WO1992009653A1 - Ameliorations apportees aux compositions de polyester - Google Patents

Ameliorations apportees aux compositions de polyester Download PDF

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Publication number
WO1992009653A1
WO1992009653A1 PCT/GB1991/002078 GB9102078W WO9209653A1 WO 1992009653 A1 WO1992009653 A1 WO 1992009653A1 GB 9102078 W GB9102078 W GB 9102078W WO 9209653 A1 WO9209653 A1 WO 9209653A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
moulding composition
per cent
weight
moulding
Prior art date
Application number
PCT/GB1991/002078
Other languages
English (en)
Inventor
Richard Stuart Williams
Original Assignee
Bip Chemicals 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 Bip Chemicals Limited filed Critical Bip Chemicals Limited
Publication of WO1992009653A1 publication Critical patent/WO1992009653A1/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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts

Definitions

  • Thermoplastic polyesters are commonly used in moulding compositions, and when flame retardant grades are required they are typically flame retarded with additives containing halogens.
  • the level of flame retardancy obtained from such materials can be very good and VO ratings in the Underwriters (UL) Flammability test are readily achieved.
  • a problem with such compositions, however, is that the resistance to electrical tracking of thermoplastic polyesters containing these additives is very low. (Typical values of Comparative Tracking Index - CTI - for a UL VO material would be around 200 volts.) It has also been proposed to use red phosphorus as a flame retardant in PET and PBT compositions, whereby some improvement in electrical tracking resistance may be achieved.
  • US Patent No 4,314,927 proposes the use of red phosphorus and melamine cyanurate in moulding compositions of Nylon 66 to improve the heat stability and lower the level of phosphorus required to achieve VO ratings. It gives no guidance as to the electrical tracking resistance of the compounds disclosed.
  • red phosphorus and melamine cyanurate may be used together in glass reinforced thermoplastic polyester compositions to enhance both flame retardancy and electrical tracking resistance.
  • a polyester moulding composition comprises a thermoplastic polyester, reinforcing fibres and as fire retardant red phosphorus with melamine cyanurate.
  • the thermoplastic polyester may be, for example, polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) or a polyester containing at least 80 per cent by weight of repeating units derived from ethylene terephthalate or butylene terephthalate.
  • the amount of thermoplastic polyester in the composition is preferably in the ranee 35 to 75 per cent by weight of the total composition.
  • red phosphorus is an essential ingredient of the polyester moulding composition but the red phosphorus is preferably treated in order to reduce its handling difficulties, since red phosphorus alone can be ver dangerous in handling.
  • the red phosphorus ma ⁇ be carried on a polymeric carrier, and/or may be encapsulated ith a suitable substance such as a polymer or resin.
  • the amount of red phosphorus in the composition is 1 to 15 per cent by weight of the total composition.
  • the composition contains reinforcing fibres, for example short lengths of inorganic reinforcing fibre such as glass fibre, although other types of fibre which will stand up to the processing conditions to which the composition is subjected may be used.
  • the amount of reinforcing fibre in the composition is preferably in the range 15 per cent to 45 per cent by weight of the composition.
  • Fillers may also be used in the composition, for example kaolinitic clays, talc, glass spheres, wollastonite , calcium carbonate, and when used in conjunction with the reinforcing fibres have the advantage of giving a composition with less warping and less anisotropic properties.
  • the composition may also contain a nucleant and the nucleant may be either a metal salt of an organic acid, for example a metal stearate, acetate or benzoate, or a finely divided material which does not melt at or below the melting point of polyethylene terephthalate, for example microtalc.
  • the preferred nucleant is a group 1 metal stearate, or microtalc with a particle size of less than 20 microns.
  • the group 1 metal stearate is sodium stearate, which is a known nucleant for polyethylene terephthalate and gives easier nucleation of the polyester.
  • the nucleant is preferably used in an amount no more than 1% -by weight of the composition, particularly in the range 0.1 to 0.7 per cent by weight. However, if a finely divided solid nucleant is used it may be used in greater proportion, eg up to six parts by weight per 100 parts by weight total polymer, and may be used, if desired, in addition to a nucleant of the other type.
  • the melamine cyanurate functions to enhance the flame retardancy of the system with an important improvement in the electrical tracking resistance of the moulded composition.
  • the amount of melamine cyanurate used may be in the range from 1 per cent to 20 per cent, preferably 4 per cent to 15 per cent, by weight of the composition.
  • the method used was the standard Underwriters Laboratories test method UL94.
  • VO means that the specimens burnt for less than 10s after removal of flame, that the total burn time for ten applications of the flame on five specimens was less than 50 seconds.
  • no flaming drops are permitted.
  • VI classification no specimen burns for longer than 30 seconds after the application of the flame and the total burning time for 10 specimens is less than 250 seconds. No flaming drops are permitted.
  • the same criteria apply in V2 classification except that some flaming drops are permitted.
  • the average burning time for each application of flame was calculated and the occurrence of non-flaming drops was noted (10 specimens).
  • the test equipment used is that of the Comparative Tracking Index test of the European Standard IEC 112 (DIN 53480). An aqueous solution containing 0.1% NH Cl was dropped at 30 second intervals on to the surface of the mouldings between two electrodes carrying the applied voltage. Platinum electrodes were used, with trips at 0.5 amps and 2 sees.
  • PET polyethylene terephthalate
  • compositions were made by first blending the ingredients shown (as parts by weight) in Table I, and then fully compounded in a Baker Perkins twin-screw extruder. TABLE I
  • red phosphorus used (MASTERFLAM P70S) was encapsulated in a polyamide carrier (70% by weight of red phosphorus).
  • the glass fibres were grade 429YZ from Owens Corning Fibreglass, chop length 4.5mm.
  • the nucleant/mould release agent was NAI/LOXIOL masterbatch and the stabiliser was IRGAF0S PEPQ.
  • NAI is a nucleant/polymer (linear low density polythene) supplied by Goodyear.
  • L0XI0L is pentaer thritol tetrastearate supplied by Henkel.
  • Sample mouldings were made by injection moulding from each composition on a standard BIPEL 60/26 machine using a barrel temperature of 270°C.
  • compositions were made by first blending the ingredients shown (as parts by weight) in Table III, and then fully compounded in a Baker Perkins twin-screw extruder. TABLE III
  • red phosphorus used (MASTERFLAM P70S) was encapsulated in a polyamide carrier (70% by weight of red phosphorus).
  • the glass fibres were grade 429YZ from Owens Corning Fibreglass, chop length 4.5mm.
  • the nucleant/mould release agent was NAI/LOXIOL masterbatch and the stabiliser was IRGAF0S PEPQ.
  • NAI is a nucleant/polyraer (linear low density polythene) supplied by Goodyear.
  • L0XI0L is pentaerythritol tetrastearate supplied by Henkel.
  • Sample mouldings were made by injection moulding from each composition on a standard BIPEL 60/26 machine using a barrel temperature of 270°C.
  • Example 3 failed and Example 2 passed.

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)

Abstract

Composition de moulage constituée d'un polyester saturé tel que le polytéréphtalate d'éhtylène ou le polybutylène, associé à des fibres de renforcement et, à titre de système ignifuge, à du phosphore rouge avec du cyanurate de mélamine.
PCT/GB1991/002078 1990-11-27 1991-11-25 Ameliorations apportees aux compositions de polyester WO1992009653A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9025727.0 1990-11-27
GB909025727A GB9025727D0 (en) 1990-11-27 1990-11-27 Improvements in or relating to polyester compositions

Publications (1)

Publication Number Publication Date
WO1992009653A1 true WO1992009653A1 (fr) 1992-06-11

Family

ID=10686026

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/002078 WO1992009653A1 (fr) 1990-11-27 1991-11-25 Ameliorations apportees aux compositions de polyester

Country Status (2)

Country Link
GB (2) GB9025727D0 (fr)
WO (1) WO1992009653A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0835904A1 (fr) * 1996-04-30 1998-04-15 Toray Industries, Inc. Composition et moulages de resine ignifuge
WO1998017720A1 (fr) * 1996-10-21 1998-04-30 Basf Aktiengesellschaft Matieres de moulage ignifugees
BE1011168A3 (fr) * 1996-03-20 1999-06-01 Gen Electric Composition de polyester retardatrice d'inflammation.
EP0919591A1 (fr) † 1997-06-13 1999-06-02 Polyplastics Co. Ltd. Composition de resine polyester thermoplastique ignifuge
US10626199B2 (en) 2014-12-22 2020-04-21 Borealis Ag Process for producing polypropylene

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543447A (en) * 1994-09-28 1996-08-06 Southwest Research Institute Stabilization of red amorphous phosphorus by ordered polymeric structures for the manufacture of non-emissive fire retardant plastics
DE19643279A1 (de) * 1996-10-21 1998-04-23 Basf Ag Flammgeschützte Formmassen
DE19651471A1 (de) * 1996-12-11 1998-06-18 Clariant Gmbh Flammwidrige ungesättigte Polyesterharze
DE10226732A1 (de) 2002-06-14 2004-01-08 Clariant Gmbh Mischungen aus einem Phosphonit und anderen Komponenten
FR2851566B1 (fr) * 2003-02-26 2007-05-11 Hexcel Fabrics Renfort fibreux utile comme agent ignifugeant, son procede de fabrication et son utilisation
EP1719796A1 (fr) * 2005-05-03 2006-11-08 DSM IP Assets B.V. Compositions de polyester à mouler pour l'utilisation dans des dispositifs électriques
CN102775814B (zh) * 2012-08-10 2014-03-19 四川省精细化工研究设计院 一种制备微胶囊化红磷的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2126923A1 (en) * 1971-05-29 1972-11-30 Hoechst Ag Flame-resistant satd polyester compsns - contg red phosphorus
US4180496A (en) * 1977-01-17 1979-12-25 Nissan Chemical Industries Ltd. Melamine cyanurate as a flame retardant agent
EP0019768A1 (fr) * 1979-06-02 1980-12-10 BASF Aktiengesellschaft Compositions à mouler ignifugées chargées à base de polyamides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2126923A1 (en) * 1971-05-29 1972-11-30 Hoechst Ag Flame-resistant satd polyester compsns - contg red phosphorus
US4180496A (en) * 1977-01-17 1979-12-25 Nissan Chemical Industries Ltd. Melamine cyanurate as a flame retardant agent
EP0019768A1 (fr) * 1979-06-02 1980-12-10 BASF Aktiengesellschaft Compositions à mouler ignifugées chargées à base de polyamides

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1011168A3 (fr) * 1996-03-20 1999-06-01 Gen Electric Composition de polyester retardatrice d'inflammation.
EP0835904A1 (fr) * 1996-04-30 1998-04-15 Toray Industries, Inc. Composition et moulages de resine ignifuge
EP0835904A4 (fr) * 1996-04-30 2000-05-17 Toray Industries Composition et moulages de resine ignifuge
WO1998017720A1 (fr) * 1996-10-21 1998-04-30 Basf Aktiengesellschaft Matieres de moulage ignifugees
EP0919591A1 (fr) † 1997-06-13 1999-06-02 Polyplastics Co. Ltd. Composition de resine polyester thermoplastique ignifuge
EP0919591B2 (fr) † 1997-06-13 2008-05-21 Polyplastics Co., Ltd. Composition de resine polyester thermoplastique ignifuge
US10626199B2 (en) 2014-12-22 2020-04-21 Borealis Ag Process for producing polypropylene

Also Published As

Publication number Publication date
GB9025727D0 (en) 1991-01-09
GB2250291A (en) 1992-06-03
GB9124977D0 (en) 1992-01-22

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