WO2002024806A1 - Composition de matiere synthetique, son procede de production et son utilisation, notamment en tant qu'agent barriere - Google Patents

Composition de matiere synthetique, son procede de production et son utilisation, notamment en tant qu'agent barriere Download PDF

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Publication number
WO2002024806A1
WO2002024806A1 PCT/EP2001/010814 EP0110814W WO0224806A1 WO 2002024806 A1 WO2002024806 A1 WO 2002024806A1 EP 0110814 W EP0110814 W EP 0110814W WO 0224806 A1 WO0224806 A1 WO 0224806A1
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WO
WIPO (PCT)
Prior art keywords
polyvinyl alcohol
plastic composition
composition according
polyolefin
maleic anhydride
Prior art date
Application number
PCT/EP2001/010814
Other languages
German (de)
English (en)
Other versions
WO2002024806B1 (fr
Inventor
Matthias Gutweiler
Martin Steuer
Sven KÖHNEN
Robert W. Fuss
Original Assignee
Kuraray Specialtities Europe Gmbh
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Filing date
Publication date
Application filed by Kuraray Specialtities Europe Gmbh filed Critical Kuraray Specialtities Europe Gmbh
Publication of WO2002024806A1 publication Critical patent/WO2002024806A1/fr
Publication of WO2002024806B1 publication Critical patent/WO2002024806B1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • Plastic composition process for its production and its use, in particular as a barrier medium
  • the present invention relates to plastic compositions which, inter alia in a multilayer structure, have excellent properties in relation to gases and organic liquids, in particular fuels, in comparison with the barrier media available on the market today.
  • Compositions contain at least one plasticized polyvinyl alcohol and at least one polyethylene-maleic anhydride copolymer and, if appropriate, further plastics, extrusion aids, drying agents and antioxidants which can be processed into barrier media using conventional extrusion methods.
  • barrier media generally consist of a combination of different plastics, since one plastic alone cannot meet the high technical requirements placed on barrier media. Such requirements are, for example, break resistance, transparency, low weight, easy processing, good printability and sealability. For many applications, both in the food and in the technical field, today's barrier media must have a great barrier effect against oxygen, water, carbon dioxide, aroma and fragrance substances as well as organic liquids.
  • the barrier packaging available on the market today consists of at least three, but usually six or more, layers.
  • the plastics used mainly as so-called support layers are polyethylene (PE), polypropylene (PP), oriented polypropylene (OPP), polyethylene terephthalate (PET), polycarbonate (PC) and polystyrene (PS).
  • the actual barrier materials consisting of ethylene vinyl alcohol (EVOH), polyamide (PA) or polyvinylidene chloride (PVDC), are embedded in a kind of sandwich structure.
  • the barrier media can be produced by all methods known to the person skilled in the art, such as, for example, by co-extrusion, laminating, painting and coating, and by laminar technology.
  • sandwich structures are also produced, for example, which have polyamide (PA) or ethylene-vinyl alcohol (EVOH) as a barrier layer, which is enclosed between support layers made of polyethylene (PE) or polypropylene (PP).
  • PA polyamide
  • EVOH ethylene-vinyl alcohol
  • barrier media are used, for example, as menu trays, underfloor heating pipes, crop protection containers and fuel tanks.
  • the production of EVOH is complex and expensive.
  • adhesion promoters is necessary to bond the individual layers together.
  • the plastic foils are connected to one another using a suitable adhesive.
  • the foils are coated or coated in particular with PVDC.
  • PVDC has the disadvantage that it is thermally sensitive, contains chlorine and is difficult to recycle.
  • the barrier material PA is incorporated into PE during the extrusion, so that overlapping lamellae are created.
  • the use of an adhesion promoter is also necessary here.
  • the actual barrier effect is based on the lamellar structure in the PE matrix caused by the PA, in which the gases have to cover a greater diffusion path through the barrier layer than in the case of a material without a lamellar structure, but ultimately diffuse through the barrier medium.
  • Barrier media can also be produced by vapor deposition with aluminum or SiO x .
  • the aluminum or SiO x is evaporated on a suitable carrier film in a high vacuum.
  • coffee packaging is made by steaming a PET film with aluminum and subsequent coating with PE.
  • a disadvantage of the production by vapor deposition with aluminum is that cracks can easily occur due to mechanical stress, which reduce the barrier effect and on the other hand the transparency is lost. In addition, the process is generally very complex and expensive.
  • Barrier media can also be produced by fluorination and sulfonation.
  • blow molded articles are inflated with fluorine or H 2 S0 3 . This causes the gas to react with the surface of the plastic, creating the barrier layer. The barrier layer is thus on the side facing the ingredient.
  • the finest cracks, caused by stress have a disadvantageous effect on the barrier effect.
  • this manufacturing process requires a great deal of safety.
  • the barrier effect also depends heavily on the environmental conditions, e.g. Temperature, pressure and / or humidity.
  • EP-A-0 015 556 describes a process for producing a laminate material from a mixture which is a polyolefin, a second polymer which is incompatible with the polyolefin, selected from the group of polyamides and polyesters, and contains an alkyl carboxyl substituted polyolefin.
  • a formulation consisting of ethylene-vinyl alcohol copolymers with crystalline nylon and ionomeric and optionally usable amorphous nylon is described in WO 97/09380.
  • the ionomer is Copolymers of ethylene and carboxylic acid, which are then neutralized with metal ions.
  • US Pat. No. 5,939,158 describes a polymer built up in a laminar structure, which consists of the materials polyolefin, nylon, polyvinyl alcohol and a compatibilizer, which can be a mixture of two different alkyl carboxyl-substituted polyolefins or a small amount of a maleic anhydride-modified polyolefin, consists.
  • WO 90/12061 describes a formulation consisting of polyolefin and internally plasticized polyvinyl alcohol.
  • the formulation is prepared by mixing the polyolefin with the internally plasticized polyvinyl alcohol in the molten state using a material mixer equipped with a flat film nozzle.
  • the internally plasticized polyvinyl alcohol is a copolymer of vinyl alcohol and an ester of methacrylic acid and polyethylene glycol.
  • the polyvinyl alcohol used is partially saponified, with a degree of hydrolysis of 88%, and has a viscosity of 4 mPas.
  • the plasticizer to be used optionally with 1 to 15% by weight is glycerol.
  • WO 99/54400 discloses a formulation consisting of polyolefin and polyvinyl alcohol. Based on 100% by weight of polyolefin are 3 to 40% by weight of a high molecular weight compatibilizer (acrylic-containing copolymer) and / or 0.1 to 5% by weight of a low molecular weight compatibilizer (maleic anhydride) and 0.01 to 0.5% by weight .-% contain an initiator (peroxide compound). Based on 100% by weight of polyvinyl alcohol, the formulation contains 3 to 50% by weight of plasticizer (glycerol / water), 1 to 10% by weight of extrusion aid and 0.01 to 5% by weight of antioxidant.
  • plasticizer glycerol / water
  • antioxidant 0.01 to 5% by weight of antioxidant.
  • the formulation is prepared by first mixing a plasticizer, the extrusion aid and the antioxidant to the polyvinyl alcohol and then homogenizing in a mixer at more than 100 revolutions / minute for at least 5 minutes.
  • This polyvinyl alcohol composition is dried at 80 to 120 ° C for more than 3 hours.
  • the high molecular and low molecular compatibilizers and the initiator to a polyolefin in the mixer and also mixed under the same conditions as in the polyvinyl alcohol blend production.
  • the two polyvinyl alcohol and polyolefin blends thus produced are mixed together again in the mixer mentioned above, extruded using a twin-screw extruder and then granulated.
  • plastic composition which contains 30 to 99% by weight, preferably 50 to 80% by weight, of a plasticizer
  • Polyethylene and polypropylene are preferred as polyolefins, with polyethylene being particularly preferred.
  • the proportion of maleic anhydride in the polyolefin-maleic anhydride (MA) copolymers is 0.1 to 20% by weight, preferably 0.1 to 10% by weight.
  • the proportion of polyolefin in the copolymer is accordingly in the range from 80 to 99.9% by weight, preferably in the range from 90 to 99.9% by weight.
  • the particularly preferred polyethylene (PE) -maleic anhydride (MSA) copolymers have melt indexes which are preferably in the range from 0.3 to 10 g / 10 minutes.
  • All fully or partially hydrolyzed polymers of vinyl acetate can be used as polyvinyl alcohol. However, it is preferred to use completely saponified polyvinyl alcohols with a degree of hydrolysis of at least 98 mol%, particularly preferably at least 99 mol%.
  • the 4% by weight aqueous solution of the polyvinyl alcohol preferably has a viscosity of 3 to 50 mPas, particularly preferably 10 to 30 mPas (measured according to Höppler at 20 ° C.).
  • plasticizers or plasticizer mixtures which are compatible with polyvinyl alcohol and are suitable and known for plasticizing them can be used as plasticizers.
  • Preferred plasticizers are organic substances containing hydroxyl groups, such as, for example, glycols, polyhydric alcohols having 1 to 10 carbon atoms, trimethylolpropane, neopentyl glycol and fatty acid monoglycerides.
  • the proportion of plasticizer in the plasticized polyvinyl alcohol is preferably in the range from 5 to 50% by weight and particularly preferably in the range from 10 to 20% by weight. Internal plasticization of the polyvinyl alcohol is also possible.
  • the plasticizer-containing polyvinyl alcohol may also contain other additives.
  • Additives which can preferably be silica, thermoplastic resins, both liquid and powder, e.g. as a dispersion or dispersion powder, particularly preferably homo- or copolymers of vinyl acetate, maleic esters, acrylic esters and long-chain and / or branched carboxylic esters being suitable as comonomer components, wax-like substances, fatty acid esters and their derivatives, and / or commercially available oxidation stabilizers.
  • a particularly preferred plasticizer-containing polyvinyl alcohol has the following composition: 50 to 99% by weight polyvinyl alcohol, 5 to 25% by weight glycerin, 2 to 8% by weight water, 0 to 10% by weight stearic acid, 0 to 5% by weight Aerosil and 0 to 4% by weight. -% polyvinyl acetate.
  • composition according to the invention can also contain up to 50% by weight, preferably up to 5% by weight, based on the total composition of polyolefins, preferably polyethylene or polypropylene and particularly preferably polyethylene.
  • a plastic composition which essentially consists of the plasticized polyvinyl alcohol and the polyolefin-maleic anhydride copolymer.
  • the invention also relates to a method for producing this composition.
  • the polyvinyl alcohol is first plasticized, then this softener-containing polyvinyl alcohol is optionally mixed with the polyolefin-maleic anhydride copolymer and compounded and granulated using an extruder.
  • the process according to the invention for the polyethylene-maleic anhydride copolymer to be used with particular preference is described in detail below.
  • the plasticizer-containing polyvinyl alcohol and the polyethylene-maleic anhydride copolymer are preferably used in granular form.
  • the two components are optionally mixed with one another and compounded in an extruder at melt temperatures of 170 to 240 ° C., preferably 210 to 230 ° C., and then granulated.
  • the granulate is characterized by good processability with various non-polar plastics, such as polyethylene. Because of this good Properties, the composition according to the invention can be used in a large number of applications.
  • the granules obtained can therefore be processed together with other plastics to form a shaped body by all processes known to the person skilled in the art, preferably by extrusion and particularly preferably by co-extrusion.
  • the subject of the present application is therefore also a molded article containing the plastic composition according to the invention.
  • the shaped body preferably contains at least one layer which essentially consists of the composition according to the invention.
  • Such a shaped body is distinguished, inter alia, by good barrier properties against gases and organic liquids, such as fuels, and also by its good processability.
  • the molded body according to the invention can be used as a barrier medium in a large number of applications, for example in single-layer or multilayer structures in the packaging sector.
  • the molded body is preferably used for the production of fuel tanks.
  • the shaped body according to the invention When using the shaped body according to the invention as a barrier medium in multilayer structures, up to two layers can be saved compared to conventional barrier media (EVOH, PA), since the composition according to the invention itself has sufficient adhesion to the carrier material and therefore no adhesion promoter is required.
  • EVOH conventional barrier media
  • GT 1000 parts by weight
  • polyvinyl alcohol 175 GT glycerol, 50 GT water and 6 GT ® Aerosil R 972 are used.
  • the polyvinyl alcohol used is saponified to 98 mol%.
  • a 4% aqueous solution has a viscosity of 10 mPas at 20 ° C.
  • the plastification takes place in a Papenmeier mixer with heatable and coolable double wall and a special stirrer system. The number of revolutions is continuously adjustable.
  • Example 1b The granules obtained in Example 1b become one in a Schwabenthan press
  • the film has the following barrier properties:
  • GT parts by weight
  • polyvinyl alcohol 25 GT ® Mowilith powder DM 117 P, 2.5 GT stearic acid, 180 GT glycerol, 50 GT water and 6 GT ® Aerosil R 972 were used.
  • the polyvinyl alcohol used is saponified to 99 mol%.
  • a 4% aqueous solution has a viscosity of 15 mPas at 20 ° C.
  • the plastification takes place in a Papenmeier mixer with heatable and coolable double wall and a special stirrer system. The number of revolutions is continuously adjustable.
  • Example 2b The granules obtained in Example 2b are processed into a film using a Göttfert blown film extruder, Buchen / Odenwald.
  • the cylinder diameter of the extrusiometer is 30 mm, its length 25 D.
  • the compression ratio of the core-progressive three-zone screw without mixing part and additional compression elements is 1: 2.5.
  • the die head diameter is 30 mm, the gap width is 0.6 mm.
  • the processing temperatures are between 200 and 220 ° C.
  • the film has the following barrier properties:
  • GT parts by weight
  • polyvinyl alcohol 25 GT ® Mowilith powder DM 117 P, 2.5 GT stearic acid, 180 GT glycerol, 50 GT water and 6 GT ® Aerosil R 972 were used.
  • the polyvinyl alcohol used is saponified to 99 mol%.
  • a 4% aqueous solution has a viscosity of 15 mPas at 20 ° C.
  • the plastification takes place in a Papenmeier mixer with heatable and coolable double wall and a special stirrer system. The number of revolutions is continuously adjustable.
  • Example 3b The granules obtained in Example 3b are processed into a film in the same way as in Example 2c using a Göttfert blown film extruder.
  • the film has the following barrier properties:
  • a film is produced from ethylene-vinyl alcohol (EVOH) copolymer using a Schwabenthan press.
  • the film has the following barrier properties: Oxygen permeability at 23 ° C / 50% rel. Humidity: 0.003 [cm 3 x mm] / [m 2 xdx bar] Fuel permeability according to CEC legislative fuel RF-08-A-85 at 40 ° C in contact with the liquid fuel: ⁇ 0.0006 [gx mm] / [m 2 xd]

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Laminated Bodies (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de matière synthétique, constituée de 30 à 99 % en poids d'un alcool polyvinylique plastifiant et de 1 à 70 % en poids d'un copolymère d'anhydride d'acide maléique polyoléfinique. La présente invention concerne également un procédé de production et l'utilisation de cette composition, notamment en tant qu'agent barrière pour réservoirs de carburant.
PCT/EP2001/010814 2000-09-20 2001-09-19 Composition de matiere synthetique, son procede de production et son utilisation, notamment en tant qu'agent barriere WO2002024806A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000146619 DE10046619A1 (de) 2000-09-20 2000-09-20 Kunststoff-Zusammensetzung, Verfahren zu deren Herstellung sowie deren Verwendung, insbesondere als Barrieremedium
DE10046619.2 2000-09-20

Publications (2)

Publication Number Publication Date
WO2002024806A1 true WO2002024806A1 (fr) 2002-03-28
WO2002024806B1 WO2002024806B1 (fr) 2002-09-19

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PCT/EP2001/010814 WO2002024806A1 (fr) 2000-09-20 2001-09-19 Composition de matiere synthetique, son procede de production et son utilisation, notamment en tant qu'agent barriere

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DE (1) DE10046619A1 (fr)
WO (1) WO2002024806A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10207592A1 (de) * 2002-02-22 2003-09-11 Kuraray Specialities Europe Kunststoff-Formkörper, die wasserfeste Beschichtungen als Gasbarrieren aufweisen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990012061A1 (fr) * 1989-04-13 1990-10-18 Neste Oy Materiau etanche aux gaz
EP0560369A2 (fr) * 1992-03-13 1993-09-15 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Composition de résine et sa production
EP0571074A2 (fr) * 1992-05-21 1993-11-24 Morton International, Inc. Procédé pour préparer une composition orientée à base d'un copolymère d'éthylène vinyl alcohol et produit orienté préparé à partir de cette composition
EP0584590A1 (fr) * 1992-08-03 1994-03-02 Air Products And Chemicals, Inc. Greffage réactif par extrusion en fusion de mélanges thermoplastiques d'alcool de polyvinyle et de polyoléfine
EP0693529A1 (fr) * 1994-07-21 1996-01-24 Sumitomo Chemical Company, Limited Composition de résine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990012061A1 (fr) * 1989-04-13 1990-10-18 Neste Oy Materiau etanche aux gaz
EP0560369A2 (fr) * 1992-03-13 1993-09-15 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Composition de résine et sa production
EP0571074A2 (fr) * 1992-05-21 1993-11-24 Morton International, Inc. Procédé pour préparer une composition orientée à base d'un copolymère d'éthylène vinyl alcohol et produit orienté préparé à partir de cette composition
EP0584590A1 (fr) * 1992-08-03 1994-03-02 Air Products And Chemicals, Inc. Greffage réactif par extrusion en fusion de mélanges thermoplastiques d'alcool de polyvinyle et de polyoléfine
EP0693529A1 (fr) * 1994-07-21 1996-01-24 Sumitomo Chemical Company, Limited Composition de résine

Also Published As

Publication number Publication date
DE10046619A1 (de) 2002-03-28
WO2002024806B1 (fr) 2002-09-19

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