WO1999045547A1 - Film de polymere syndiotactique aromatique a base de monovinylidene - Google Patents

Film de polymere syndiotactique aromatique a base de monovinylidene Download PDF

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Publication number
WO1999045547A1
WO1999045547A1 PCT/US1999/002710 US9902710W WO9945547A1 WO 1999045547 A1 WO1999045547 A1 WO 1999045547A1 US 9902710 W US9902710 W US 9902710W WO 9945547 A1 WO9945547 A1 WO 9945547A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
syndiotactic
percent
styrene
monovinylidene aromatic
Prior art date
Application number
PCT/US1999/002710
Other languages
English (en)
Inventor
Gregg A. Motter
Robert P. Brentin
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to EP99905867A priority Critical patent/EP1060479A1/fr
Priority to JP2000535011A priority patent/JP2002506269A/ja
Priority to KR1020007009662A priority patent/KR20010041494A/ko
Publication of WO1999045547A1 publication Critical patent/WO1999045547A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—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 aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to impact modified syndiotactic monovinylidene aromatic polymers and film produced therefrom.
  • Electrical insulating film is used to provide insulation between an electrically conductive metallic support structure and current conducting magnet wire.
  • Such films have typically been produced from polymers such as polyester, polyethylene terephthalate, polypropylene, atactic polystyrene and polyimide. Polyesters are known to absorb moisture, resulting in poor dimensional stability. Additionally, polyester has a relatively low glass transition temperature (-52 °C) which allows the film to soften under the load of tightly wound magnet wire. Polyester is also subject to hydrolysis which, over time in humid environments, will cause molecular weight degradation and insulation failure. Furthermore, polyester film requires the use of a secondary orientation step to achieve a sufficiently high level of crystallinity to increase heat resistance.
  • Polyethylene terephthalate, polypropylene and atactic polystyrene polymers do not offer sufficient heat resistance in such insulation applications.
  • Polyimide film provides excellent electrical insulation and heat resistance performance.
  • Other insulation substrates include kraft paper, rag paper, vulcanized fiber, and rag paper/PET. However, these materials can undergo considerable dimensional change due to moisture conditions.
  • US-A-5, 093,758 by Funaki et al. discloses an electrical insulating film which comprises a styrene polymer having a syndiotactic configuration (SPS) and containing not more than 1 ,000 ppm of residual aluminum derived from the catalyst used in the production of styrene polymer, and not more than 3,000 ppm residual styrene monomer.
  • SPS syndiotactic configuration
  • unmodified SPS film is inherently brittle which can cause film cracking during the slitting, cutting, and folding operations required in the fabrication of an electrical device.
  • this application requires SPS having very low levels of impurities which requires further polymer treatment.
  • the present invention is an electrical insulating film comprising an impact modified syndiotactic monovinylidene aromatic polymer.
  • the electrical insulating film can be used to provide electrical insulation between energized wires and a ground potential support structure.
  • the impact modified polymer used in the films of the present invention has high dielectric strength and is less affected by moisture than polyester, therefore, thinner film sheets can be used. Thinner insulation film sheets provide an increase in volume in the motor slot which can be used to add additional windings, increasing motor efficiency.
  • the present invention is an electrical insulating film comprised of a rubber modified syndiotactic monovinylidene aromatic polymer.
  • stereotactic refers to polymers having a stereoregular structure of greater than 90 percent syndiotactic, preferably greater than 95 percent syndiotactic, of a racemic triad as determined by 13 C nuclear magnetic resonance spectroscopy.
  • Syndiotactic monovinylidene aromatic polymers are homopolymers and copolymers of vinyl aromatic monomers, that is, monomers whose chemical structure possess both an unsaturated moiety and an aromatic moiety.
  • the preferred vinyl aromatic monomers have the formula
  • H 2 C CR-Ar; wherein R is hydrogen or an alkyl group having from 1 to 4 carbon atoms, and
  • Ar is an aromatic radical of from 6 to 10 carbon atoms.
  • vinyl aromatic monomers are styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl toluene, para-t-butylstyrene, vinyl naphthalene, and divinylbenzene.
  • Syndiotactic polystyrene is the currently preferred syndiotactic vinyl aromatic polymer.
  • Typical polymerization processes for producing syndiotactic vinyl aromatic polymers are well known in the art and are described in US-A-4,680,353, US-A-5,066,741 ,
  • the weight average molecular weight (Mw) of the syndiotactic monovinylidene aromatic polymer is sufficient such that the polymer obtains
  • the impact modifier used in the films of the present invention can be any impact modifier which will impart sufficient strength and flexibility within the syndiotactic polymer such that it can be used in an insulating film. Typically this means that the film can be folded back onto itself without cracking.
  • impact modifiers include but are not limited to styrene- ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene- propylene-styrene block copolymers (SEPS), polyolefins such as ethylene- octene and ethylene-hexene copolymers, polybutadiene, polyisoprene and copolymers of dienes with vinyl aromatic monomers such as butadiene- styrene and isoprene-styrene copolymers.
  • SEBS styrene- ethylene-butylene-styrene block copolymer
  • SEPS styrene-ethylene- propylene-styrene block copolymers
  • polyolefins such as ethylene- octene and ethylene-hexene copolymers
  • polybutadiene polyisoprene and copolymers of dienes
  • the impact modified syndiotactic monovinylidene aromatic polymer typically contains from 50, more preferably from 55, and most preferably from 60 to 95, preferably to 90 and most preferably to 85 percent by weight of the syndiotactic monovinylidene aromatic polymer, based on the total weight of the impact modified composition.
  • the impact modified syndiotactic monovinylidene aromatic polymer typically contains from 5, more preferably from 10 and most preferably from 15 to 50, preferably to 45 and most preferably to 40 weight percent of impact modifier, based on the total weight of the rubber modified composition.
  • additives include as flame retardants, antioxidants, including hindered phenols such as IRGANOXTM 1010, IRGANOXTM 555, SEENOXTM 412S, and IRGANOXTM 1076, AND ULTRANOXTM 626, ULTRANOXTM 815, STAB PEPTM 36, EthanoxTM 398, HostanoxTM PAR 24 and HostanoxTM 03, 2,6-di-t-butyl-4-methylphenol, stearyl- ⁇ -(3,5-di-tert-butyl-4- hydroxyphenol)propionate, and triethylene glycol-bis-3-(3-tert-butyl-4-hydroxy- 5-methylphenyl)propionate or phosphorus-based compounds such as tris(2,4- tert-butylphenyl)phosphite and 4,
  • Nucleators can be used in the present invention and are compounds capable of reducing the time required for onset of crystallization of the syndiotactic monovinylidene aromatic polymer upon cooling from the melt. Nucleators provide a greater degree of crystallinity in an extruded sheet and more consistent distribution of crystallinity under a variety of extrusion conditions. Higher levels of crystallinity are desired in order to achieve increased chemical resistance and improved heat performance. In addition, crystal morphology may be desirably altered.
  • nucleators for use herein are monoiayer of magnesium aluminum hydroxide, calcium carbonate, mica, wollastonite, titanium dioxide, silica, sodium sulfate, lithium chloride, sodium benzoate, aluminum benzoate, talc, and metal salts, especially aluminum salts or sodium salts of organic acids or phosphonic acids.
  • Especially preferred compounds are aluminum and sodium salts of benzoic acid and C MO alkyl substituted benzoic acid derivatives.
  • a most highly preferred nucleator is aluminum t s(p-tert-butyl)benzoate.
  • the amount of nucleator used should be sufficient to cause nucleation and the onset of crystallization in the syndiotactic vinylaromatic polymer in a reduced time compared to compositions lacking in such nucleator. Preferred amounts are
  • the impact modified syndiotactic monovinylidene aromatic polymer is prepared by blending the impact modifier with the syndiotactic monovinylidene polymer and other additives. Any means can be used to adequately reach uniform dispersion of the impact modifier and other additives in the syndiotactic monovinylidene aromatic polymer. This is generally accomplished by compounding the materials in an extruder and pelletizing. The compounded pellets are then melted and metered in an extruder to a sheet die to produce a sheet web which is cast onto a three roll stack to cool the web while maintaining uniform thickness and smooth surface quality. The extruded web is typically wound onto a roll for subsequent processing. The sheet is then slit to the proper width and cut to length. In preparing a motor assembly, small sections of plastic sheet are folded, cuffed and inserted into the slot liner of the motor to act as the electrical insulation.
  • the electrical insulating film can be produced on a conventional cast film/sheet extrusion line or on a cast tenter film/sheet line as disclosed in US-A-5, 093,758.
  • the extruded sheet/film can be uni- or bi-axially stretched.
  • conventional cast film/sheet line such as a single screw extruder feeding a coat-hanger type die which casts the molten web onto a three roll cooling stack
  • a faster production rate can be achieved while obtaining crystallinity in the sheet of 10 - 50 percent.
  • Levels of less than 10 percent are achieved in compositions containing high levels of impact modifier. High levels of crystallinity are preferred to ensure dimensional stability in end use applications which involves elevated temperatures and/or thermal cycling.
  • Syndiotactic monovinylidene aromatic polymers such as SPS
  • the extrusion line path will be from 5 - 50 cm, preferably from 20 to 40 cm with the melt temperature ranging from 310 to 330°C.
  • the crystallinity is from 15, preferably from 20 and most preferably from 25 to 50, preferably to 45, and most preferably to 40 percent.
  • the electrical insulating film is typically obtained in thicknesses of from 100 to 500 microns ( ⁇ m), preferably from 150 to 400, more preferably from 150 to 300, and most preferably from 200 to 300 ⁇ m.
  • the electrical insulating film of the present invention is characterized by a glass transition temperature of 100°C. This allows the film to maintain a higher modulus at elevated temperatures compared to alternative materials such as polyester. Additionally, the film has good dead fold characteristics which is highly desirable for electrical ground insulation applications. Polymers used to make this film are non-hydroscopic, therefore dimensional changes in the fabricated electrical insulation component are minimal. This allows for more predictable, tighter tolerance engineering of the electrical insulation system.
  • the electrical insulating film of the present invention has superior dielectric strength and breakdown voltage properties compared to commonly used polyester films and vulcanized papers. This will enable the electrical designer to down gauge the film thickness to allow more space in the device for copper windings leading to a more electrically efficient machine.
  • An additional advantage of the electrical insulating film of the present invention is its inherently bright white color obtained without the addition of pigments.
  • Commonly used polyester films are tinted white with pigments such as titanium dioxide which incurs a loss in physical and electrical properties.
  • the bright white color also provides a contrast background for the visual detection of flaws in the magnet wire coating.
  • the electrical insulating film of the present invention is useful for electrical insulation in slot liners, wedges and phase insulation for motors and generators. This includes hermetic motor/compressor sealed units, fractional horsepower motors, diaphragms and industrial laminations.
  • SPS, impact modifier and nucleator are compounded on a twin screw extruder and pelletized. The pellets are then melted and extruded into thin (approximately 250 ⁇ m thick) sheet under the conditions listed in Table II.
  • Crystallinity in the thin sheet samples is determined using differential scanning calorimetry.
  • the need for a secondary operation to increase crystallinity is eliminated by selecting process conditions that keep the polymer melt above its glass transition temperature for a sufficient amount of time for crystallinity to develop before cooling. This includes having a melt temperature of 310°C and increasing the distance between the die lips and the first roll to approximately 25 cm.
  • the film is slit and die stamped to the appropriate physical dimensions for insertion into a wire-wound electromechanical device.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

Le procédé de l'invention utilise un styrène-polymère syndiotactique pour produire un film mince pouvant isoler parfaitement des structures porteuses d'un métal conducteur d'un fil de bobinage conducteur. L'addition de modificateurs d'impact permet au film mince de résister à la contrainte mécanique de fabrication pendant des opérations d'assemblage d'un moteur. Le film ainsi obtenu présente de bonnes qualités de résistance thermique, de rigidité diélectrique et d'insensibilité à l'humidité, et donc une plus grande stabilité dimensionnelle et résistance à l'hydrolyse.
PCT/US1999/002710 1998-03-02 1999-02-09 Film de polymere syndiotactique aromatique a base de monovinylidene WO1999045547A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP99905867A EP1060479A1 (fr) 1998-03-02 1999-02-09 Film de polymere syndiotactique aromatique a base de monovinylidene
JP2000535011A JP2002506269A (ja) 1998-03-02 1999-02-09 シンジオタクチックモノビニリデン芳香族ポリマーフィルム
KR1020007009662A KR20010041494A (ko) 1998-03-02 1999-02-09 신디오택틱 모노비닐리덴 방향족 중합체 필름

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7656698P 1998-03-02 1998-03-02
US60/076,566 1998-03-02

Publications (1)

Publication Number Publication Date
WO1999045547A1 true WO1999045547A1 (fr) 1999-09-10

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PCT/US1999/002710 WO1999045547A1 (fr) 1998-03-02 1999-02-09 Film de polymere syndiotactique aromatique a base de monovinylidene

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EP (1) EP1060479A1 (fr)
JP (1) JP2002506269A (fr)
KR (1) KR20010041494A (fr)
WO (1) WO1999045547A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010060176A1 (de) * 2010-10-26 2012-04-26 Ensinger Gmbh Isoliersteg

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019049922A1 (fr) * 2017-09-08 2019-03-14 倉敷紡績株式会社 Film de matériau de base pour câbles plats et film isolant pour câbles plats l'utilisant

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093758A (en) * 1989-10-09 1992-03-03 Idemitsu Kosan Co., Ltd. Electrical insulation film and condenser
EP0587098A1 (fr) * 1992-09-10 1994-03-16 Idemitsu Kosan Company Limited Composition de polystyrène
EP0591823A1 (fr) * 1992-10-08 1994-04-13 Idemitsu Kosan Company Limited Composition de résine thermoplastique
JPH06116454A (ja) * 1992-10-07 1994-04-26 Idemitsu Kosan Co Ltd 熱可塑性樹脂組成物
EP0639616A1 (fr) * 1993-03-03 1995-02-22 Idemitsu Kosan Company Limited Compositions de resine de polystyrene a forte resistance aux chocs
EP0733675A1 (fr) * 1994-10-05 1996-09-25 Idemitsu Kosan Company Limited Composition de resine de polystyrene extremement resistante aux chocs
EP0757064A1 (fr) * 1994-11-29 1997-02-05 Idemitsu Petrochemical Co., Ltd. Polymere au styrene et articles moules
WO1997032928A1 (fr) * 1996-03-05 1997-09-12 The Dow Chemical Company Composition de moulage contenant un polymere vinylaromatique syndiotactique
US5760105A (en) * 1993-06-04 1998-06-02 Idemitsu Kosan Co., Ltd. Styrenic resin composition
WO1999014273A1 (fr) * 1997-09-12 1999-03-25 The Dow Chemical Company Melanges de polymeres durcis
WO1999016825A1 (fr) * 1997-09-29 1999-04-08 The Dow Chemical Company Composition a mouler renfermant un polymere aromatique de monovinylidene syndiotactique

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093758A (en) * 1989-10-09 1992-03-03 Idemitsu Kosan Co., Ltd. Electrical insulation film and condenser
EP0587098A1 (fr) * 1992-09-10 1994-03-16 Idemitsu Kosan Company Limited Composition de polystyrène
JPH06116454A (ja) * 1992-10-07 1994-04-26 Idemitsu Kosan Co Ltd 熱可塑性樹脂組成物
EP0591823A1 (fr) * 1992-10-08 1994-04-13 Idemitsu Kosan Company Limited Composition de résine thermoplastique
EP0639616A1 (fr) * 1993-03-03 1995-02-22 Idemitsu Kosan Company Limited Compositions de resine de polystyrene a forte resistance aux chocs
US5760105A (en) * 1993-06-04 1998-06-02 Idemitsu Kosan Co., Ltd. Styrenic resin composition
EP0733675A1 (fr) * 1994-10-05 1996-09-25 Idemitsu Kosan Company Limited Composition de resine de polystyrene extremement resistante aux chocs
EP0757064A1 (fr) * 1994-11-29 1997-02-05 Idemitsu Petrochemical Co., Ltd. Polymere au styrene et articles moules
WO1997032928A1 (fr) * 1996-03-05 1997-09-12 The Dow Chemical Company Composition de moulage contenant un polymere vinylaromatique syndiotactique
WO1999014273A1 (fr) * 1997-09-12 1999-03-25 The Dow Chemical Company Melanges de polymeres durcis
WO1999016825A1 (fr) * 1997-09-29 1999-04-08 The Dow Chemical Company Composition a mouler renfermant un polymere aromatique de monovinylidene syndiotactique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 121, no. 20, 14 November 1994, Columbus, Ohio, US; abstract no. 232323, OKADA, AKIHIKO ET AL: "Heat- and impact-resistant syndiotactic polystyrene compositions with goo mechanical properties" XP002102644 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010060176A1 (de) * 2010-10-26 2012-04-26 Ensinger Gmbh Isoliersteg
EP2447459A1 (fr) * 2010-10-26 2012-05-02 Ensinger GmbH Isolateur

Also Published As

Publication number Publication date
EP1060479A1 (fr) 2000-12-20
JP2002506269A (ja) 2002-02-26
KR20010041494A (ko) 2001-05-25

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