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CN1431954A - Improved barrier compsns. for multilayer extrusion and barrier performance - Google Patents

Improved barrier compsns. for multilayer extrusion and barrier performance Download PDF

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Publication number
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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China
Prior art keywords
shaped article
layer
barrier layer
modified
polyolefin
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Inventor
M·A·巴杰
R·拉马纳坦
J·A·朔马克
M·F·芬利森
C－w·A·张
K·塞哈诺比斯
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Dow Chemical Co
Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication of CN1431954A publication Critical patent/CN1431954A/en
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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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

本发明公开了具有至少一个阻隔层和一个支持层的改进的多层共挤出吹塑制品(例如油箱)，以及制备这种制品的改良方法。阻隔层包括一定量的改性聚烯烃，其密度与支持层大致相同，其中所述的改性聚烯烃通过把一种不饱和羧酸或其衍生物接枝到聚烯烃上制得，其中所述改性聚烯烃以一定量加入，以便气体阻隔层充分地粘合在相邻层上，而且制品仍然保持充分的气体阻隔性能。本发明还涉及基底树脂，如PET(用于阻隔层的优选材料)的流变改性，以便它们与高密度聚乙烯(用于支持层的优选材料)的流变性能更匹配。The present invention discloses improved multi-layer coextrusion blow molded articles having at least one barrier layer and one support layer, such as fuel tanks, and improved methods of making such articles. The barrier layer includes a certain amount of modified polyolefin, whose density is about the same as that of the support layer, wherein said modified polyolefin is prepared by grafting an unsaturated carboxylic acid or its derivatives onto the polyolefin, wherein the The modified polyolefin is added in an amount such that the gas barrier layer is sufficiently bonded to the adjacent layer and the article still maintains sufficient gas barrier properties. The present invention also relates to the rheological modification of base resins such as PET (the preferred material for the barrier layer) so that they better match the rheological properties of high density polyethylene (the preferred material for the support layer).

Description

Be used for multilayer and extrude and keep the improved barrier compositions of barrier property
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 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
Embodiment 5-8
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)

1.一种多层塑料成形制品，包括至少两层，其一为气体阻隔层，另一层是聚烯烃支持层，其中阻隔层包括一定量具有大约与支持层相同密度的改性聚烯烃，其中改性聚烯烃通过把一种不饱和羧酸或其衍生物接枝到聚烯烃上制得，加入一定量改性聚烯烃，这样气体阻隔层充分地粘合在相邻层上，并使得成形制品的气体阻隔性能与阻隔层不包含一定量改性聚烯烃的制品的气体阻隔性能相比不会减少。1. A multilayer plastic shaped article comprising at least two layers, one being a gas barrier layer and the other being a polyolefin support layer, wherein the barrier layer comprises an amount of modified polyolefin having about the same density as the support layer, The modified polyolefin is prepared by grafting an unsaturated carboxylic acid or its derivatives onto the polyolefin, adding a certain amount of modified polyolefin so that the gas barrier layer is fully bonded to the adjacent layer and makes The gas barrier properties of the shaped article are not reduced compared to the gas barrier properties of an article whose barrier layer does not contain an amount of modified polyolefin. 2.根据权利要求1中所述的成形制品，其中所述的阻隔层是结晶聚酯、结晶聚酰胺、结晶多芳基化合物或结晶乙烯-乙烯醇共聚物树脂。2. The shaped article according to claim 1, wherein said barrier layer is a crystalline polyester, crystalline polyamide, crystalline polyarylate or crystalline ethylene-vinyl alcohol copolymer resin. 3.根据权利要求2中所述的成形制品，其中所述的阻隔层包括聚对苯二甲酸乙二醇酯的均聚物或共聚物。3. The shaped article of claim 2, wherein said barrier layer comprises a homopolymer or copolymer of polyethylene terephthalate. 4.根据权利要求1中所述的成形制品，其中所述的改性聚烯烃是改性高密度聚乙烯。4. The shaped article according to claim 1, wherein said modified polyolefin is a modified high density polyethylene. 5.根据权利要求1中所述的成形制品，其中所述的改性聚烯烃包括从0.5wt％到5.0wt％的羧酸或其衍生物。5. The shaped article according to claim 1, wherein said modified polyolefin comprises from 0.5 wt% to 5.0 wt% of carboxylic acid or its derivatives. 6.根据权利要求1中所述的成形制品，其中所述的改性聚烯烃包括从0.8wt％到1.2wt％的羧酸或其衍生物。6. The shaped article according to claim 1, wherein said modified polyolefin comprises from 0.8 wt% to 1.2 wt% of carboxylic acid or its derivatives. 7.根据权利要求1中所述的成形制品，其中所述的羧酸衍生物是马来酸酐。7. The shaped article according to claim 1, wherein said carboxylic acid derivative is maleic anhydride. 8.根据权利要求1中所述的成形制品，其中所述的改性聚烯烃在阻隔层中的含量占阻隔层的2wt％到10wt％。8. The shaped article according to claim 1, wherein the content of the modified polyolefin in the barrier layer is 2wt% to 10wt% of the barrier layer. 9.根据权利要求1中所述的成形制品，其中所述的阻隔层直接粘合在聚烯烃支持层上。9. The shaped article of claim 1, wherein said barrier layer is bonded directly to the polyolefin support layer. 10.根据权利要求1中所述的成形制品，其中所述的成形制品是容器、导管或膜。10. The shaped article of claim 1, wherein said shaped article is a container, conduit or film. 11.根据权利要求1中所述的成形制品，其中所述聚烯烃支持层是高密度聚乙烯。11. The shaped article of claim 1, wherein the polyolefin support layer is high density polyethylene. 12.根据权利要求3中所述的成形制品，其中所述的改性聚对苯二甲酸乙二醇酯已经被改变流变性使之可以与聚烯烃层达到理想共挤出。12. The shaped article according to claim 3, wherein said modified polyethylene terephthalate has been rheologically modified to allow for the desired coextrusion with the polyolefin layer. 13.根据权利要求12中所述的成形制品，其中所述的聚对苯二甲酸乙二醇酯通过支化被改变流变性。13. The shaped article of claim 12, wherein said polyethylene terephthalate is rheologically modified by branching. 14.根据权利要求1中所述的成形制品，其中所述的阻隔层的结晶度至少21％。14. The shaped article of claim 1, wherein said barrier layer has a crystallinity of at least 21%. 15.根据权利要求14中所述的成形制品，其中所述的阻隔层的结晶度至少34％。15. The shaped article of claim 14, wherein said barrier layer has a crystallinity of at least 34%. 16.根据权利要求1中所述的成形制品，其中所述的成形制品通过吹塑、热成型、双片成型或多元注射模塑得到。16. The shaped article according to claim 1, wherein said shaped article is obtained by blow molding, thermoforming, two-piece molding or multi-component injection molding. 17.一种提高聚酯和聚烯烃材料的粘合性能的方法，包括引入一种在高密度聚乙烯中接枝上一种不饱和羧酸或其衍生物的改性高密度聚乙烯，其中加到聚对苯二甲酸乙二醇酯中的改性高密度聚乙烯的量为聚酯的2wt％到10wt％之间。17. A method for improving the bonding properties of polyester and polyolefin materials, comprising introducing a modified high-density polyethylene grafted with a kind of unsaturated carboxylic acid or derivatives thereof in high-density polyethylene, wherein The amount of modified high-density polyethylene added to the polyethylene terephthalate is between 2 wt% and 10 wt% of the polyester. 18.根据权利要求17中所述的方法，其中所述的聚酯是聚对苯二甲酸乙二醇酯，不饱和羧酸或其衍生物是马来酸酐。18. The method according to claim 17, wherein said polyester is polyethylene terephthalate, and the unsaturated carboxylic acid or derivative thereof is maleic anhydride. 19.一种改进的树脂，包含聚对苯二甲酸乙二醇酯和马来酸酐改性聚乙烯，其中包含的聚对苯二甲酸乙二醇酯占组合物的90％到98％，包含的改性聚乙烯占组合物的10％到2％，包含的马来酸酐占改性聚乙烯的0.5wt％到5.0wt％。19. An improved resin comprising polyethylene terephthalate and maleic anhydride modified polyethylene, wherein the polyethylene terephthalate comprises from 90% to 98% of the composition, comprising The modified polyethylene accounts for 10% to 2% of the composition, and the contained maleic anhydride accounts for 0.5wt% to 5.0wt% of the modified polyethylene. 20.一种改进的共挤出多层制品，包括一种长链支化的聚酯材料和一个包含高密度聚乙烯的支持层，其中聚酯材料中长链支化的量是选定的，只要这样的聚酯材料的流变特性与支持层流变特性更相匹配。20. An improved coextruded multilayer article comprising a long chain branched polyester material and a support layer comprising high density polyethylene, wherein the amount of long chain branching in the polyester material is selected , as long as the rheological properties of such a polyester material more closely match the rheological properties of the support layer. 21.一个用于提高具有两个或更多个聚合层的吹塑制品的加工性能的方法，包括：21. A method for improving the processability of a blow molded article having two or more polymeric layers comprising: 通过促进长链支化调节其中一层的流变性，这样调节过的层的流变特性与没有调节过的层的流变特性更相匹配。The rheology of one of the layers is adjusted by promoting long chain branching so that the rheology of the adjusted layer more closely matches the rheology of the unmodified layer. 22.根据权利要求21中所述的方法，其中所述的长链支化通过引入多官能团单体来调节。22. The method of claim 21, wherein said long chain branching is modulated by introducing multifunctional monomers. 23.根据权利要求21中所述的方法，其中所述的长链支化通过与多官能团支化剂一起反应挤出调节。23. The method of claim 21, wherein said long chain branching is modulated by reactive extrusion with a multifunctional branching agent.
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CN102427942A (en) * 2009-05-18 2012-04-25 东洋制罐株式会社 multilayer structure
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CN109721912A (en) * 2019-02-28 2019-05-07 康泰塑胶科技集团有限公司 A barrier layer, multi-layer plastic composite pipe and preparation method
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