; WO99/10423; WO99/10424; WO99/10425; The method of describing among WO99/10426 or the WO99/10427 can be used for these polyolefine materials of modification, makes them obtain higher melt strength.
Container of the present invention can only be made of two-layer, but the use of extra play can be benefited.For example, people may wish that two supporting layers surround barrier layer, and supporting layer and container contents and container institute exposed exterior environment all touches like this.
In addition, though the bonding force of resin improved of the present invention allows to eliminate articulamentum as a rule, in some application scenario, each interlayer may need higher bonding force, in this case, uses articulamentum to remain preferred.Should be realized that as the bonding force of resin raising barrier layer of the present invention and supporting layer, it also can improve the bonding force of barrier layer and articulamentum.Be preferred for articulamentum of the present invention and comprise what those were described in ' 781 patents.
One embodiment of the present of invention, promptly laminated vessel can prepare with any method known in the art.This comprises that blow molding and coextrusion sheet heat forming form container, can two parts or more parts welding can not welded yet in the thermoforming.Blow molding method generally is preferred.For example, the resin of each layer can be in two or more extruders by plasticising respectively, place identical molds, when regulating the parison that each concentration has the monofilm appearance with preparation in mould lamination.Parison can expand by being pressed in the model in the air then, and parison contacts with mould and cools off like this.
In coextrusion blowing, it is favourable that each layer has similar rheological property.The result it has been found that typical polyester will have the rheological characteristic similar to HDPE by improve the long chain branching degree in being used as the polyester material of substrate barrier material.No matter whether barrier material comprises that improved polyalkene improves bonding force, and this all is favourable.The substrate polyester that can change in this way comprises PET, poly-(mutual-phenenyl two acid bromide two alcohol ester), and poly-(naphthalenedicarboxylic acid second diester) gathers 2 hydroxy propanoic acid, contains the polyester copolymer of terephthalic acids ester moiety, and the liquid crystal polyarylate.
The long chain branching degree can improve by add polyfunctional monomer in initial polymerization, perhaps by the post-reactor modification, extrudes as reacting with polyfunctional group branching agent one.These processes (are seen as US-A-5,536,793 generally known in the art; US-A-5,556,926; US-A-5,422,381; US-A-5,362,763; And US-A-5,422,381).Known in the artly may branching agent comprise 1,2,4-benzenetricarboxylic anhydride, 1,3,5-benzenetricarboxylic anhydride, phthalic anhydride, PMDA (PMDA) and any monomer that contains 3 or more a plurality of oh groups.Using the PMDA reaction to extrude is a method for optimizing that promotes long chain branching.The branching agent addition should be avoided significantly crosslinked and/or gel forms.Branching agent preferably is less than 1wt%.
Alternatively, the additive that can make good nucleator can be used for promoting the crystallization of branched polyester, helps the following unfavorable factor of compensation, because compare with thread like material, the crystallization that has the side chain material is generally in the comparatively disadvantageous fact of thermodynamics.In the art, suitable nucleator is (seeing as US-A-4,572,852 of extensively knowing; US-A-5,431,972; US-A-5,843,545; Or US-A-5,747,127).
Therefore, particularly advantageous scheme of the present invention comprises polymolecular stratification goods, and it comprises at least one barrier layer and a supporting layer.The preferred HDPE of supporting layer, barrier layer comprise the PETG of long chain branching and relatively small amount grafting the HDPE of a small amount of maleic anhydride.Goods in this particularly advantageous scheme prepare by coextrusion blowing.Such goods particularly suitable is made fuel tank, is fit to the dress oxygenated fuel.
In addition, have been found that the barrier property of barrier layer depends on the percent crystallinity (X of the polymer that constitutes barrier layer greatly
c).When using PET as barrier layer, adopt determine with dsc method, the crystallinity of polymer in the preferred container finished product is greater than 8%, and more preferably 21%, most preferably 34%, and preferably be no more than 50%, more preferably no more than 40%.Wish to have similar relation between the barrier layer performance of other barrier layer resin and the degree of crystallinity quantity.These barrier layer resin crystallinity can be with those in method change known in the art, as control cooling velocity and/or annealing.
Should be realized that degree of crystallinity may be subjected to the influence of certain propellant composition, as methyl alcohol.Methyl alcohol is considered to destroy the hydrogen bond of EVOH, and therefore reduces the obstructing capacity of EVOH.Yet for PET, we find that methyl alcohol can cause solvent-induced crystallization, and this has improved degree of crystallinity, and therefore further improve barrier property.Hydrogen bond among the EVOH also is considered to and can be destroyed by humidity, and the obstructing capacity of PET is not subjected to humidity effect.This has especially influenced the total structure and the design of multilayer fuel container structure.EVOH should avoid directly contacting with the fuel bed that contains moisture or methyl alcohol.On the other hand, PET does not show same defective, can directly contact with fuel.
Also generally be known that the quantity except degree of crystallinity, crystal morphology is to improve another factor that resin intercepts resistance, and still the influence relevant with crystallization degree compared, and this influence is less.
Embodiment
Following term should have the meaning of appointment among the embodiment:
" PET1 " refers to the conventional P ET (Lighter of Dow Chemical (Dow Chemical Company)
TML90A), its inherent viscosity is 0.77, in phenol/1, measures in the 2-dichlorobenzene solution (weight ratio 60/40) under 23 ℃ of the concentration with 0.5% (w/v).
" PET2 " is a kind of modified PET, and it is that PET1 reacts under 0.45wt% PMDA (PDMA) existence condition and extrudes, then 196 ℃ down solid-state processing obtained in 14 hours.Use GPC-DV to analyze resulting polymers, determine to compare with PET1, PET2 has shown the raising (bringing up to 135kg/mol from 46) of number-average molecular weight, has a wideer polydispersity index (from 1.9 to 5.3).The inherent viscosity of PET2 is 2.28, be concentration (w/v) with 0.5% under 23 ℃ in phenol/1, measure in the 2-dichlorobenzene solution (weight ratio 60/40).
" PET3 " is the coring PET (Versatray of Eastman chemical company (Eastman ChemicalCompany)
TM12822), its inherent viscosity is 0.89, measures in phenol/tetrachloroethanes (weight ratio 60/40) solution under the concentration with 0.5% (w/v), 23 ℃.
Embodiment 1-4
Following examples are to be used for proving the improved caking property of multi-layer product, and according to of the present invention, the barrier layer of these goods comprises improved polyalkene.The multilayer bottle prepares on blow moulding machine Bekum BM-502, and throughput rate is per hour about 42 pounds during this machine operation.The great about 60g of bottle (total injection volume 85-90g).The PET barrier layer is an internal layer, and about 254 ℃ of the melt temperature that demonstrates in all cases.Supporting layer in each situation is the HDPE (Lupolen of BASF AG
TM4261A HDPE).If articulamentum is arranged, it is ADMER
TMSF-700, what a kind of Mitsui petrochemical industry (Mitsui Petrochmicals) provided is the adhesive of substrate with EVA.
These assessment results as shown in Table I.Table I
Embodiment 5-8
| Embodiment | Barrier layer | Articulamentum | Effect |
| ??1 | ??PET1 | Have | Good bonding |
| ??2 | ??PET2 | Have | Bonding better than embodiment 1 |
| ??3 | ??PET1 | Do not have | Leafing in one hour |
| ??4 | ??PET2 | Do not have | Even delamination occurs yet after 2 weeks |
Following examples are to be used for proving improved processing characteristics, according to of the present invention, processing characteristics is to obtain by the polyester material that uses a kind of long chain branching, wherein the amount of long chain branching is selected in the polyester material, and the rheological property of the rheological property of polyester material and supporting layer mates more like this.
HDPE (the Lupolen of BASF AG then
TM4261A HDPE), PET1, the melt viscosity feature of PET2 and PET3 is equipped with the parallel-plate device by use and is set to the flow graph RMS800 that can operate in linear viscoelastic region to be described.Data reproduction is in Fig. 1, and data show that PET2 shows the rheological characteristic similar to HDPE, has substantial different with PET1 or PET3.
Fig. 1
Embodiment 9-13-penetration testing
The self-supporting permeability of the membrane that fuel C M15 sees through barrier material uses following steps to measure down at 41 ℃ (+/-1 ℃).A test membrane, diameter be 4 inch thickness 1 and 100mil (mil) between disk be placed between two Room of test trough.(comprise toluene/isooctane that percent by volume is 42.5/42.5/15/methanol mixture, 95mL) be added in the upper chamber, layer is layered on above the specimen film fuel C M15, passes through helium flow with 10mL/min in lower chamber.Along with fuel infiltrate barrier layer enters lower chamber, it is rolled out test trough by helium flow and passes through the injection ring of a gas chromatograph (GC).In particular time interval, the content in the injection ring is injected into one at 140 ℃ of 25m that operate down, 0.53mmID, and the anterior tail end of ChrompackPoraplot-U capillary column, the helium flow that utilizes 10mL/min is as carrier gas.Determine that with retention time GC separates and quantize to see through the propellant composition of sample film.The date and the time of injection, Penetration Signature and the peak original area calculated value that sees through composition are stored in the computer document in order to further analyzing.Use a kind of multi-ported valve, 16 helium sample flow are monitored by GC; With 8 hours interval, measure the propellant composition content in each fluid streams.In 16 sample flow 15 link to each other with the sample film permeable tank.The 16th fluid streams flows out from comprising a kind of gas collecting jar with ground-on cover plate by the reference mixture of respectively forming for the toluene of 50ppm, isooctane and methyl alcohol, and constantly supplies helium.The reference gas data are used to calibrate GC original area calculated value data to determine the ppm level of propellant composition from the sample flow that permeable tank is come.
The sample test film is at Pasadena Hydraulics, carries out compression moulding=obtain with one 6 inches * 6 inches thick moulds of 5mil in the Inc. forcing press.The EVOH material is Eval
TMF101A, its ethylene contents are 32mol%.EVOH utilizes following condition compression moulding to obtain: 1) at 210 ℃, under 1000 pounds of impressed pressures in mould molten resin 4 minutes; 2), under 40,000 pounds of impressed pressures resin was pressed 6 minutes at 210 ℃; And 3) under 40,000 pounds of impressed pressures mould is slowly cooled off above one hour to 50 ℃.The PET resin is with the condition of similarity moulding, except mould in the step 1 is to be heated to 280 ℃.
Fuel-barrier can be measured in the film sample of being made by some materials.These appraisal procedures produce following result, as shown in Table II.Table II
| Permeability, (g *mil/m 2*day)，@41℃ | |||
| Material | 400 hours | 900 hours | 3500 hours |
| EVOH | 50 | ||
| PET3 | 4+ | ||
| PET1 | 7+ | 15 | |
| PET2 | 3+ | 10 | |
Infiltration is not to be in stable state during+this test, and infiltration capacity is also in slow rising.
As shown in Table II, EVOH reaches the steady seepage state in 400 hours, and experiment stops.Infiltration relevant with 3 PET samples in the time of 900 hours does not also reach stable state, though infiltration is substantially on the level of the low about order of magnitude of the infiltration state more stable than EVOH.The permeability test of PET3 is terminated at this moment.The infiltration of PET1 and PET2 reached stable state after 3500 hours.Against one's expectation, the permeability of PET2 material is lower than PET1.The PET2 of long chain branching is not hoped the crystallization effectively as PET1.Though it is believed that, shown in 900 hours permeation data like that, the branching among the PET2 is that the equal phase point with nucleation plays a role, this is similar to the heterogeneous nucleation among the PET3.
Embodiment 14-17
The influence of crystallinity level on PET fuel-barrier energy assessed according to following steps.The PET2 sample of preparation has different crystallinity (X
C) level.The preparation of embodiment 14-16 is by the material fusion, quench, then under 130 ℃ respectively with anneal of material 10,20 or 30 seconds.The preparation of embodiment 17 is fusion slowly cooling then.Crystallinity level DSC assessment.Detect permeability as embodiment 9-13 then, infiltration rate such as Table III after 350 hours are reported: Table III
| Sample | X C | Infiltration rate (g after 350 hours *mil/m 2*day) |
| 14 | 2 | The too high and immeasurability of numerical value |
| 15 | 8 | 12 |
| 16 | 21 | 6 |
| 17 | 34 | 4 |
Claims (23)
1. laminated plastics molded article, comprise two-layer at least, one is a gas-barrier layer, another layer is the polyolefin supporting layer, wherein barrier layer comprises a certain amount of improved polyalkene with about and supporting layer equal densities, wherein improved polyalkene makes by a kind of unsaturated carboxylic acid or derivatives thereof is grafted on the polyolefin, add a certain amount of improved polyalkene, gas-barrier layer is bonded on the adjacent layer fully like this, and makes the gas barrier property of molded article not compare and can reduce with the gas barrier property that barrier layer does not comprise the goods of a certain amount of improved polyalkene.
2. according to the molded article described in the claim 1, wherein said barrier layer is crystalline polyester, crystalline polyamide, crystallization polyarylate or crystalline ethylene-vinyl alcohol copolymer resin.
3. according to the molded article described in the claim 2, wherein said barrier layer comprises the homopolymers or the copolymer of PETG.
4. according to the molded article described in the claim 1, wherein said improved polyalkene is a modification high-density polyethylene.
5. according to the molded article described in the claim 1, wherein said improved polyalkene comprises the carboxylic acid or derivatives thereof from 0.5wt% to 5.0wt%.
6. according to the molded article described in the claim 1, wherein said improved polyalkene comprises the carboxylic acid or derivatives thereof from 0.8wt% to 1.2wt%.
7. according to the molded article described in the claim 1, wherein said carboxylic acid derivates is a maleic anhydride.
8. according to the molded article described in the claim 1, the content of wherein said improved polyalkene in barrier layer accounts for the 2wt% of barrier layer to 10wt%.
9. according to the molded article described in the claim 1, wherein said barrier layer directly is bonded on the polyolefin supporting layer.
10. according to the molded article described in the claim 1, wherein said molded article is container, conduit or film.
11. according to the molded article described in the claim 1, wherein said polyolefin supporting layer is a high density polyethylene (HDPE).
12. according to the molded article described in the claim 3, wherein said modification PETG has been changed rheological characteristic and has made it and can reach desirable coextrusion with polyolefin layer.
13. according to the molded article described in the claim 12, wherein said PETG is changed rheological characteristic by branching.
14. according to the molded article described in the claim 1, the degree of crystallinity at least 21% of wherein said barrier layer.
15. according to the molded article described in the claim 14, the degree of crystallinity at least 34% of wherein said barrier layer.
16. according to the molded article described in the claim 1, wherein said molded article is by blowing, thermoforming, biplate moulding or polynary injection-molded obtaining.
17. method that improves the bond properties of polyester and polyolefine material, comprise introduce a kind of in high density polyethylene (HDPE) a kind of modification high-density polyethylene of unsaturated carboxylic acid or derivatives thereof in the grafting, the amount that wherein is added to the modification high-density polyethylene in the PETG is that the 2wt% of polyester is between the 10wt%.
18. according to the method described in the claim 17, wherein said polyester is a PETG, the unsaturated carboxylic acid or derivatives thereof is a maleic anhydride.
19. improved resin, comprise PETG and maleic anhydride modified polyethylene, the PETG that wherein comprises accounts for 90% to 98% of composition, the modified poly ethylene that comprises accounts for 10% to 2% of composition, and the maleic anhydride that comprises accounts for the 0.5wt% of modified poly ethylene to 5.0wt%.
20. improved coextruded multilayer goods, polyester material and a supporting layer that comprises high density polyethylene (HDPE) of comprising a kind of long chain branching, wherein the amount of long chain branching is selected in the polyester material, as long as the rheological behavior and the supporting layer rheological behavior of such polyester material more are complementary.
21. a method that is used to improve the processing characteristics of the blow-molded article with two or more polymer layers comprises:
By promoting long chain branching to regulate the wherein rheological characteristic of one deck, the rheological behavior of the layer of regulating so more is complementary with the rheological behavior of the layer of not regulating.
22. according to the method described in the claim 21, wherein said long chain branching is regulated by introducing polyfunctional monomer.
23. according to the method described in the claim 21, wherein said long chain branching is extruded adjusting by reacting with polyfunctional group branching agent one.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20782000P | 2000-05-30 | 2000-05-30 | |
| US60/207,820 | 2000-05-30 |
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| Publication Number | Publication Date |
|---|---|
| CN1431954A true CN1431954A (en) | 2003-07-23 |
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ID=22772121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01810282A Pending CN1431954A (en) | 2000-05-30 | 2001-05-11 | Improved barrier compsns. for multilayer extrusion and barrier performance |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1289753A2 (en) |
| JP (1) | JP2003534946A (en) |
| KR (1) | KR20030007740A (en) |
| CN (1) | CN1431954A (en) |
| AU (1) | AU2001261524A1 (en) |
| BR (1) | BR0111663A (en) |
| CA (1) | CA2408229A1 (en) |
| MX (1) | MXPA02011932A (en) |
| WO (1) | WO2001092007A2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102022234A (en) * | 2010-12-31 | 2011-04-20 | 新康电脑科技（苏州）有限公司 | Six-layer coextruded functional type blown plastic fuel tank for automobile |
| CN102202885A (en) * | 2008-11-06 | 2011-09-28 | 陶氏环球技术有限责任公司 | Co-extruded, multilayered polyolefin-based backsheet for electronic device modules |
| CN102427942A (en) * | 2009-05-18 | 2012-04-25 | 东洋制罐株式会社 | Multilayered structure |
| CN109721912A (en) * | 2019-02-28 | 2019-05-07 | 康泰塑胶科技集团有限公司 | A kind of barrier layer, laminated plastics multiple tube and preparation method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100143546A1 (en) | 2008-12-09 | 2010-06-10 | The Coca-Cola Company | Container and composition for enhanced gas barrier properties |
| US8110265B2 (en) | 2008-12-09 | 2012-02-07 | The Coca-Cola Company | Pet container and compositions having enhanced mechanical properties and gas barrier properties |
| KR200452421Y1 (en) * | 2010-07-21 | 2011-02-28 | 주식회사 빌드넷 | Structure of Shore Cover for Guard Rail |
| KR101948333B1 (en) | 2010-09-30 | 2019-02-14 | 다우 글로벌 테크놀로지스 엘엘씨 | Method for manufacturing flexible multilayer electrical articles with improved layer adhesion |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5831106B2 (en) * | 1979-04-24 | 1983-07-04 | 出光興産株式会社 | thermoplastic resin composition |
| US5240525A (en) * | 1988-10-17 | 1993-08-31 | The Standard Oil Company | Method of fabricating a multilayer barrier packaging material |
| DE4433664A1 (en) * | 1994-09-21 | 1996-03-28 | Buna Sow Leuna Olefinverb Gmbh | Thermoplastic molding compounds with gas barrier properties |
| RU2113125C1 (en) * | 1997-08-06 | 1998-06-20 | Общество с ограниченной ответственностью - Производственно-коммерческая фирма "Атлантис-ПАК" | Polyamide-based tubular film |
| GB9804143D0 (en) * | 1998-02-26 | 1998-04-22 | Bp Chem Int Ltd | Adhesive blends |
-
2001
- 2001-05-11 BR BR0111663-0A patent/BR0111663A/en not_active Application Discontinuation
- 2001-05-11 MX MXPA02011932A patent/MXPA02011932A/en not_active Application Discontinuation
- 2001-05-11 WO PCT/US2001/015431 patent/WO2001092007A2/en not_active Application Discontinuation
- 2001-05-11 JP JP2001588001A patent/JP2003534946A/en active Pending
- 2001-05-11 EP EP01935425A patent/EP1289753A2/en not_active Withdrawn
- 2001-05-11 CA CA002408229A patent/CA2408229A1/en not_active Abandoned
- 2001-05-11 KR KR1020027016156A patent/KR20030007740A/en not_active Application Discontinuation
- 2001-05-11 CN CN01810282A patent/CN1431954A/en active Pending
- 2001-05-11 AU AU2001261524A patent/AU2001261524A1/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102202885A (en) * | 2008-11-06 | 2011-09-28 | 陶氏环球技术有限责任公司 | Co-extruded, multilayered polyolefin-based backsheet for electronic device modules |
| CN102202885B (en) * | 2008-11-06 | 2013-11-13 | 陶氏环球技术有限责任公司 | Co-extruded, multilayered polyolefin-based backsheet for electronic device modules |
| CN102427942A (en) * | 2009-05-18 | 2012-04-25 | 东洋制罐株式会社 | Multilayered structure |
| CN102427942B (en) * | 2009-05-18 | 2014-09-17 | 东洋制罐株式会社 | Multilayered structure |
| CN102022234A (en) * | 2010-12-31 | 2011-04-20 | 新康电脑科技（苏州）有限公司 | Six-layer coextruded functional type blown plastic fuel tank for automobile |
| CN102022234B (en) * | 2010-12-31 | 2012-08-29 | 新康电脑科技（苏州）有限公司 | Six-layer coextruded functional type blown plastic fuel tank for automobile |
| CN109721912A (en) * | 2019-02-28 | 2019-05-07 | 康泰塑胶科技集团有限公司 | A kind of barrier layer, laminated plastics multiple tube and preparation method |
| CN109721912B (en) * | 2019-02-28 | 2021-05-25 | 康泰塑胶科技集团有限公司 | Barrier layer, multilayer plastic composite pipe and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003534946A (en) | 2003-11-25 |
| WO2001092007A2 (en) | 2001-12-06 |
| EP1289753A2 (en) | 2003-03-12 |
| BR0111663A (en) | 2003-05-27 |
| CA2408229A1 (en) | 2001-12-06 |
| MXPA02011932A (en) | 2003-05-27 |
| WO2001092007A3 (en) | 2002-04-25 |
| KR20030007740A (en) | 2003-01-23 |
| AU2001261524A1 (en) | 2001-12-11 |
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