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WO1996034047A1 - Composition polymere thermoplastique ignifuge exempte d'halogene - Google Patents

Composition polymere thermoplastique ignifuge exempte d'halogene Download PDF

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Publication number
WO1996034047A1
WO1996034047A1 PCT/NL1996/000171 NL9600171W WO9634047A1 WO 1996034047 A1 WO1996034047 A1 WO 1996034047A1 NL 9600171 W NL9600171 W NL 9600171W WO 9634047 A1 WO9634047 A1 WO 9634047A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
group
retardant thermoplastic
thermoplastic polyester
polyester composition
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/NL1996/000171
Other languages
English (en)
Inventor
Richerdes Johanna Mathilda Hulskotte
Martinus Louis Maria Bos
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Priority to AU54090/96A priority Critical patent/AU5409096A/en
Publication of WO1996034047A1 publication Critical patent/WO1996034047A1/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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers

Definitions

  • the invention relates to a flame-retardant thermoplastic polymer composition
  • a flame-retardant thermoplastic polymer composition comprising (a) a polyester derived from alkylene glycol and an aromatic dicarboxylic acid and (b) an oxalate complex.
  • Such a composition is known from GB-A- 1541296, which discloses a composition that consists of polyalkylene terephthalate and an oxalate complex with a complex anion [Z(C 2 0 4 ) n ] ⁇ , where Z is chosen from the group comprising Mg, Ca, Sr, Ba, Zr, Hf, Ce, V, Cr , Mn, Fe, Co, Ni, Cu, Zn, Cd, B, Al, Ga, In, Sn, Pb and Sb, n is an integer and -e indicates the anion's negative charge.
  • One or more alkali ions serve as the cation.
  • the use of the complex oxalate results in an increase in the 'Limiting Oxygen Index' (the LOI).
  • the LOI is the oxygen concentration of a nitrogen/oxygen mixture at which the combustion of a vertically attached test specimen whose top end has been ignited is just sustained, ASTM D 2863. In practice it is however very important that, when a source of ignition is present, the plastic composition spontaneously stops burning and does not generate burning droplets which could further propagate the fire.
  • a test that is representative of this is the UL-94 test method, according to which a test specimen is vertically suspended and a flame is held beneath it for 10 seconds. This procedure is repeated as soon as the test specimen has stopped burning.
  • the different classifications V-0 and V-l and V-2 are based on the observed burning and after-glowing times and on whether or not burning droplets are formed.
  • the test's execution is laid down in UL-94.
  • Another test is the glow-wire test, in which a glow wire is pressed against a vertically placed test specimen at a prescribed pressure for 30 seconds.
  • the glow wire's temperature can be varied between 550 and 960°C. According to IEC 695-2-1, the highest temperature at which the test specimen still stops burning within 60 seconds from the beginning of the test, without afterglowing, is the glow-wire temperature.
  • the compositions known from GB-A-1541296 do not meet these stringent reguirements and in the presence of for example 30 wt.% glass fibre the flame does not extinguish at all in the UL 94 test.
  • EP-A-0026956 yields improved dripping behaviour due to the use of 0.1-0.5 wt.% polytetrafluoroethylene with a molecular weight of over IO 5 .
  • a V-0 classification again reguires the absence of fibrous fillers.
  • the aim of the invention is a halogen-free flame-retardant polyester composition which, also in the presence of fibre reinforcement, meets the highest flame-retardancy reguirements.
  • the polyester is based on ethylene glycol and if, in addition to the complex oxalate, it also contains an inorganic compound chosen from the group comprising the oxides of the metals of groups 8-10 and 15 and compounds derived therefrom, borates and silicates.
  • the halogen-free flame-retardant thermoplastic polyester composition containing a complex oxalate as the flame retardant comprises: (a) a polyester derived from alkylene glycol, at least 50 mol.% of which consists of ethylene glycol, and one or more aromatic dicarboxylic acids, (b) 2 to 50 wt.%, relative to (a), of a complex oxalate, (c) 5 to 100 wt.%, relative to (b), of an inorganic compound chosen from the group comprising oxides of metals of groups 8-10 1J and group 15 X) and compounds derived therefrom, borates and silicates.
  • the thermoplastic polyester is derived from one or more alkylene glycols, at least 50 mol.% of which is ethylene glycol, preferably at least 75 mol.% and most preferably at least 95 mol.%, and one or more aromatic dicarboxylic acids.
  • the aromatic dicarboxylic acids are preferably chosen from the group comprising phthalic acids, for example iso- and terephthalic acid, naphthalene dicarboxylic acids, for example 2,6- naphthalene dicarboxylic acid, and diphenyl dicarboxylic acids, for example 4,4 '-diphenyl dicarboxylic acid.
  • Terephthalic acid is very suitable.
  • the thermoplastic polyester is polyethylene terephthalate, PET.
  • polyesters can be obtained through polycondensation of the monomers concerned.
  • the preparation method is for example extensively described in Encyclopedia of Polymer Science and Engineering, Vol. 12, pp. 1-69 (1988), ISBN 0-471-80943-8 (v. 12) and the references mentioned therein.
  • Some of the aforementioned polyesters are commercially available.
  • the polyester 's molecular weight may vary over a wide range, expressed in the relative viscosity r ⁇ l , measured in a 1 wt.% solution in m-cresol, for example between 1.2 and 2.2. Preferably between 1.5 and 1.9.
  • the complex oxalate (b) is preferably an oxalate from the group described in the introduction to this application's description.
  • the complex oxalate is chosen from the group comprising double oxalates whose first metal is chosen from the group comprising alkali metals (group 1) and the other metal is chosen from the group comprising alkaline earth metals (group 2) or metals of group 13, for example potassium-aluminium oxalate, potassium- magnesium oxalate and rubidium-aluminium oxalate.
  • the complex oxalates can for example be obtained with the aid of the method described in GB-A-1541296.
  • the concentration of complex oxalate (b) in the composition may vary over a wide range, for example between 2 and 50 wt.%, relative to (a). Preferably the concentration of (b) is between 10 and 40 wt.%, relative to (a).
  • the inorganic compound (c) is chosen from the group comprising oxides of metals of group 15, for example Sb, and groups 8-10, for example Fe, alkali antimonates, borates, for example zinc borate, and silicates.
  • examples of preferable silicates are calcined kaolin and wollastonite. Such silicates are commercially available under various trade names. These silicates are used in a finely dispersed form, preferably in a particle size smaller than 50 ⁇ m , more preferably 10 ⁇ m.
  • Antimony trioxide is very suitable for use as component (c). It is very surprising that antimony trioxide shows a synergistic effect when combined with a complex oxalate.
  • the concentration of component (c) may vary over a wide range and is generally between 5 and 100 wt.%, relative to component (b), preferably between 10 and 60 wt.%, even more preferably between 10 and 40 wt.%, relative to component (b).
  • the composition contains up to approx.
  • the composition furthermore optionally contains the usual additives, including nucleating agents, such as sodium acetate, softeners, such as polyethylene glycol compounds, stabilisers, pigments and release agents.
  • nucleating agents such as sodium acetate
  • softeners such as polyethylene glycol compounds
  • stabilisers such as polyethylene glycol compounds
  • pigments and release agents such as polyethylene glycol compounds
  • the invention is particularly suitable if the composition contains a fibrous reinforcement.
  • the fibrous materials are organic, for example aramide, or inorganic, for example glass fibres.
  • the fibre content may vary over a wide range, for example between 1 and 150 parts by weight, preferably between 2 and 100 parts by weight per 100 parts by weight of polyester (a).
  • the composition according to the invention can be prepared in different ways.
  • the different components are mixed in the melt.
  • This can take place in various apparatuses suitable for that purpose, for example in a Brabender or Haake kneader, preferably in an extruder, a twin-screw extruder being the most preferable.
  • the extrudate obtained is then granulated and processed into the desired end products by means of for example injection-moulding, (blow) extrusion, rolling and/or compression.
  • the granules of the composition after the melt-mixing are subjected to after-condensation in the solid state to obtain a relative viscosity desired for the further processing by means of for example extrusion.
  • the various components are preferably mixed in the melt in dry condition, with the exclusion of oxygen. They may be fed to the melt-mixing apparatus separately or premixed in dry condition. It is also possible to use the so-called masterbatch method, according to which the individual components (b) and/or (c) are first premixed in the melt.
  • the polymer used in this method may differ from polymer (a).
  • PET (2) polyethylene terephthalate r ⁇ l 1.62,
  • Sb 2 0 3 antimony trioxide, Blue Star R , regular, from Campine Sb 2 0 3 -MB-PBT: 80 wt.% Sb 2 0 3 in polybutylene terephthalate (masterbatch)
  • NaSb0 2 sodium antimonite, average particle size 2 ⁇ m, Pyrobloc SAP2, from ANZON.
  • CDP cresyldiphenylphosphate, from FMC
  • Nyad 400 R wollastonite with aspect ratio 5, from Nyco
  • Translink R 445 calcined clay, average particle size 1.4 ⁇ m, from Engelhard
  • PTFE polytetrafluoroethylene, Hostaflon R 1750, from Hoechst.
  • PTFE tyrene resin
  • KAloxalate a polystyrene resin
  • Henschler mixer a Henschler mixer
  • the glass-fibre-filled compositions were produced using a ZSK twin-screw extruder. Glass fibre was dosed to the melt; the other components to the extruder's throat. The temperature was set to 275-280°C, the screw speed to 200 rpm and the throughput to 90 kg/hour. The measured melt temperatures varied between 290 and 310°C and were partly dependent on the set temperature and the glass content. The granules obtained after drying were subjected to after-condensation at about 210°C for 4-16 hours.
  • the relative viscosity was measured at 25°C in a 1 wt.% solution in m-cresol or a trichlorophenol/phenol mixture (72:100 parts by weight) and converted to m- cresol.
  • the release agent was mixed with the granules before the injection-moulding.
  • the UL-94 test specimens and the specimens for mechanical testing were produced using an injection- moulding machine at a set temperature of 285-295°C.
  • the mould temperature was 150°C.
  • test specimens for the UL-94 test were 1.6 mm; the thickness of the test specimens for the glow-wire test was 1.0 mm.
  • the following tables specify the flame retardancy, UL-94 classification and/or the glow-wire temperature for the different compositions.
  • compositions obtained according to the invention are good.

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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 concerne une composition ignifuge à base d'un polyester dérivé d'alkylène glycol et constituée en majeure partie d'éthylène glycol, de 2-50 % en poids, par rapport au polyester, d'un oxalate complexe et de 5-100 % en poids, par rapport à l'oxalate, d'un agent synergique sélectionné dans le groupe composé d'oxydes de métaux des groupes 8-10 et du groupe 15, de composés dérivés desdits oxydes, de borates et de silicates. On utilise de préférence du trioxyde d'antimoine. L'invention est particulièrement appropriée pour des compositions de polyester renforcé par des fibres de verre, qui répondent à la norme UL-94 V-0.
PCT/NL1996/000171 1995-04-28 1996-04-18 Composition polymere thermoplastique ignifuge exempte d'halogene Ceased WO1996034047A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU54090/96A AU5409096A (en) 1995-04-28 1996-04-18 Halogen-free flame-retardant thermoplastic polymer compositi on

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9500396A BE1009351A3 (nl) 1995-04-28 1995-04-28 Halogeenvrije vlamdovende thermoplastische polyestersamenstelling.
BE9500396 1995-04-28

Publications (1)

Publication Number Publication Date
WO1996034047A1 true WO1996034047A1 (fr) 1996-10-31

Family

ID=3888952

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1996/000171 Ceased WO1996034047A1 (fr) 1995-04-28 1996-04-18 Composition polymere thermoplastique ignifuge exempte d'halogene

Country Status (3)

Country Link
AU (1) AU5409096A (fr)
BE (1) BE1009351A3 (fr)
WO (1) WO1996034047A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6974846B2 (en) * 2002-04-29 2005-12-13 E. I. Du Pont De Nemours And Company Hydrolysis resistant polyester compositions and related articles and methods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026956A1 (fr) * 1979-10-08 1981-04-15 Akzo N.V. Composition de téréphtalate de polyéthylène ayant une inflammabilité réduite et produits moulés à partir de cette composition
GB2135323A (en) * 1983-02-18 1984-08-30 Akzo Nv Process for the production of polyester fibres

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0026956A1 (fr) * 1979-10-08 1981-04-15 Akzo N.V. Composition de téréphtalate de polyéthylène ayant une inflammabilité réduite et produits moulés à partir de cette composition
GB2135323A (en) * 1983-02-18 1984-08-30 Akzo Nv Process for the production of polyester fibres

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6974846B2 (en) * 2002-04-29 2005-12-13 E. I. Du Pont De Nemours And Company Hydrolysis resistant polyester compositions and related articles and methods
US7008983B2 (en) 2002-04-29 2006-03-07 E. I. Du Pont De Nemours And Company Hydrolysis resistant polyester compositions and related articles and methods

Also Published As

Publication number Publication date
AU5409096A (en) 1996-11-18
BE1009351A3 (nl) 1997-02-04

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