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WO1990012063A1 - Materiau etanche aux gaz - Google Patents

Materiau etanche aux gaz Download PDF

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Publication number
WO1990012063A1
WO1990012063A1 PCT/FI1990/000107 FI9000107W WO9012063A1 WO 1990012063 A1 WO1990012063 A1 WO 1990012063A1 FI 9000107 W FI9000107 W FI 9000107W WO 9012063 A1 WO9012063 A1 WO 9012063A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
polyolefin
acid
sealed material
material according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/FI1990/000107
Other languages
English (en)
Inventor
Hanneli Seppänen
Christer BERGSTRÖM
Leila Kettunen
Helge Lindström
Maria Stjernberg
Olli Tuominen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Neste Oyj
Original Assignee
Neste Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FI891757A external-priority patent/FI86875C/fi
Priority claimed from FI891756A external-priority patent/FI86874C/fi
Application filed by Neste Oyj filed Critical Neste Oyj
Publication of WO1990012063A1 publication Critical patent/WO1990012063A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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

  • the present invention concerns a gas-sealed material and products containing gas-sealed material.
  • the invention concerns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide, and products containing the same.
  • Polyolefins are widely used, for instance, in packaging industry in manufacturing various film products. Advantages of polyolefins are in particular appropriate strength and water resistance properties. Among the drawbacks may be mentioned permeability to certain gases and liquids, concerning particularly oxygen and hydrocarbon dissolvents.
  • multiple layer film 20 structures in which materials of different layers are selected for a given purpose. Therefore, such multiple layer structures may contain layers which form a good barrier against gases, such as oxygen, and layers which provide other properties for the product, such as strength properties.
  • multiple layer structures may 25 contain- other layers which generate, for instance, adhesion between different layers. Products of this kind are, however, expensive to manufacture.
  • Polyvinyl alcohol is one of such polymers which has a low oxygen 30 permeability property. Said property has most often been utilized in olefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers. It is also known in the art to manufacture products containing polyolefin and polyvinyl alcohol in the form of mixtures, which have a low oxygen permeability and which therefore 35 a re exceedingly appropriate for manufacturing e.g. packaging films. In the Finnish patent application No. 87-5772 is disclosed a mixture of polyolefin and polyvinyl alcohol, moreover containing optionally 1 plasticizers. When polyolefin and polyvinyl alcohol are mixed in molten state, a mixture is obtained which is composed of two phases, a continuous phase and a dispersed phase, when the diameter of the particles in the dispersed phase is small enough, totally transparent
  • the mixing is usually carried out in a separate compounding phase prior to the extrusion of the end product.
  • the object of the present invention is a material containing polyolefin, polyvinyl alcohol, and polyamide, in which the moisture sensitivity of the product regarding oxygen sealing is reduced, the lightness of the product has increased, and the need for plasticizers
  • the invention concerns a gas-sealed material containing polyolefin, vinyl alcohol polymer, and polyamide.
  • the gas-sealed material of the invention is characterized in that it is produced by mixing in molten state 3 to 60 per cent by weight of polyolefin, and
  • internally plasticized vinyl alcohol polymer refers to a vinyl alcohol polymer which contains polyglycol groups (polyether
  • plasticizer groups are connected into a chain by copolymerizing, grafting or by means of reactive compounding.
  • One such internally plasticized polyvinyl alcohol is Vinex polymer (trade name, Air Products and Chemicals Inc.) , in which for comonomer is 5 used an ester of methacrylic acid and of polyethylene glycol.
  • Said internally plasticized vinyl alcohol polymers may be manu- 1 factured, for instance in the manner as disclosed in the US. patent No. 4,709,999. Said patent presents that the product is provided with good oxygen sealing and that it is appropriate for cast, in ⁇ jection moulding and extrusion products, and that it is characterized
  • Q polyamide mixture of the invention is advantageously such in which in the poly(alkyleneoxy)ester derivative for use as a comonomer the alkylene of the alcohol component is an ethylene or propylene, and the acid component is an acrylic acid or methacrylic acid.
  • Said modified vinyl alcohol polymers may be manufactured, for instance, by poly- ⁇ J5 merizing vinyl acetate monomer and poly(alkyleneoxy)aerylate co ⁇ monomer, and hydrolyzing the copolymer thus obtained in order to produce an internally plasticized vinyl alcohol polymer.
  • the quantity of the internally plasticized vinyl alcohol polymer in 0 the polyethylene-polyvinyl alcohol-polyamide mixture of the invention may be in the range from 10 to 96 per cent by weight, preferably in the range of from 30 to 60 per cent by weight. In some instances, it may be preferable to substitute part of the internally plasticized vinyl alcohol polymer used in the gas-sealed material for unmodified 5 polyvinyl al ⁇ hol if the purpose of the product allows.
  • the polyolefin in a gas-sealed material of the invention may be based on homopolymers or copolymers of the olefins. Therefore, it may be low density polyethylene (LDPE) , medium density polyethylene 0 (MDPE) or high density polyethylene (HDPE) , polypropylene, or poly- butene.
  • LDPE low density polyethylene
  • MDPE medium density polyethylene 0
  • HDPE high density polyethylene
  • the polyolefin may also be a copolymer of ethylene together with other olefins, such as propylene, butene, hexene and octene.
  • the polyolefin may also be an olefin-ester copolymer, such as ethylene-vinyl acetate copolymer, ethylene-acrylate-ester copolymer, 5 or ethylene-methacrylate ester copolymer, or it may be a thermoplastic olefin-based elastomer, such as EP or EPD rubber.
  • the polyolefin in the process according to the invention may also be a homopolymer or a copolymer of the above-mentioned olefins which has been modified with the aid of carboxylic acid. To such a modified olefin polymer is copolymerized or grafted 0.1 to 10 per cent by weight of carboxylic acid.
  • the carboxylic acid may comprise any unsaturated carboxylic acid or carboxylic acid anhydride which can be grafted or copolymerized in polyolefin.
  • examples of such acids are, for instance, acrylic acid, methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, sorbic acid, and anhydrides of the afore-mentioned acids. In grafting or in copolymerizing one or several above acids may be used.
  • the polyolefin grafted or copolymer ⁇ ized with carboxylic acid may also be a mixture containing a poly ⁇ olefin modified in the manner described above, and un unmodified polyolefin.
  • the quantity of the polyolefin in the gas-sealed material of the invention may be in the range 1 to 99 per cent by weight, but preferably in the range from 30 to 60 per cent by weight of the quantity of the entire mixture.
  • a third component in a gas-sealed material of the invention is amorphous polyamide.
  • the quantity of amorphous polyamide in a material of the invention may be selected from the range 1 to 50 per cent by weight.
  • the amorphous polyamide enhances the viscosity and deep-drawing properties of the mixture of polyolefin and polyvinyl alcohol co ⁇ polymer.
  • the gas-sealed polyolefin/PVA/PA mixture of the invention can be manufactured mixing the polyolefin component, vinyl alcohol/copolymer component, and polyamide component in a melt mixer simultaneously as a dry mixture, premixed in solid or in molten state, or then various components are added separately.
  • various products may be prepared by combining the mixture with polyolefins, other plastics or other materials, such as fibre-based materials.
  • Multiple layer products may be manufactured by coextrusion, (co)extrusion
  • products containing a gas-sealed material of the invention e.g. films, moulded-blown bottles and containers, plates, tubes, injection
  • P02 - LT.DPE linear low density polyethylene
  • melt index 0.5 g/10 min (190°C)
  • PVA2 - polyvinyl alcohol, viscosity 4, hydrolysis degree 88%
  • PA1 amorphous polyamide, degree of crystallization
  • PA2 - polyamide 6 ⁇ J5 PA3 - polyamide 11 PA4 - polyamide 12
  • Polyolefin/PVA/polyamide mixtures of the invention were prepared by 25 mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
  • the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 220 to 215 to 215 to 210.
  • the production rate was 10 kilograms per hour.
  • the thicknesses of the obtained films were 150 to 200 ⁇ m.
  • the com ⁇ pounds thereof are presented in the accompanying Table 1 A.
  • the properties of the films are presented in the accompanying Table 1 B.
  • the oxygen permeability values of the films are calculated for 25 ⁇ m 35 thickness.
  • the lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab. TABLE ]L A
  • the quantity of polyvinyl alcohol includes 4.5% glycerol of the PVA quantity.
  • Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
  • the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 220 to 215 to 210.
  • the production rate was 10 kilograms per hour.
  • the thicknesses of the obtained films were 140 to 190 ⁇ m.
  • the com- pounds thereof are presented in the accompanying Table 2 A.
  • the properties of the films are presented in the accompanying Table 2 B.
  • the oxygen permeability values of the films are calculated for 25 ⁇ m thickness.
  • the lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
  • the quantity of polyvinyl alcohol includes 4.5% glycerol of the PVA quantity.

Landscapes

  • 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)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention se rapporte à un matériau étanche aux gaz, qui contient une polyoléfine, un alcool polyvinylique et un polyamide. On fabrique un tel matériau en mélangeant à l'état de fusion 3 à 60 % en poids d'une polyoléfine, 10 à 96 % en poids d'un polymère d'alcool vinylique intérieurement plastifié, et 1 à 50 % en poids d'un polyamide amorphe.
PCT/FI1990/000107 1989-04-13 1990-04-11 Materiau etanche aux gaz Ceased WO1990012063A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FI891757A FI86875C (fi) 1989-04-13 1989-04-13 Gastaett material, som innehaoller invaendigt mjukgjord polyvinylalkohol
FI891756 1989-04-13
FI891756A FI86874C (fi) 1989-04-13 1989-04-13 Gastaett material, som innehaoller invaendigt mjukgjord polyvinylalkohol
FI891757 1989-04-13

Publications (1)

Publication Number Publication Date
WO1990012063A1 true WO1990012063A1 (fr) 1990-10-18

Family

ID=26158539

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1990/000107 Ceased WO1990012063A1 (fr) 1989-04-13 1990-04-11 Materiau etanche aux gaz

Country Status (5)

Country Link
EP (1) EP0423270A1 (fr)
JP (1) JPH04500538A (fr)
AU (1) AU5417190A (fr)
CA (1) CA2032122A1 (fr)
WO (1) WO1990012063A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0483695A3 (en) * 1990-10-29 1992-09-23 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Resin composition and use thereof
EP0519617A1 (fr) * 1991-06-19 1992-12-23 Chevron Research And Technology Company Mélanges de polyoléfine, polyamide et un copolymère d'éthylène modifié
EP0519616A1 (fr) * 1991-06-19 1992-12-23 CHEVRON U.S.A. Inc. Mélange homogène d'une polyoléfine modifiée, d'un polymère oxidable et d'un sel métallique pour l'élimination d'oxygène
WO1999048974A1 (fr) * 1998-03-24 1999-09-30 E.I. Du Pont De Nemours And Company Articles stratifies ameliores et realises a partir d'une polyolefine et d'un melange de nylon/polyalcool de vinyle, et procedes associes
WO2005042639A1 (fr) * 2003-11-03 2005-05-12 Kuraray Specialities Europe Gmbh Procede de production de corps moules en polyamide-alcool polyvinylique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU631205B2 (en) * 1989-04-13 1992-11-19 Neste Oy Gas-sealed material containing polyolefin, polyvinyl alcohol and polyamide

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0152180A2 (fr) * 1984-02-08 1985-08-21 QUANTUM CHEMICAL CORPORATION (a Virginia corp.) Alliages polymères à base d'alcool polyvinylique
EP0247326A2 (fr) * 1986-03-31 1987-12-02 Kuraray Co., Ltd. Compositions de résine, laminés et copolymères séquencés comme composants de celles-ci
EP0255733A2 (fr) * 1986-08-08 1988-02-10 Air Products And Chemicals, Inc. Copolymères d'acétate de vinyle et de poly(alkylèneoxy)acrylates
EP0275900A2 (fr) * 1987-01-16 1988-07-27 Air Products And Chemicals, Inc. Copolymères d'acétate de vinyle et d'acrylates
EP0280455A2 (fr) * 1987-02-25 1988-08-31 Du Pont Canada Inc. Procédé pour le moulage par injection d'articles ayant des propriétés de barrières
EP0305146A1 (fr) * 1987-08-24 1989-03-01 E.I. Du Pont De Nemours And Company Mélanges de copolymère éthylène-alcool vinylique et de polyamide amorphe et conteneurs multi-couches préparés à partir de ceux-ci
EP0309095A1 (fr) * 1987-08-24 1989-03-29 E.I. Du Pont De Nemours And Company Compositions barrières basées sur un polyamide amorphe et un copolymère éthylène-alcool vinylique
EP0333471A2 (fr) * 1988-03-17 1989-09-20 E.I. Du Pont De Nemours And Company Produits laminaires d'une polyoléfine et d'un mélange d'un polyamide et d'un alcool polyvinylique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0152180A2 (fr) * 1984-02-08 1985-08-21 QUANTUM CHEMICAL CORPORATION (a Virginia corp.) Alliages polymères à base d'alcool polyvinylique
EP0247326A2 (fr) * 1986-03-31 1987-12-02 Kuraray Co., Ltd. Compositions de résine, laminés et copolymères séquencés comme composants de celles-ci
EP0255733A2 (fr) * 1986-08-08 1988-02-10 Air Products And Chemicals, Inc. Copolymères d'acétate de vinyle et de poly(alkylèneoxy)acrylates
EP0275900A2 (fr) * 1987-01-16 1988-07-27 Air Products And Chemicals, Inc. Copolymères d'acétate de vinyle et d'acrylates
EP0280455A2 (fr) * 1987-02-25 1988-08-31 Du Pont Canada Inc. Procédé pour le moulage par injection d'articles ayant des propriétés de barrières
EP0305146A1 (fr) * 1987-08-24 1989-03-01 E.I. Du Pont De Nemours And Company Mélanges de copolymère éthylène-alcool vinylique et de polyamide amorphe et conteneurs multi-couches préparés à partir de ceux-ci
EP0309095A1 (fr) * 1987-08-24 1989-03-29 E.I. Du Pont De Nemours And Company Compositions barrières basées sur un polyamide amorphe et un copolymère éthylène-alcool vinylique
EP0333471A2 (fr) * 1988-03-17 1989-09-20 E.I. Du Pont De Nemours And Company Produits laminaires d'une polyoléfine et d'un mélange d'un polyamide et d'un alcool polyvinylique

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0483695A3 (en) * 1990-10-29 1992-09-23 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Resin composition and use thereof
EP0519617A1 (fr) * 1991-06-19 1992-12-23 Chevron Research And Technology Company Mélanges de polyoléfine, polyamide et un copolymère d'éthylène modifié
EP0519616A1 (fr) * 1991-06-19 1992-12-23 CHEVRON U.S.A. Inc. Mélange homogène d'une polyoléfine modifiée, d'un polymère oxidable et d'un sel métallique pour l'élimination d'oxygène
US5641825A (en) * 1991-06-19 1997-06-24 Chevron Chemical Company Oxygen scavenging homogeneous modified polyolefin-oxidizable polymer-metal salt blends
WO1999048974A1 (fr) * 1998-03-24 1999-09-30 E.I. Du Pont De Nemours And Company Articles stratifies ameliores et realises a partir d'une polyolefine et d'un melange de nylon/polyalcool de vinyle, et procedes associes
WO2005042639A1 (fr) * 2003-11-03 2005-05-12 Kuraray Specialities Europe Gmbh Procede de production de corps moules en polyamide-alcool polyvinylique

Also Published As

Publication number Publication date
CA2032122A1 (fr) 1990-10-14
JPH04500538A (ja) 1992-01-30
AU5417190A (en) 1990-11-05
EP0423270A1 (fr) 1991-04-24

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