WO2016012558A1 - Récipient moulé par soufflage - Google Patents

Récipient moulé par soufflage Download PDF

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Publication number
WO2016012558A1
WO2016012558A1 PCT/EP2015/066924 EP2015066924W WO2016012558A1 WO 2016012558 A1 WO2016012558 A1 WO 2016012558A1 EP 2015066924 W EP2015066924 W EP 2015066924W WO 2016012558 A1 WO2016012558 A1 WO 2016012558A1
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WO
WIPO (PCT)
Prior art keywords
blow molded
composition
ppm
molded container
amount ranging
Prior art date
Application number
PCT/EP2015/066924
Other languages
English (en)
Inventor
Wilhelmus Josephus Maria Sour
Tim Leonardus Maria VORAGE
Original Assignee
Dsm Ip Assets B.V.
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Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Publication of WO2016012558A1 publication Critical patent/WO2016012558A1/fr

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Classifications

    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • 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
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/004—Semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0089—Impact strength or toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

  • This invention relates to a blow molded container, as well as a process for preparing a blow molded container.
  • Blow molded containers are known and are for example used as fuel containers, for chemical storage, liners for composite vessels etc. These containers require low temperature impact performance and a certain elongation at break.
  • Small containers are known to be blow molded from composition comprising polyamides, as polyamides offer the advantage of having low permeability towards hydrocarbon fuels, good mechanical properties and good chemical resistance.
  • Larger containers are difficult to be blow molded from compositions comprising polyamides, as polyamide based blow molding material does not have a sufficient stable parison that allows the production of blow molding, monolayer, heavy weight, large volume containers. Therefore, mostly tubes are extruded, domes are injection molded after which these are joint via welding. This method is more costly and introduces a liability around the weldline.
  • Another possibility to prepare larger containers by blow molding is to increase the extrusion speed in order to have a stable parison.
  • this also causes shear at the die due to friction, and therefore thermal degradation. Decreasing the extrusion speed to have less shear at the die may result in parison sagging and makes it difficult to get a homogeneous wall thickness distribution.
  • Sagging is a known phenomenon in blow molding and relates to the elongation of a parison under the load of the weight of the parison. Sagging is of increasing importance when the parison is longer and/or thicker, as this increases the load on the upper part of the parison.
  • At least one impact modifier in an amount ranging from 1 wt% to 50 wt%; iii. At least one silicone oil in an amount ranging from 50 ppm to 1000 ppm; iv. At least one branching agent in an amount ranging from 0.01 wt% to 6.0 wt%;
  • At least one stabilizer in an amount ranging from 0.05 wt% to 2.0 wt%; wherein L is at least 75 cm, and in which L> 2W ⁇ D, and the melt volume flow rate of the composition is in the range of 15 to 50 cm 3 /10 min, as measured according to ISO 1 133 with 21.6 kg and 275 °C and in which wt% and ppm is with respect to the total amount of composition.
  • this composition provides for blow molded containers, which exhibits better mechanical properties than compared to blow molded containers of the prior art.
  • the blow molded container according to the invention shows a stable parison upon production. This allows for production of larger containers, and/or thicker wall thicknesses. Another advantage of the blow molded container according to the invention is that a more homogeneous wall thickness distribution can be obtained. Another advantage is that the container does not need to be welded, and can thus be free of weld lines. This results in less weak spots in a container. Yet another advantage is that a good pinch line is obtained. A pinch line is a known phenomenon in blow molding and refers to the area where the parison is pinched.
  • a parison is herein understood to be a tube-like piece of molten composition with a hole in one end through which compressed gas can pass.
  • the parison is pinched and clamped into a mold after which a gas is blown into it.
  • the gas pressure then pushes the composition out to match the mold. After this the composition is cooled and solidifies, the mold opens up and the part is ejected.
  • gases may be employed to push the composition out to match the mold, such as for example air or nitrogen.
  • air is used, as this is readily available and is safe to use during processing.
  • blow molded container a container prepared by blow molding a composition.
  • the blow molded container has a length L, a width W and a depth D as defined in a 3 dimensional Cartesian coordinate system.
  • the length is defined as the largest dimension compared to the width and depth.
  • the width is defined as the largest dimension in a plane perpendicular to the length.
  • the width and the depth may differ, such as in a rectangular shape.
  • the width and the depth may be the same such as in for example a cylindrical shape.
  • width and depth are the same, as this allows for more homogeneous stress distribution.
  • the blow molded container according to the invention has an L of at least 75 cm, and L> 2W ⁇ D.
  • L is at least 100 cm, more preferably at least 150 cm and most preferred at least 250 cm.
  • the blow molded container has L> 3W ⁇ D, more preferred L> 4W ⁇ D, and most preferred L> 5W ⁇ D.
  • the volume of the blow molded container according to the invention is preferably at least 40 liters, more preferably at least 70 liters and even more preferred at least 120 liters, and most preferred at least 250 liters.
  • the volume of a container may be as high as 2500 liters.
  • the blow molded container has a weight of at least 3 kg, more preferably the weight is at least 4 kg and most preferred at least 5 kg.
  • the blow molded containers according to the invention may have a weight as high as 75 kg.
  • the blow molded container has an L of at least 100 cm and L> 3W ⁇ D. In a more preferred embodiment the blow molded container has an L of at least 250 cm and L> 5W ⁇ D.
  • the blow molded container may be part of a tank and may be wrapped with for example fiber reinforced thermoset or thermoplast in order to provide higher strength.
  • Applications include pressure containers for gas storage, as well as storage containers for chemicals, foods etc.
  • the average wall thickness of the blow molded container is at least 0.8 mm in order to provide sufficient strength. More preferably, the average wall thickness is at least 1 .0 mm, even more preferred at least 1 .5 mm. Wall thicknesses of 3, 4, 5 and 6 mm can be prepared, depending on the desired application.
  • the blow molded containers have at least one opening which is parallel to the extrusion direction of the parison.
  • the blow molded containers preferably have a cylindrical shape, as this allows for more homogenous wall thickness distribution.
  • Semi-crystalline polyamides are herein to be understood as being homopolymers, copolymers, blends and grafts of synthetic long-chain polyamides having recurring amide groups in the polymer main chain as an essential constituent.
  • polyamide homopolymers are polyamide-6 (PA 6, polycaprolactam, polycondensation of epsilon-caprolactam), polyamide-10 (PA 10, polydecanoamide), polyamide-1 1 (PA 1 1 , polyundecanolactam), polyamide-12 (PA 12,
  • polydodecanolactam polyamide-6, 6
  • PA 66 polyhexamethyleneadipamide, polycondensation product of hexamethylene diamine and adipic acid
  • PA 69 condensation product of polycondensation product of 1 ,6-hexamethylene diamine and and azelaic acid
  • PA 410 polycondensation product of diaminobutane and 1 ,10-decanedioic acid
  • polyamide-6, 10 PA 610,
  • PA 1012 polycondensation product of 1 ,6-hexamethylene diamine and 1 ,10-decanedioic acid
  • PA 612 polycondensation product of 1 ,6-hexamethylenediamine and 1 ,12-dodecanedioic acid
  • PA 1010 polycondensation product of 1 ,10-decamethylenediamine and 1 ,10-decanedicarboxylic acid
  • PA 1012 PA 1012
  • PA 1212 polycondensation product of 1 ,12-dodecamethylenediamine and dodecanedicarboxylic acid
  • Polyamide copolymers may comprise the polyamide building blocks in various ratios.
  • polyamide copolymers are polyamide 6/66 and polyamide 66/6 (PA 6/66, PA 66/6, copolyamides made from PA 6 and PA 66 building blocks, i.e. made from epsilon caprolactam, hexamethylenediamine and adipic acid).
  • PA 66/6 (90/10) may contain 90 percent of PA 66 and 10 percent of PA 6.
  • Further examples are polyamide 66/ 610 (PA 66/610, made from hexamethylenediamine, adipic acid and sebacic acid).
  • Polyamide copolymers may also comprise cyclic building blocks including aromatic building blocks, such as isophorone diamine, terephtalic acid, isophtalic acid, such as for example PA 6/IPDT and PA6I/6T.
  • the polyamide copolymers comprise cyclic building blocks in an amount less than building blocks of chosen from the group of epsilon-caprolactam,
  • hexamethylene diamine hexamethylene diamine, adipic acid and combinations thereof.
  • the semi-crystalline polyamides have as main building blocks epsilon-caprolactam and/or building blocks hexamethylene diamine and adipic acid, including PA-6, PA-66, PA6/66 and PA66/6 and blends thereof.
  • the semi-crystalline polyamide is preferably present in an amount ranging from 50 to 98.96 wt%, more preferably in an amount ranging from 60 to 80 wt%, most preferred in an amount ranging from 70 to 80 wt%.
  • Suitable impact modifiers are rubber-like polymers that not only contain apolar monomers such as olefins, but also polar or reactive monomers such as, among others, acrylates and epoxide, acid or anhydride containing monomers. Examples include a copolymer of ethylene with (meth)acrylic acid or an
  • impact modifiers are ethylene/propylene copolymer functionalized with anhydride groups.
  • the advantage of impact modifiers is that they do not only improve the impact strength of the composition but also contribute to less sagging.
  • impact modifiers are rubbers containing apolar monomers such as olefins, and also polar or reactive monomers such as, among others, acrylates, epoxide, acid or anhydride containing monomers. Examples include a copolymer of ethylene with (meth)acrylic acid or an ethylene/propylene copolymer functionalized with anhydride groups.
  • rubber is herein meant a flexible rubber with a low modulus and a glass transition temperature lower than 0 °C, preferably lower than -25 °C, more preferably lower than -40 °C, and most preferred lower than -50 °C.
  • polymers falling under this definition are copolymers of ethylene and a-olefins, for example propene and butene.
  • plastomers, being copolymers of for example ethylene and 1 -octene, that can be obtained by polymerization in the presence of a metallocene catalyst, are suitable as component of the rubber mixture.
  • a functionalized rubber is a rubber containing groups being reactive with polyamide.
  • Such functionalized rubbers are known.
  • US-4.174.358 describes a large number of suitable functionalized rubbers as well as the methods for preparing such functionalized rubbers.
  • Highly suitable are olefinic rubbers that are chemically modified by reaction with maleic anhydride or
  • entcopolymers of the rubber with a unsaturated dicarboxylic acid, anhydride and/or esters thereof for example maleic acid anhydride, itaconic acid and itaconic acid anhydride, fumaric acid and ester of maleic acid and glycidyl acrylate for example glycidylmethacrylate.
  • the polyamide preferably contains sufficient amino-end groups which can react with the functional groups.
  • the functionalized ethylene-oolefin copolymer is in case of a polyamide-6 preferably functionalized with maleic acid anhydride.
  • the maleic acid anhydride content of the functionalized rubber may vary within wide limits, for example ranging from 0.1 to 10 wt.%, preferably ranging from 0.1 to 5 wt.%, more preferably ranging from 0.1 to 2 wt.%.
  • the amount of impact modifiers is at least 1 wt % with respect to the total amount of the composition, preferably at least 5 wt%, more preferably at least 7.5 wt% and most preferred at least 10 wt%. This has the advantage that the impact strength is good.
  • the amount of impact modifiers is at most 50 wt % with respect to the total amount of the composition, preferably at most 40 wt%, and even more preferred at most 30 wt%. This has the advantage that the barrier properties remain sufficient.
  • the impact modifier is a maleic anhydride functionalized polyolefin.
  • Suitable silicone oils are polymerized siloxanes with organic side chains, and include for example polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the kinematic viscosity of the silicone oils is ranging from 50 cSt (centiStokes) to 12500 cSt.
  • the amount of silicone oil is at least 50 ppm with respect to the total composition, more preferably at least 75 ppm, and most preferred at least 100 ppm.
  • the composition comprises at most 1000 ppm, more preferably at most 800 ppm and most preferred at most 500 ppm.
  • composition for the container according to the invention comprises a branching agent in an amount ranging from 0.01 to 6.0 wt% relative to the total composition, preferably from 0.03 to 3 wt%, and most preferred from 0.06 to 1 .5 wt%.
  • Suitable branching agents that can be used in the composition of the container according to the invention are branching agents that have functional groups that can react with amino, amide and/or carboxylic end-groups in the polyamide.
  • the branching agent comprises functional groups chosen from the group of carboxylic acids and carboxylic acid anhydrides, or derivatives thereof, and epoxies.
  • the advantage of these groups is that these can react with the functional groups in the polyamide during melt-processing of the composition in regular compounding processes in an extruder.
  • suitable branching agents are oligomers and polymers comprising monomers having said functional groups.
  • the branching agent comprises a copolymer of at least an unsaturated dicarboxylic acid or a derivative thereof and a vinyl aromatic monomer. At least is here understood to mean that the copolymer may also contain a minor amount of one or more other monomers.
  • the advantage is that the branching agent can be prepared by easy processes and from cheap raw materials, and that the effect of the copolymer when used as a branching agent can be controlled by the composition of the copolymer.
  • suitable unsaturated dicarboxylic acids or derivatives thereof that can be used as monomer for the copolymer are maleic acid or itaconic acid, or derivatives thereof, for example maleic anhydride (MA), N-phenyl maleinimide or itaconic anhydride.
  • Dicarboxylic acid derivatives are here understood to be in particular anhydride or imide derivatives.
  • Suitable vinyl aromatic monomers are styrene, or styrenics in which the aromatic ring contains a halogen or alkyl substituent.
  • styrene or styrenics in which the aromatic ring contains a halogen or alkyl substituent.
  • SMA copolymer of maleic anhydride and styrene
  • the MA content of the copolymer generally ranges from 5 to 40 wt%, preferably ranges from 10 to 35 wt% with respect to the copolymer.
  • the advantage of a MA content above 10 weight % is that a higher degree of branching can be achieved through reaction with the polyamide.
  • the advantage of a MA content below 35 weight % is that the risk of gel formation is reduced. More preferably the MA content ranges from 20 to 30 weight %. With these ranges the above mentioned advantages are further increased.
  • the branching agent comprises (a) a copolymer of at least an unsaturated dicarboxylic acid or a derivative thereof and a vinylaromatic monomer, preferably styrene maleic anhydride copolymer (SMA), and (b) a copolymer of acrylonitrile and a vinylaromatic monomer, preferably styrene-acrylonitrile copolymer (SAN) wherein (a) and (b) are miscible and the ratio (a) / (b) is between 1/3 to 3/1.
  • SMA styrene maleic anhydride copolymer
  • SAN styrene-acrylonitrile copolymer
  • the branching agent comprises
  • branching agent is a much better reproducibility when preparing a polyamide composition with non-Newtonian melt flow behaviour and a much more accurate control of the viscosity, while in addition hardly any problems are caused by formation of gel particles.
  • a further advantage is that a high MA content can be used without occurring of any undesirable crosslinking and formation of insoluble particles (gel particles).
  • Another advantage is that larger amounts of branching agent can be added, so that there are fewer dosing problems in the production of a composition.
  • Suitable vinyl aromatic monomers in component (b) are the same as described for the copolymer (a), with (b) preferably being a copolymer of styrene and acrylonitrile (SAN).
  • the acrylonitrile (AN) content of (b) generally ranges from 5 to 40 wt %, preferably from 10 to 35 wt%, and more preferably from 20 to 30 wt%.
  • the advantage of a higher AN content is a higher polarity of the copolymer, which improves the compatibility with polyamides.
  • an SMA copolymer is miscible with a SAN copolymer if the ratio between the MA content and the AN content, thus MA content / AN content, of the respective copolymers is roughly between 1.6 and 0.6.
  • the branching agent therefore contains SMA and SAN copolymers with a ratio between the MA content and the AN content of between 1 .6 and 0.6, more preferably between 1.2 and 0.8.
  • the ratio between the amounts of components (a) and (b) may in principle vary between 3/1 and 1/3.
  • Preferably the (a)/(b) ratio lies between 2/1 and 1/2. This has the advantage that a better dispersion of the branching agent is obtained.
  • the branching agent contains 10-80 weight % of an inert processing aid.
  • a thermoplastic polymer is an example of a suitable inert processing aid. This has the advantage that dosing of the branching agent is greatly improved and can be controlled much more accurately.
  • This inert processing aid also serves as carrier material for the preparation of a branching agent in the form of a SMA and SAN concentrate. Inert is understood to mean that the processing aid or the carrier material does not react with the other components (a) and (b) and with amine groups of the polyamide to which the branching agent is later added, and neither does it interfere to any undesirable extent with the reaction between anhydride groups and amine groups.
  • the inert processing aid is preferably a thermoplastic polyolefin.
  • LDPE low- and high-density polyethylene
  • ethylene/oolefin copolymers such as plastomers, ethylene copolymers with a vinyl monomer or an alkyl(meth)acrylate, such as for example vinyl acetate or ethyl acrylate, and propylene homopolymer and copolymers.
  • the branching agent preferably contains an LDPE as inert processing aid in view of its good processability. In a special embodiment the branching agent contains between 40 and 80 weight % of an inert processing aid.
  • branching agent is preferred when an SMA with a low anhydride group content is used and a lower amounts are preferred when an SMA with a high anhydride content is used.
  • a larger amount of branching agent and/or a higher anhydride groups content in the branching agent generally results in a stronger increase in the viscosity and more pronounced non-Newtonian melt flow behaviour of the composition.
  • the blow molded container according to the invention comprises at least one stabilizer in an amount ranging from 0.05 wt% to 2.0 wt% with respect to the total amount of composition, preferably the amount ranges from 0.1 to 1.5 wt% and most preferred ranges from 0.3 wt% to 1 .2 wt%.
  • Stabilizers are known per se and are intended to counter deterioration as a result of the effects of for example heat, light and radicals thereby formed.
  • Known stabilizers that can be applied in the composition of the blow molded container according to the invention are for example hindered amine stabilizers, hindered phenols, phenolic antioxidants, copper salts and halogenides, preferably bromides and iodides, and mixtures of copper salts and halogenides, for example copper iodide/potassium iodide compositions and also phosphites, phosphonites, thioethers and hindered benzoates.
  • the stabilizer is chosen from the group consisting of inorganic, hindered phenolic oxidant, hindered amine stabilizer and combinations thereof. More preferably, the stabilizers are a combination of inorganic stabilizer, a phenolic antioxidant and a hindered amine.
  • Other optional ingredients are for example hindered amine stabilizers, hindered phenols, phenolic antioxidants, copper salts and halogenides, preferably bromides and iodides, and mixtures of copper
  • the blow molded container according to the invention preferably comprises a nucleating agent. More preferably, the nucleating agent is micro talcum.
  • Micro talcum may be present in the composition in very low amounts, such as in an amount of at least 0.001 wt% with respect to the total amount of the polymer composition, preferably at least 0.01 wt%, more preferably at least 0.02 wt%, even more preferably at least 0.04 wt%.
  • micro talcum may be present in the polymer composition in an amount of at most 1 wt% with respect to the total amount of the composition, more preferably at most 0.5 wt% and even more preferred at most 0.2 wt%.
  • Presence of micro talcum in a blow molded container according to the invention has the advantage that it improves the barrier performance against hydrocarbon fuels.
  • melt volume flow rate (MVR) of the composition is in the range of
  • the MVR is in the range from 25 to 45 cm 3 /10 min, and most preferred in the range from 30 to 40 cm 3 /10 min, as this is the optimum between sagging and heat increase due to friction at the die upon preparing the blow molded container.
  • a person skilled in the art can attain this value by routine experiments by choosing a polyamide with a certain viscosity and the appropriate amount of branching agent, as well as varying the time of post condensation. When employing a polyamide with a lower viscosity, a higher amount of branching agent is necessary and vice versa.
  • Blow-molding is here understood to comprise at least the following steps:
  • the invention also relates to a process for preparing a blow molded container. Surprisingly it has been found that a process for preparing a blow molded container comprising at least the following steps:
  • At least one impact modifier in an amount ranging from 5 wt% to 30 wt%;
  • At least one silicone oil in an amount ranging from 50 ppm to 1000 ppm;
  • At least one branching agent in an amount ranging from 0.01 wt% to 6.0 wt%;
  • At least one stabilizer in an amount ranging from 0.05 wt% to 2.0 wt%;
  • the parison has a length of at least 80 cm, more preferred, the length is at least 100 cm and most preferred at least 200 cm.
  • the length of the parison can be as high as 500 cm.
  • the length of the parison is defined as being parallel to the extrusion direction of the parison.
  • the composition is prepared by melt mixing components i), ii), iv) and v), after which the composition is cooled and granulated and optionally postcondensed in the solid state.
  • the silicone oil is then added to the granules, by for example dusting. This has the advantage over melt mixing all components, in that the silicone oil is more effective and thus allows lower amounts of silicone oil.
  • the MVR of the composition in step a) is in the range from 25 to 45 cm 3 /10 min, and most preferred in the range from 30 to 40 cm 3 /10 min, as this is the optimum between sagging and heat increase due to friction at the die upon preparing the blow molded container.
  • the composition in step a) comprises silicone oil in an amount of at least 75 ppm, and most preferred at least 100 ppm.
  • the composition of step a) comprises at most 1000 ppm of silicone oil, more preferably at most 800 ppm and most preferred at most 500 ppm.
  • silicone oil preferably PDMS is employed.
  • the composition in step a) comprise a semi-crystalline polyamide having as main building blocks epsilon- caprolactam and/or building blocks hexamethylene diamine and adipic acid, including PA-6, PA-66, PA6/66 and PA66/6 and blends thereof.
  • the blow-molded container according to the invention shows sagging times of between 900 and 1200 sec, which is favourable for blow molding.
  • the blow molded containers according to the invention also show a total energy of at least 40 J, preferably at least 50 J and more preferably at least 70 J, during an impact falling dart test as described below. Examples
  • composition is suitable for blow molding of containers according to the invention and also to be employed in the process according to the invention, if the following criteria are met:
  • a sagging time between about 900 to 1200 s to reach 785 mm from a capillary of a Rheograph 6000;
  • Blow molded containers with an L of 36 cm and W of 14 cm were prepared as test container with a wall thickness of 3.2 mm and from these containers plates with a dimension of 80x80x3.2mm were cut and were dried until constant weight in a vacuum stove at 80 °C.
  • Impact falling dart test at -40 °C was performed on the plates using the guidelines ISO 6603-2.
  • the diameter of the spherical falling dart was 20 mm and the mass of the falling dart was 23 kg.
  • the test speed was 4.4 m/sec. At least five plates were tested. Plates of each material had been placed in a -40 °C freezer overnight prior to testing.
  • the MVR of the composition was measured according to ISO 1 133 with a weight of 21.6 kg and at 275 °C prior to blow molding. MVR of a composition is steered by post condensation at 190 °C of the composition as listed in table 1 , which is a known process to a person skilled in the art.
  • the relative solution viscosity of the polyamide was measured using a solvent of 90 % formic acid and a solution of the polyamide at a concentration of 1 g in 100 ml in that solvent and measured at 25 °C, the same capillary viscometer being used for both measurements.
  • the relative solution viscosity (RSV) value is calculated from these measurements.
  • Sagging test was performed at 250 °C on dried pellets of a composition as described in Table 1 using a Rheograph 6000 having a capillary l/d 50/3 mm and a shear rate 2.1 1/s at a piston speed of 0.05 mm/sec. The time is recorded starting when the melt leaves the die head of the rheograph until the melt reaches a length of 78.5 cm as measured from the die head. This time is denoted as sagging in table 1 .
  • Example 1 fulfills the criteria as set above.
  • This composition shows a sagging time of between 900 and 1200 sec, a total energy of 1 15 J, which is well above 40J, and a good pinch line quality.
  • This composition is suitable for preparing blow molded containers according to the invention.
  • the blow molded test container exhibited good mechanical properties.
  • Comparative examples B and C show that if the MVR is very low due to extended post condensation time, the sagging time is too high, also resulting in a bad pinch line quality, which also indicates insufficient mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un récipient moulé par soufflage présentant une longueur L, une largeur W et une profondeur D telles que définies dans un système de coordonnées cartésiennes tridimensionnel, et préparé à l'aide d'une composition comprenant : au moins un polyamide semi-cristallin ; ii. au moins un agent antichoc dans une quantité comprise entre 1 % en poids et 50 % en poids ; iii. au moins une huile de silicone dans une quantité comprise entre 50 ppm et 1 000 ppm ; iv. au moins un agent de ramification dans une quantité comprise entre 0,01 % en poids et 6,0 % en poids ; v. au moins un stabilisant dans une quantité comprise entre 0,05 % en poids et 2,0 % en poids ; L étant au moins 75 cm, et L > 2W ≥ D, et l'indice de fluidité à chaud en volume de la composition étant dans la plage de 25 à 45 cm3/10 min, tel que mesuré selon la norme ISO 1133 avec 21,6 kg et 275 °C. Les % en poids et ppm sont indiqués par rapport à la quantité totale de composition. L'invention concerne également un procédé de préparation d'un récipient moulé par soufflage.
PCT/EP2015/066924 2014-07-25 2015-07-23 Récipient moulé par soufflage WO2016012558A1 (fr)

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EP14178526 2014-07-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944309A (zh) * 2020-09-24 2020-11-17 江苏金发科技新材料有限公司 一种可稳定成型加工的聚酰胺组合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321336A (en) * 1977-08-02 1982-03-23 Bayer Aktiengesellschaft High impact polyamide blends
WO2004092274A1 (fr) * 2003-04-14 2004-10-28 E.I. Dupont De Nemours And Company Composition polyamide pour articles moules par soufflage
WO2012076677A2 (fr) * 2010-12-09 2012-06-14 Dsm Ip Assets B.V. Revêtement intérieur pour réservoir de stockage de gaz

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321336A (en) * 1977-08-02 1982-03-23 Bayer Aktiengesellschaft High impact polyamide blends
WO2004092274A1 (fr) * 2003-04-14 2004-10-28 E.I. Dupont De Nemours And Company Composition polyamide pour articles moules par soufflage
WO2012076677A2 (fr) * 2010-12-09 2012-06-14 Dsm Ip Assets B.V. Revêtement intérieur pour réservoir de stockage de gaz

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111944309A (zh) * 2020-09-24 2020-11-17 江苏金发科技新材料有限公司 一种可稳定成型加工的聚酰胺组合物

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