WO1992020731A1 - Composition polymere - Google Patents

Composition polymere Download PDF

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Publication number
WO1992020731A1
WO1992020731A1 PCT/GB1992/000922 GB9200922W WO9220731A1 WO 1992020731 A1 WO1992020731 A1 WO 1992020731A1 GB 9200922 W GB9200922 W GB 9200922W WO 9220731 A1 WO9220731 A1 WO 9220731A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
polymer
red phosphorus
phosphate
polyether
Prior art date
Application number
PCT/GB1992/000922
Other languages
English (en)
Inventor
Kathleen Hood
Original Assignee
Raychem Limited
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 Raychem Limited filed Critical Raychem Limited
Priority to JP4510503A priority Critical patent/JPH06507660A/ja
Publication of WO1992020731A1 publication Critical patent/WO1992020731A1/fr

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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
    • C08K3/02—Elements
    • 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
    • C08K3/32—Phosphorus-containing compounds

Definitions

  • This invention relates to the flame retarding of polymer compositions, and especially to polymers containing polyether units.
  • halogenated flame retardants have been flame retarded for many years by means of halogenated flame retardants, but these have the disadvantage that toxic and corrosive gases are evolved when the flame retarded compositions are burned. Accordingly a number of halogen-free flame retardants have been proposed for use with polymers, one such flame retardant being red phosphorus.
  • the red phosphorus may be used on its own or may be mixed with co-agents in the flame retardant package.
  • Japanese patent application publication No. 61-223045 to Sekisui KK describes the use of red phosphorus and ammonium phosphate to flame retard polyolefins.
  • the present invention provides a polymer composition which comprises a polymer containing polyether units and a flame retardant comprising red phosphorus and an ammonium phosphate.
  • a flame retardant comprising red phosphorus and an ammonium phosphate.
  • red phosphorus has been proposed as a flame retardant in some polymers, on its own it appears to exhibit no significant flame retardant activity whatsoever in the polymers employed in the invention.
  • the polymer is preferably a polyether ester.
  • the polymer may be a polyether ester based thermoplastic elastomer and especially one based on a segmented copolyester polymer comprising recurring intralinear long chain ester units and short chain ester units randomly joined head-to-tail, the long chain ester units being represented by the formula:
  • G is a divalent radical remaining after the removal of terminal hydroxyl groups from at least one long chain glycol having a molecular weight of about 600 - 6000; R is a divalent radical remaining after removal of carboxyl groups from at least one dicarboxylic acid having a molecular weight less than about 300; and D is a divalent radical remaining after removal of hydroxyl groups from at least one low molecular weight diol having a molecular weight less than 250.
  • segmented copolyester polymers are the segmented polyether ester copolymers derived from terephthalic acid, polytetramethylene ether glycol and 1,4-butanediol. These are random block copolymers having crystallizable hard blocks with the repeating unit
  • an ammonium phosphate as used herein is intended to include both inorganic ammonium compounds and ammonium compounds derived from organic amines (provided that the organic moieties do not interfere with the effectiveness of the flame retardant.
  • phosphate includes polyphosphates and salts derived from other oxyacids of phosphorus.
  • the preferred ammonium phosphates are ammonium polyphosphate and melamine phosphate.
  • the composition preferably contains at least 5% by weight, and more preferably at least 10% by weight of the ammonium phosphate.
  • the flame retardancy appears to increase with the level of the ammonium phosphate used, so that it is preferably employed at levels of at least 15%, especially at least 20% by weight. Levels greater than 60% and especially 40% are generally not employed since at such high filler levels some deterioration of the physical properties of the polymer will occur. All percentages given herein are based on the total weight of the composition.
  • the blend will normally contain at least 0.1% by weight red phosphorus. Preferably the blend contains at least 1%, more preferably at least 2% and especially at least 3% red phosphorus by weight.
  • the composition will not normally contain more than 10%, preferably not more than 7% red phosphorus by weight. All percentages given herein are percentages by weight based on the total weight of the composition.
  • the polymer composition may be crosslinked. They may be crosslinked by any convenient method, for example by irradiation or, by chemical crosslinking using, for example, a peroxide. Suitable peroxides are those that decompose rapidly within the range of 150°C - 250°C. These include, for example, dicumyl peroxide, 2,5-bis (t-butylperoxy)-2,5-dimethylhexane, and t , * -bis (t- butylperoxy) di-isopropylbenzene. In a typical chemically crosslinkable composition there will be about 0.5 - 5 parts by weight of peroxide per 100 parts of polymer composition.
  • the peroxide may be absorbed on an inert carrier such as a calcium carbonate, carbon black, or kieselguhr; however, the weight of the carrier is not included in the above range.
  • the polymer compositions of the present invention are crosslinked using high energy radiation. Radiation dose levels to achieve crosslinking according to the present invention may range from about 20 to 800 kGy or more, but a dose of about 50 to 500 kGy is preferred. For most purposes a dose of about 80 to 200 kGy will be effective.
  • a co-agent to assist in the crosslinking reaction.
  • Such co-agents usually contain multiple unsaturated groups such as allyl or acrylic esters. While their mode of action is not known with certainty, it is believed that they react with the initial radical formed on the polymer backbone to form a more stable radical, which undergoes a coupling reaction to form crosslinks more readily than chain scission reactions.
  • the co-agent can be for example, N,N'-m(phenylene)- dimaleimide, trimethylolpropane trimethylacrylate, tetra(allyloxy)- ethane, triallyl cyanurate, triallyl isocyanurate, or polyethylene oxide glycol dimethacrylate.
  • the amount of the co-agent is preferably up to about 5 parts by weight per 100 parts of the polymer composition and preferably from 1 to 3 parts by weight per 100 parts of the polymer composition.
  • Crosslinked polymer compositions according to the present invention may be used in a wide range of applications, and the preferred compositions find particular application as electrical insulation or jacketing in electrical wire or cable or in electrical harnesses. For example they may be used for primary insulation and/or primary jackets in electrical wires or they may be used as extruded cable jackets.
  • compositions according to the invention may be used for the production of heat-recoverable articles for a wide variety of purposes.
  • a heat-recoverable article is one which is in a dimensionally unstable condition and is capable of altering its physical form upon the application of heat alone to assume a dimensionally heat stable condition.
  • the article is elastomeric in both its heat unstable and heat stable forms.
  • Heat-recoverable articles may be produced for example deforming an article under heat and pressure from an original dimensionally heat stable form to a dimensionally heat unstable form from which it is capable of recovery towards it original form upon the application of heat alone. Heat-recoverable articles and methods for their production are described, for example in US Patents Nos. 2,027,962, 3,086,242 and 3,957,372.
  • polymers may be blended with the composition according to the invention.
  • any polymer may be blended with the composition provided that it does not destroy the improvement in thermal stability of the polyether polymer given by the red phosphorus.
  • Preferred polymers for blending with the compositions include ethylene homo- and copolymers eg. low, medium or high density polyethylene and ethylene vinyl acetate copolymers (or so-called vinyl acetate ethylene copolymers which have a higher vinyl acetate content), ethylene acrylic acid copolymers, polyamides (including polyether amides), and polyesters for example polybutylene terephthalate.
  • ethylene acrylic acid copolymers include ternary copolymers such as those sold by DuPont under the tradename "Vamac”.
  • the composition according to the invention may contain additional conventional additives for example fillers, ultraviolet stabilizers, antioxidants, acid acceptors, anti-hydrolyis stabilizers, pigments, fungicides and the like.
  • additional conventional additives for example fillers, ultraviolet stabilizers, antioxidants, acid acceptors, anti-hydrolyis stabilizers, pigments, fungicides and the like.
  • additives will not normally be employed other than in small quantities, eg. up to 30% by weight, although in some instances eg, in the case of halogen-free flame retardants, larger quantities may be employed.
  • Crosslinking promoter 5 (triallyl cyanurate)
  • the components were blended, extruded, injection moulded and then irradiated with high energy electrons to a dose of 100 kGy.
  • the LOI of the polymer blend containing no ammonium polyphosphate was determined for various levels of phosphorus. It was found that the LOI remained constant at 19.5 for phosphorus levels between 0% and 10%.
  • Example 1 was repeated with the exception that the ammonium polyphosphate was replaced with melamine phosphate.
  • the results are given in Table II and are shown graphically in Figure 2 from which it can be seen that rate of increase in LOI with melamine phosphate content is greater in the presence of red phosphorus, indicating a synergistic effect.
  • Example 1 and 2 were repeated with the exception that the polyetherester polymer were replaced with a polyester ester block copolymer sold by Akzo NV under the trade name Arnitel.
  • the LOI results are given in Tables III and IV and are shown graphically in Figures 3 and 4, from which it can be seen that the presence of red phosphorus alone increases the LOI by about 2 units but the presence of both red phosphorus and the ammonium phosphate does not exhibit any synergism as shown by the fact that the rate of increase of LOI with phosphate level is unchanged by the presence of red phosphorus.

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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)

Abstract

L'invention se rapporte à une composition polymère, par exemple pour l'isolation de fils électriques ou pour des articles thermorétrécissables, qui comprend un polymère contenant des unités de polyéther et un enrobage ignifuge contenant du phosphore rouge et un phosphate d'ammonium, tels que du polyphosphate d'ammonium ou du phosphate de mélamine. Le polymère est de préférence constitué par un ester de polyéther et plus particulièrement par un copolymère bloc d'ester de polyéther segmenté, tiré de l'acide téréphtalique, du polytétraméthylène-glycol d'éther et du 1,4-butanediol. La combinaison du phosphore rouge et du phosphate d'ammonium produit un effet synergique qui améliore les propriétés ignifuges des copolymères à l'ester de polyéther, mais elle n'a pas un tel effet dans des polymères similaires, tels que des copolymères au polyester qui ne contiennent pas d'unités de polyéther.
PCT/GB1992/000922 1991-05-24 1992-05-21 Composition polymere WO1992020731A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4510503A JPH06507660A (ja) 1991-05-24 1992-05-21 ポリマー組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919111220A GB9111220D0 (en) 1991-05-24 1991-05-24 Polymer composition
GB9111220.1 1991-05-24

Publications (1)

Publication Number Publication Date
WO1992020731A1 true WO1992020731A1 (fr) 1992-11-26

Family

ID=10695525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/000922 WO1992020731A1 (fr) 1991-05-24 1992-05-21 Composition polymere

Country Status (6)

Country Link
EP (1) EP0586433A1 (fr)
JP (1) JPH06507660A (fr)
CA (1) CA2109308A1 (fr)
GB (1) GB9111220D0 (fr)
IL (1) IL101977A0 (fr)
WO (1) WO1992020731A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998503A (en) * 1996-08-29 1999-12-07 E. I. Du Pont De Nemours And Company Polymer flame retardant
WO2001075907A1 (fr) * 2000-03-30 2001-10-11 Pirelli Cavi E Sistemi S.P.A. Cables autoextinguibles et compositions ignifuges entrant dans leur composition
US6797200B2 (en) 2000-03-30 2004-09-28 Pirelli Cavi E Sistemi S.P.A. Self-extinguishing cable and fire retardant composition used therein
WO2012024280A1 (fr) 2010-08-17 2012-02-23 E. I. Du Pont De Nemours And Company Compositions élastomères thermoplastiques de copolyester ignifugeantes sans halogène, stables à la chaleur
WO2012119057A1 (fr) 2011-03-02 2012-09-07 E. I. Dupont De Nemours And Company Compositions d'élastomères thermoplastiques, ignifuges, exemptes d'halogène, à très faible émission de fumées, contenant des zéolites
WO2012119067A1 (fr) 2011-03-02 2012-09-07 E. I. Du Pont De Nemours And Company Compositions de vulcanisats thermoplastiques, ignifuges, exemptes d'halogène, à très faible émission de fumées, contenant des zéolites
US8598298B2 (en) 2010-03-26 2013-12-03 Dow Global Technologies Llc Flame retardant thermoplastic elastomer composition with resistance to scratch-whitening
US9527998B2 (en) 2009-10-28 2016-12-27 Dow Global Technologies Llc Thermoplastic polyurethane composition with high insulation resistance
WO2017172723A1 (fr) 2016-03-31 2017-10-05 E I Du Pont De Nemours And Company Compositions d'élastomères thermoplastiques ignifuges, exemptes d'halogène, contenant des cyclodextrines
WO2019137753A1 (fr) * 2018-01-15 2019-07-18 Gkn Driveline International Gmbh Procédé de fabrication d'un soufflet
US11066533B2 (en) 2014-10-01 2021-07-20 Dupont Polymers. Inc. Low smoke halogen free flame retardant thermoplastic elastomer compositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0083768A1 (fr) * 1981-12-19 1983-07-20 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition de résine résistant à la flamme

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0083768A1 (fr) * 1981-12-19 1983-07-20 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition de résine résistant à la flamme

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN *
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 73-74656U & JP,A,48 007 043 (POLYPLASTICS INC) *
WORLD PATENTS INDEX Derwent Publications Ltd., London, GB; AN 74-06241V & JP,A,48 007 044 (POLYPLASTICS INC) *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6015510A (en) * 1996-08-29 2000-01-18 E. I. Du Pont De Nemours And Company Polymer flame retardant
US5998503A (en) * 1996-08-29 1999-12-07 E. I. Du Pont De Nemours And Company Polymer flame retardant
WO2001075907A1 (fr) * 2000-03-30 2001-10-11 Pirelli Cavi E Sistemi S.P.A. Cables autoextinguibles et compositions ignifuges entrant dans leur composition
US6797200B2 (en) 2000-03-30 2004-09-28 Pirelli Cavi E Sistemi S.P.A. Self-extinguishing cable and fire retardant composition used therein
US9527998B2 (en) 2009-10-28 2016-12-27 Dow Global Technologies Llc Thermoplastic polyurethane composition with high insulation resistance
US8598298B2 (en) 2010-03-26 2013-12-03 Dow Global Technologies Llc Flame retardant thermoplastic elastomer composition with resistance to scratch-whitening
WO2012024280A1 (fr) 2010-08-17 2012-02-23 E. I. Du Pont De Nemours And Company Compositions élastomères thermoplastiques de copolyester ignifugeantes sans halogène, stables à la chaleur
US8415415B2 (en) 2010-08-17 2013-04-09 E I Du Pont De Nemours And Company Heat stable halogen-free flame retardant copolyester thermoplastic elastomer compositions
WO2012119067A1 (fr) 2011-03-02 2012-09-07 E. I. Du Pont De Nemours And Company Compositions de vulcanisats thermoplastiques, ignifuges, exemptes d'halogène, à très faible émission de fumées, contenant des zéolites
US8781278B2 (en) 2011-03-02 2014-07-15 E I Du Pont De Nemours And Company Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites
WO2012119057A1 (fr) 2011-03-02 2012-09-07 E. I. Dupont De Nemours And Company Compositions d'élastomères thermoplastiques, ignifuges, exemptes d'halogène, à très faible émission de fumées, contenant des zéolites
US11066533B2 (en) 2014-10-01 2021-07-20 Dupont Polymers. Inc. Low smoke halogen free flame retardant thermoplastic elastomer compositions
WO2017172723A1 (fr) 2016-03-31 2017-10-05 E I Du Pont De Nemours And Company Compositions d'élastomères thermoplastiques ignifuges, exemptes d'halogène, contenant des cyclodextrines
WO2019137753A1 (fr) * 2018-01-15 2019-07-18 Gkn Driveline International Gmbh Procédé de fabrication d'un soufflet
US11326021B2 (en) 2018-01-15 2022-05-10 Gkn Driveline International Gmbh Producing a bellows

Also Published As

Publication number Publication date
IL101977A0 (en) 1992-12-30
GB9111220D0 (en) 1991-07-17
CA2109308A1 (fr) 1992-11-25
EP0586433A1 (fr) 1994-03-16
JPH06507660A (ja) 1994-09-01

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