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WO1991001347A1 - Interpolymere de chlorure de vinylidene - Google Patents

Interpolymere de chlorure de vinylidene Download PDF

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Publication number
WO1991001347A1
WO1991001347A1 PCT/US1989/003117 US8903117W WO9101347A1 WO 1991001347 A1 WO1991001347 A1 WO 1991001347A1 US 8903117 W US8903117 W US 8903117W WO 9101347 A1 WO9101347 A1 WO 9101347A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinylidene chloride
amount
mixture
percent
total weight
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/US1989/003117
Other languages
English (en)
Inventor
Stephen R. Betso
Duane F. Foye
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to KR1019910700282A priority Critical patent/KR0151109B1/ko
Priority to EP19890911512 priority patent/EP0434763A4/en
Priority to PCT/US1989/003117 priority patent/WO1991001347A1/fr
Priority to JP1510629A priority patent/JPH04500829A/ja
Publication of WO1991001347A1 publication Critical patent/WO1991001347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride

Definitions

  • the present invention relates to a vinylidene chloride interpolymer possessing an improved combination of properties. Specifically, this invention relates to an improved barrier resin comprising a mixture of vinylidene chloride interpolymer and magnesium hydroxide, which resin has good clarity and, after being subject to elevated processing temperatures, good color characteristics.
  • Resins of vinylidene chloride interpolymers are well-known in the prior art.
  • vinylidene chloride interpolymers have been produced by an emulsion or suspension polymerization process. Both emulsion and suspension polymerization processes typically produce an aqueous dispersion of polymer particles having a relatively small particle diameter. The polymer particles are recovered from the aqueous dispersion by drying or other means for removing a majority of the aqueous phase.
  • the practice has been to extrude the vinylidene chloride interpolymer directly from the form in which it is recovered.
  • such compounds are fabricated mainly from vinylidene chloride interpolymers and an adequate amount of modifiers such as stabilizers, plasticizers, etc.
  • modifiers such as stabilizers, plasticizers, etc.
  • the melt viscosity of the resin is so high that the load on the extruder screw is too large and the extruded compound is subject to thermal decomposition and discoloration due to the close proximation of the compound's thermal decomposition point and melting point.
  • the decomposed interpolymer may generate an undesirable level of carbon contamination in the extrudate, which could have an effect upon the gas barrier of the extrudate.
  • such interpolymers typically have extremely poor extrudability.
  • the present is a process for improving the clarity of a thermally
  • 15 sensitive resin comprising the step of blending into a generally homogeneous mixture, a vinylidene chloride interpolymer and a quantity of a magnesium hydroxide in an amount of from 0.01 to 5 weight percent of the total monomer mixture, excluding a process which comprises the
  • a vinylidene chloride interpolymer and a combination of additives which comprises an extrusion aid selected from the group consisting of oxidized polyethylene; oxidized p .- polypropylene; or mixtures thereof, in an amount of from about 0.01 to about 0.05 weight percent; an ethylene- vinyl acetate copolymer present in an amount of from about 0.01 to about 2 weight percent; a paraffin wax present in an amount of from about 0.005 to about 1
  • the present invention is a composition
  • a composition comprising a generally homogeneous mixture of a vinylidene chloride interpolymer and magnesium hydroxide in an amount of from 0.01 to 5 weight percent, based on the total weight of the mixture.
  • Vinylidene chloride interpolymers suitable for use in the present invention are those vinylidene chloride interpolymers formed from vinylidene chloride and an amount of one or more monoethylenically unsaturated monomer copolymerizable with vinylidene chloride.
  • the vinylidene chloride interpolymers have polymerized therein vinylidene chloride-in an amount of from 40 to 98 weight percent, beneficially from 50 to 96 weight percent, and desirably from 60 to 94 weight percent, based on total weight of the vinylidene chloride interpolymer.
  • the vinylidene chloride interpolymer comprises one or more monoethylenically unsaturated monomer copolymerizable with vinylidene chloride.
  • the amount of monoethylenically unsaturated monomer is suitably from 60 to 2 weight percent, beneficially from 50 to 4 weight percent, and desirably from 40 to 6 weight percent, based on total weight of the vinylidene chloride interpolymer.
  • Monoethylenically unsaturated monomers suitable for use in the present invention include vinyl chloride, alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, and methacrylonitrile, and the like.
  • the ethylenically unsaturated monomers are desirably selected from the group consisting of vinyl chloride, alkyl acrylates, and alkyl methacrylates, the alkyl acrylates and alkyl methacrylates having from 1 to 8 carbon atoms per alkyl group.
  • the alkyl acrylates and alkyl methacrylates preferably have from 1 to 4 carbon atoms per alkyl group.
  • the alkyl acrylates and alkyl methacrylates are most preferably selected from the group consisting of methylacrylates, ethylacrylates, and methyl methacrylates.
  • the vinylidene chloride interpolymers suitable for use in the present invention are well-known in the prior art.
  • the vinylidene chloride interpolymer is generally formed through an emulsion or suspension polymerization process. Exemplary of such processes are U.S. Patents 2,558,728; 3,007,903; 3,642,743; and 3,879,359; and the methods described by R. A. Wessling, in Polvvinylidene Chloride, Gordon and Breach Science Publishers, New York, 1977, Chapter 3.
  • the monomeric materials are emulsified or suspended in an aqueous phase.
  • the aqueous phase contains a polymerization initiator and a surface active agent capable of emulsifying or suspending the monomeric materials in the aqueous phase.
  • the polymerization of the monomeric materials is usually carried out with heating and agitation.
  • the aqueous phase is the majority phase in the resulting suspension or emulsion of vinylidene chloride interpolymer.
  • the resultant polymeric material is vacuum stripped. Thereafter, the slurry is cooled down, unloaded and dewatered, and the resin is collected and further dried.
  • One aspect of the present invention concerns a process for improving the clarity of the above described vinylidene chloride interpolymer.
  • the process comprises blending the vinylidene chloride interpolymer with magnesium hydroxide.
  • j- Magnesium hydroxide is suitably blended with the vinylidene chloride interpolymer in an amount of from 0.01 to 5 weight percent of stabilizer.
  • the stabilizer is blended with the vinylidene chloride interpolymer in an amount of from
  • the stabilizer is blended with the vinylidene chloride interpolymer in an amount of from 0.5 to 2 weight percent of stabilizer.
  • additives may be added to the compatibilized blends of the present invention. Additive type and amount thereof will depend upon several factors. One factor is the intended use of the blends. A second factor is tolerance of the blends for
  • Additives which may be incorporated into the mixture of the present invention are selected from the group consisting of plasticizers, heat stabilizers,
  • a preferred combination of additives has been -,j- found to provide uniquely beneficial results when the mixture of vinylidene chloride interpolymer and magnesium hydroxide is formulated into a pellet.
  • the preferred combination of additives comprises the following components.
  • a first additive is selected from the group consisting of oxidized polyethylene; oxidized polypropylene; or mixtures thereof.
  • a preferred first additive is Allied 629A, an oxidized polyethylene commercially available from Allied Corp. The first additive is present in an amount between 0.01 to 0.5 weight percent, based on the total
  • a second additive is ethylene- vinyl acetate copolymer.
  • a preferred second additive is EVA 3180, an ethylene-vinyl acetate copolymer commericially available from E. I. DuPont Demours Co. -
  • the second additive is present in an amount between about 0.01 to about 2 weight percent, based on the total weight of the mixture.
  • a third additive is paraffin wax.
  • a preferred third additive is Bohler 1421, a paraffin wax commercially available from Bohler 0 Industries.
  • the third additive is present in an amount between about 0.005 and about 1, based on the total weight of the mixture.
  • a fourth additive is epoxidized oils or resins.
  • a preferred fourth additive is Vikoflex 7177, an epoxidized oil commercially available from the 5 Viking Chemical Company. The fourth additive is present in an amount of between 0.1 to 3 weight percent, based on the total weight of the mixture.
  • Blending of the vinylidene chloride 0 interpolymer, the magnesium hydroxide, and any other additives can be accomplished by using conventional melt processing, as well as dry blending techniques.
  • melt processing must be accomplished at a temperature below that at which decomposition of the vinylidene chloride interpolymer becomes significant.
  • Conventional melt processing equipment which may be used includes heated two-roll compounding mills, Brabender mixers, Banbury mixers, single screw extruders, twin screw extruders, and the like. Desirable results are obtained when an extruder, either single screw or twin screw, is used for melt blending the vinylidene chloride interpolymer and the magnesium hydroxide.
  • Suitable dry blending equipment includes Hobart mixers, Welex mixers, Henschel High Intensity mixers, and the like.
  • the mixture of vinylidene chloride interpolymer and magnesium hydroxide is then extruded.
  • the mixture is physically blended and then melt processed into any suitable final product.
  • the mixture of vinylidene chloride interpolymer and .magnesium hydroxide may suitably be pelletized.
  • Methods of forming the mixture into pellets are well-known to those skilled in the art. Any method capable of forming the mixture into pellets is suitable for use in the present invention.
  • the terms "pellet” or “pellets” refer to particles having a minimum cross- sectional dimension of at least 1/32 inch, preferably of at least 1/16 inch, and most preferably of at least 1/8 inch, said pellets suitably have a maximum cross- sectional dimension of at least 1/2 inch, preferably of at least 3/8 inch, and most preferably of at least 1/4 inch.
  • Exemplary of a method suitable for use in forming the pellets of the mixture are extrusion through a strand die and pelletization by chopping the extruded strand into pellets.
  • the process and composition according to the present invention improves the clarity of the vinylidene chloride interpolymer and allows for the satisfactory extrusion of vinylidene chloride interpolymer pellets formed therefrom.
  • the pellets are considered to possess "improved extrudability" when the mixture of vinylidene chloride interpolymer and magnesium hydroxide can be formed into a pellet which possesses less carbon contamination and less discoloration than a pellet formed from the vinylidene chloride interpolymer alone.
  • the process of the present invention can be used to form a variety of films or other articles.
  • the films and articles are fabricated with conventional coextrusion, e.g, feedblock coextrusion, multimanifold die coextrusion, or combinations of the two; injection molding; extrusion molding; and lamination techniques.
  • Articles formed therefrom include blown and cast, mono and multilayer, films; rigid and foam sheet; tubes; pipes; rods; fibers; and various profiles.
  • Lamination techniques are particularly suited to produce multi-ply sheets.
  • specific laminating techniques include fusion, i.e., whereby self-sustaining lamina are bonded together by applications of heat and pressure; wet combining, i.e., whereby two or more plies are laminated using a tie coat adhesive, which is applied wet, the liquid driven off, and combining by subsequent pressure laminating in one continuous process; or by heat reactivation, i.e., combining a precoated film with another film by heating and reactivating the precoat adhesive so that it becomes receptive to bonding after subsequent pressure laminating.
  • Exemplary articles include rigid containers used for the preservation of food, drink, medicine and other perishables. Such containers should have good mechanical properties, as well as low gas permeabilities to, for example, oxygen, carbon dioxide, water vapor, odor bodies or flavor bodies, hydrocarbons or agricultural chemicals. Most organic polymers such as the polyolefins, styrene polymers and the like, by themselves, do not possess sufficient resistance to transmission of atmospheric gases and vapors. Consequently, multilayer sheet structures employed in packaging materials have organic polymer skin layers laminated on each side of a vinylidene chloride interpolymer barrier layer, generally with glue layers used to promote adhesion between the barrier layer and dissimilar material layers.
  • a vinylidene chloride interpolymer is formed through a suspension polymerization process.
  • the vinylidene chloride interpolymer is formed from a monomer mixture comprising about 80 weight percent vinylidene chloride and about 20 weight percent vinyl chloride, based on total monomer mixture weight.
  • the vinylidene chloride interpolymer is dry c blended into a generally homogeneous mixture with various quantities of magnesium hydroxide as shown in Table 1 below.
  • the magnesium hydroxide is commercially available from Kyowa Chemical Company, under the trade designation Kisuma 5B.
  • the powdery mixtures are formed 10 by dry blending the two components in a Hobart mixer, for a period of approximately one hour.
  • the mixtures are extruded through a 3/4" extruder having a length to diameter ratio of 20/1.
  • the extruder has the following set temperatures: (a) hopper temperature of 160°C; (b)
  • the blends are passed to a slit-type die and extruded into a tape. Total dwell time in the extruder is about 20 minutes. 0
  • the extrudate tape is visually inspected to determine its "color” and "clarity” by the following tests. "Color” is qualitatively rated on a scale of 1 to 5 over a continuous range of discoloration, wherein 1 »- represents a creamy color and 5 a rather dark brown.
  • “Clarity” is qualitatively rated on a scale of 1 to 5 over a continuous range of transparency, wherein 1 represents a transparent sample and 5 an opaque sample.
  • Mg(0H) 2 magnesium hydroxide, commercially available from Kyowa Chemical Company, under the trade designation Kisuma 5B.
  • compositions of the present invention possess good color and clarity.
  • Examples 2-6 also exhibited relatively low level of carbon contamination as compared with Comparative Example 1.
  • Examples 1-7 are repeated with the following exception: the mixture of vinylidene chloride interpolymer and magnesium hydroxide is extruded through a single strand die, passed through a water bath, and then pelletized.
  • the strand die had an internal diameter of 0.32 centimeter.
  • Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated. The pellets exhibited similarly good color and clarity, and reduced carbon contamination.
  • the vinylidene chloride interpolymer is formed from a monomer mixture comprising about 94 weight percent vinylidene chloride and about 6 weight percent methyl acrylate, based on total monomer mixture weight.
  • the copolymer has a weight average molecular weight of 100,000.
  • the extrudate tape exhibited similarly good color and clarity, and reduced carbon contamination.
  • Examples 15-23 are repeated with the following exception: the mixture of vinylidene chloride interpolymer and magnesium hydroxide is extruded through a single strand die, passed through a water bath, and then pelletized.
  • the strand die had an internal diameter of 0.32 centimeter.
  • Pelletizing was accomplished using a Model 304, 15.24 centimeter strand cutter commercially available from Conair Incorporated. The pellets exhibited similarly good color and clarity, and reduced carbon contamination.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention se rapporte à une composition et à un procédé permettant d'obtenir un interpolymère de chlorure de vinylidène ayant des caractéristiques de clarté améliorée, dans lequel l'interpolymère de chlorure de vinylidène est mélangé, pour former un mèlange généralement homogène, avec de l'hydroxyde de magnésium dont la quantité est comprise entre 0,01 et 5 % en poid, calculée sur le poids total du mélange.
PCT/US1989/003117 1989-07-19 1989-07-19 Interpolymere de chlorure de vinylidene Ceased WO1991001347A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019910700282A KR0151109B1 (ko) 1989-07-19 1989-07-19 염화 비닐리덴 인터폴리머
EP19890911512 EP0434763A4 (en) 1989-07-19 1989-07-19 Vinylidene chloride interpolymer
PCT/US1989/003117 WO1991001347A1 (fr) 1989-07-19 1989-07-19 Interpolymere de chlorure de vinylidene
JP1510629A JPH04500829A (ja) 1989-07-19 1989-07-19 塩化ビニリデン共重合体

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1989/003117 WO1991001347A1 (fr) 1989-07-19 1989-07-19 Interpolymere de chlorure de vinylidene

Publications (1)

Publication Number Publication Date
WO1991001347A1 true WO1991001347A1 (fr) 1991-02-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/003117 Ceased WO1991001347A1 (fr) 1989-07-19 1989-07-19 Interpolymere de chlorure de vinylidene

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EP (1) EP0434763A4 (fr)
JP (1) JPH04500829A (fr)
KR (1) KR0151109B1 (fr)
WO (1) WO1991001347A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424347A (en) * 1989-12-28 1995-06-13 American National Can Company MA-PVDC formulations, films, and structures which maintain high barrier properties after retorting

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140178666A1 (en) 2011-07-27 2014-06-26 Asahi Kasei Chemicals Corporation Vinylidene chloride-based resin composition, manufacturing method thereof, and vinylidene chloride-based resin molded product
JP7478613B2 (ja) * 2019-08-28 2024-05-07 旭化成株式会社 ラップフィルム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446765A (en) * 1965-03-29 1969-05-27 Ici Ltd Rigid compositions comprising polyvinyl chloride,calcium carbonate and an oxide or hydroxide
US3891598A (en) * 1973-01-12 1975-06-24 Dow Chemical Co Bubble-free, high barrier vinylidene chloride polymer films and process of preparation
US4751261A (en) * 1986-08-14 1988-06-14 Kyowa Chemical Industry Co., Ltd. Stabilized polyvinyl chloride resin composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1289202A (fr) * 1960-05-13 1962-03-30 Wacker Chemie Gmbh Masses isolantes pour conducteurs électriques
KR970006904B1 (ko) * 1987-10-09 1997-04-30 더 다우 케미칼 캄파니 비닐리덴 클로라이드 인터폴리머
JP2801323B2 (ja) * 1988-03-07 1998-09-21 ザ ダウ ケミカル カンパニー 感熱性樹脂のための押出配合物パッケージおよび前記パッケージを含むポリマー組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446765A (en) * 1965-03-29 1969-05-27 Ici Ltd Rigid compositions comprising polyvinyl chloride,calcium carbonate and an oxide or hydroxide
US3891598A (en) * 1973-01-12 1975-06-24 Dow Chemical Co Bubble-free, high barrier vinylidene chloride polymer films and process of preparation
US4751261A (en) * 1986-08-14 1988-06-14 Kyowa Chemical Industry Co., Ltd. Stabilized polyvinyl chloride resin composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0434763A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5424347A (en) * 1989-12-28 1995-06-13 American National Can Company MA-PVDC formulations, films, and structures which maintain high barrier properties after retorting

Also Published As

Publication number Publication date
EP0434763A1 (fr) 1991-07-03
JPH04500829A (ja) 1992-02-13
EP0434763A4 (en) 1992-01-02
KR0151109B1 (ko) 1999-05-15
KR920702860A (ko) 1992-10-28

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