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WO1999011702A1 - Composition de polyester ignifuge - Google Patents

Composition de polyester ignifuge Download PDF

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Publication number
WO1999011702A1
WO1999011702A1 PCT/NL1998/000502 NL9800502W WO9911702A1 WO 1999011702 A1 WO1999011702 A1 WO 1999011702A1 NL 9800502 W NL9800502 W NL 9800502W WO 9911702 A1 WO9911702 A1 WO 9911702A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
retardant
thermoplastic polyester
reinforced
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/NL1998/000502
Other languages
English (en)
Inventor
Richerdes Johanna Mathilda Hulskotte
Johanna Gertruda Kersjes
Renier Henricus Maria Kierkels
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 AU90072/98A priority Critical patent/AU9007298A/en
Publication of WO1999011702A1 publication Critical patent/WO1999011702A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C08K5/16—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

  • the present invention relates to a flame-retardant , reinforced, thermoplastic polyester composition.
  • Such a composition is known, for example, from US 5618865.
  • This publication describes the use of melamine phosphate combined with a carbon-forming catalyst, or the use of melamine pyrophosphate as a flame retardant in reinforced, thermoplastic polyester compositions.
  • a drawback of melamine phosphate and melamine pyrophosphate is that the thermal stability of these compositions is low. As a result, preparation (compounding) and processing of the flame-retardant composition are limited to processes and applications that would be subject to elevated temperatures.
  • the invention's goal is a flame-retardant , reinforced, thermoplastic polyester composition with improved thermal stability. This is achieved because the polyester composition contains 5-50 wt.%, relative to the overall composition, of a salt of a 1, 3 , 5-triazine derivative and a polyphosphoric acid derivative as flame retardant.
  • the thermal stability of the composition according to the invention is substantially improved relative to the state of the art. It has surprisingly been found that the polyester in the composition according to the invention is less susceptible to degradation, which is advantageous with respect to the composition's mechanical properties. Another advantage of the composition of the invention is the improved processing stability. A further advantage of the composition of the invention is its excellent flame retardant behavior.
  • the flame retardant in the composition according to the invention is a salt of a 1, 3, 5-triazine derivative and a polyphosphoric acid derivative.
  • suitable 1, 3 , 5-triazine derivatives include 2 , 4, 6-triamine-l, 3 , 5-triazine (melamine) , melam, melem, melone, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine , diamine phenyl triazine, or mixtures hereof.
  • Melamine, melam, melem, or mixtures hereof are preferable. Melam and melem can be simply obtained by causing melamine to condense in the presence of a catalyst.
  • Crude melamine generally contains small amounts of melam and/or melem.
  • the polyphosphoric acid derivative of the salt of the 1, 3 , 5-triazine derivative is, for example, a partial ester of polyphosphoric acid, a salt of polyphosphoric acid or polyphosphoric acid itself.
  • Polyphosphoric acid is preferable.
  • Polyphosphoric acid can be represented by the following general formula:
  • n > 2.
  • n is between 2 and 200, and most preferably n is between 2 and 100.
  • Commercially available polyphosphoric acid is characterized by a P 2 0 5 content higher than 68 wt . % .
  • Polyphosphoric acid with a P 2 0 s content between 70 and 90 wt . % is preferable.
  • Most preferable is polyphosphoric acid with a P 2 0 5 content between 74 and 87 wt . % .
  • Examples of commercially available polyphosphoric acids are ALBRITER ® polyphosphoric acid 105, 111, 113, or 116.
  • the salt of the 1, 3 , 5-triazine derivative and the polyphosphoric acid derivative can be simply prepared by causing polyphosphoric acid to react with the triazine derivative, as described in PL 143704.
  • melamine polyphosphate can likewise be prepared by using phosphoric acid as a starting product instead of polyphosphoric acid, and subjecting the melamine salt obtained to the heat treatment described.
  • the concentration of the flame retardant in the composition of the invention is generally between 5 and 50 wt . % (relative to the overall composition), preferably between 10 and 40 wt.%, and most preferably between 15 and 35 wt.%.
  • thermoplastic polyester of the composition according to the invention can be chosen from the group comprising thermoplastic homopolyesters, thermoplastic copolyesters and/or thermoplastic polyester elastomers.
  • the thermoplastic homopolyesters and copolyesters can be obtained through self-polycondensation of hydroxycarboxylic acids or through polycondensation of one or more alkylene glycols and one or more dicarboxylic acids, preferably aromatic dicarboxylic acids .
  • aromatic dicarboxylic acids are preferably chosen from the group comprising phthalic acids, for example isophthalic and terephthalic acid, naphthalene dicarboxylic acids, for example 2, 6-naphthalene dicarboxylic acid, and diphenyl dicarboxylic acids, for example
  • thermoplastic polyester is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) . Most preferable is PBT.
  • Other thermoplastic polyesters that are very suitable for use in the composition according to the invention are polyalkylene adipates, poly ( ⁇ -caprolactone) , polyethylene naphthalate (PEN) , copolyester of ethylene glycol, terephthalic acid and isophthalic acid, and copolyesters of ethylene glycol, 2 , 6-naphthalene dicarboxylic acid and 4, 4 ' -diphenyl dicarboxylic acid.
  • thermoplastic polyester elastomers that are suitable for the invention are the usual thermoplastic copolyester elastomers according to the state of the art, which are, for example, extensively described in the Encyclopedia of Polymer Science and Engineering, Vol. 12, pages 75 et seg. (1988), and the references mentioned therein.
  • the hard segments in these thermoplastic copolyester elastomers generally consist of units derived from an aromatic dicarboxylic acid and an aliphatic dial, and the soft segments of polyester units derived from aliphatic dicarboxylic acids and aliphatic dials, or of lactones or soft segments of aliphatic polyether units.
  • Reinforcing materials are frequently added to thermoplastic polyester compositions to alter the mechanical properties.
  • the concentration of reinforcing materials in the composition of the invention may vary within a wide range and is partly determined by the level of mechanical properties desired. In general, the concentration of reinforcing materials in the composition of the invention will not amount to more than 60 wt.%, preferably 5-50 wt.%, and most preferably 15-35 wt.%.
  • the reinforcing material is chosen from the group of inorganic reinforcing materials, for example mica or glass fibers, or carbon fibers. Glass fibers are preferred.
  • the composition's flame-retardant effect can be further strengthened by the presence of a compound that is synergistic with respect to the flame retardant.
  • the synergist is generally a compound with several radicals that can esterify with the polyphosphoric acid, for example starch, glucose and compounds with at least two hydroxyl groups .
  • examples of compounds with at least two hydroxyl groups are alcohols with at least two hydroxyl groups, for example pentaerythritol, dipentaerythritol, tripentaerythritol and mixtures thereof .
  • the concentration of the synergistic compound with respect to the flame retardant is generally between 0 and 15 wt.% by weight, preferably between 0.1 and 10 wt.%.
  • composition's flame-retardant effect can be further strengthened by the presence of a second flame-retardant component.
  • a second flame-retardant component In principle all known flame retardants are suitable for this.
  • antimony oxide preferably antimony trioxide
  • alkaline earth metal oxides for example magnesium oxide and other metal oxides such as alumina, silica, iron oxide and manganese oxide
  • metal hydroxides for example aluminum hydroxide
  • metal borates for example zinc borate, and phosphorus-containing compounds.
  • Examples of phosphorus-containing compounds are zinc phosphate, ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, ethylene diamine phosphate, piperazine phosphate, piperazine pyrophosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine metaphosphate, guanidine phosphate, dicyanodiamide phosphate and urea phosphate.
  • the concentration thereof may vary within a wide range, but is generally not more than the concentration of the salt of 1, 3 , 5-triazine derivative and polyphosphoric acid.
  • composition may furthermore contain the other usual additives, for example stabilizers, mold - release agents, plasticizers , dispersing agents, colorants and/or pigments, etc., in amounts that are commonly suitable for these additives, providing the properties are not adversely affected.
  • additives for example stabilizers, mold - release agents, plasticizers , dispersing agents, colorants and/or pigments, etc.
  • composition according to the invention can be prepared using the conventional techniques known per se, for example by mixing all or a number of components in dry condition in a tumbler mixer, followed by melting in a melt mixer, for example a Brabender mixer or a single or twin-screw extruder.
  • a twin-screw extruder is used for mixing, melting, and extruding the ingredients.
  • composition of the invention can be fed to the extruder's throat together, or they can be fed at different places along the length of the extruder.
  • glass fibers are present in the composition, they are preferably not fed at the extruder's throat to prevent the risk of the glass fibers tearing.
  • Some of the components can be added in the form of a master batch in the thermoplastic polyester or a different polymer.
  • composition according to the invention can be processed into semi-finished or finished products using techniques commonly known to persons skilled in the art, such as injection-molding, compression-molding, blow-molding, or reactive injection-molding (RIM) .
  • injection-molding compression-molding
  • blow-molding blow-molding
  • RIM reactive injection-molding
  • Test bars were injection moulded.
  • the thermal stability of the flame retardant compound was excellent and therefore no foaming occured during injection moulding of the testbars .
  • Notched Charpy impact (ISO 180-1A) : 4 kg J/m 2
  • Unnotched Charpy impact (ISO 180-1C) : 8 kg J/m 2

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

Cette invention se rapporte à une composition de polyester thermoplastique renforcée ignifuge, qui contient 5 à 50 % en poids (par rapport à la totalité de la composition) d'un sel d'un dérivé de 1,3,5-triazine et de l'acide polyphosphorique (dérivé) comme agent ignifuge.
PCT/NL1998/000502 1997-09-04 1998-09-03 Composition de polyester ignifuge Ceased WO1999011702A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU90072/98A AU9007298A (en) 1997-09-04 1998-09-03 Flame-retardant polyester composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1006936 1997-09-04
NL1006936A NL1006936C2 (nl) 1997-09-04 1997-09-04 Vlamdovende polyestersamenstelling.

Publications (1)

Publication Number Publication Date
WO1999011702A1 true WO1999011702A1 (fr) 1999-03-11

Family

ID=19765610

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1998/000502 Ceased WO1999011702A1 (fr) 1997-09-04 1998-09-03 Composition de polyester ignifuge

Country Status (4)

Country Link
AU (1) AU9007298A (fr)
NL (1) NL1006936C2 (fr)
WO (1) WO1999011702A1 (fr)
ZA (1) ZA988080B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048778A1 (fr) * 1999-04-30 2000-11-02 Clariant GmbH Composition de revêtement ignifuge pour matériaux fibreux
WO2001081470A1 (fr) * 2000-04-19 2001-11-01 General Electric Company Compositions de polyester ignifuges
EP1142964A3 (fr) * 2000-03-30 2004-02-11 Clariant GmbH Revêtement ignifuge
EP1322702B2 (fr) † 2000-10-05 2014-04-02 Basf Se Composition ignifuge exempte d'halogene et composition polyamidique ignifuge
US11207863B2 (en) 2018-12-12 2021-12-28 Owens Corning Intellectual Capital, Llc Acoustic insulator
US11666199B2 (en) 2018-12-12 2023-06-06 Owens Corning Intellectual Capital, Llc Appliance with cellulose-based insulator
CN117586582A (zh) * 2024-01-18 2024-02-23 广东顺威赛特工程塑料开发有限公司 一种无卤耐候阻燃耐烧蚀聚丙烯复合材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0025082A2 (fr) * 1979-07-13 1981-03-18 Chemische Werke Hüls Ag Préparation d'un agent ignifuge solide, intumescent, contenant du phosphore, et son application dans des résines synthétiques
EP0241605A1 (fr) * 1984-10-30 1987-10-21 Marubishi Yuka Kogyo Kabushiki Kaisha Procédé de préparation d'un retardateur de flamme pour polyoléfines
PL143704B1 (en) * 1984-09-21 1988-03-31 Inst Chemii Nieorganicznej Method of obtaining melamine polyphosphate
WO1996009344A1 (fr) * 1994-09-21 1996-03-28 Dsm Melapur B.V. Composition de resine de polyamide ignifugee renforcee fibres de verre, comportant des produits de reaction d'acide phosphorique et de melamine ou de melem comme agents ignifugeants
WO1997044377A1 (fr) * 1996-05-22 1997-11-27 Nissan Chemical Industries, Ltd. Polymetaphosphate de melamine et procede pour sa production
WO1998045364A1 (fr) * 1997-04-07 1998-10-15 E.I. Du Pont De Nemours And Company Compositions de resine ignifuges

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0025082A2 (fr) * 1979-07-13 1981-03-18 Chemische Werke Hüls Ag Préparation d'un agent ignifuge solide, intumescent, contenant du phosphore, et son application dans des résines synthétiques
PL143704B1 (en) * 1984-09-21 1988-03-31 Inst Chemii Nieorganicznej Method of obtaining melamine polyphosphate
EP0241605A1 (fr) * 1984-10-30 1987-10-21 Marubishi Yuka Kogyo Kabushiki Kaisha Procédé de préparation d'un retardateur de flamme pour polyoléfines
WO1996009344A1 (fr) * 1994-09-21 1996-03-28 Dsm Melapur B.V. Composition de resine de polyamide ignifugee renforcee fibres de verre, comportant des produits de reaction d'acide phosphorique et de melamine ou de melem comme agents ignifugeants
WO1997044377A1 (fr) * 1996-05-22 1997-11-27 Nissan Chemical Industries, Ltd. Polymetaphosphate de melamine et procede pour sa production
WO1998045364A1 (fr) * 1997-04-07 1998-10-15 E.I. Du Pont De Nemours And Company Compositions de resine ignifuges

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 112, no. 6, 5 February 1990, Columbus, Ohio, US; abstract no. 37343, MUSZKO ET AL.: "Preparation of melamine polyphosphate" XP002065260 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048778A1 (fr) * 1999-04-30 2000-11-02 Clariant GmbH Composition de revêtement ignifuge pour matériaux fibreux
US6617382B1 (en) 1999-04-30 2003-09-09 Clariant Gmbh Flame-retardant coating for fiber materials
EP1142964A3 (fr) * 2000-03-30 2004-02-11 Clariant GmbH Revêtement ignifuge
WO2001081470A1 (fr) * 2000-04-19 2001-11-01 General Electric Company Compositions de polyester ignifuges
EP1322702B2 (fr) † 2000-10-05 2014-04-02 Basf Se Composition ignifuge exempte d'halogene et composition polyamidique ignifuge
US11207863B2 (en) 2018-12-12 2021-12-28 Owens Corning Intellectual Capital, Llc Acoustic insulator
US11666199B2 (en) 2018-12-12 2023-06-06 Owens Corning Intellectual Capital, Llc Appliance with cellulose-based insulator
CN117586582A (zh) * 2024-01-18 2024-02-23 广东顺威赛特工程塑料开发有限公司 一种无卤耐候阻燃耐烧蚀聚丙烯复合材料及其制备方法

Also Published As

Publication number Publication date
NL1006936C2 (nl) 1999-03-05
AU9007298A (en) 1999-03-22
ZA988080B (en) 1999-03-04

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