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WO2008071719A1 - Polyamide résistant aux flammes et son procédé de fabrication - Google Patents

Polyamide résistant aux flammes et son procédé de fabrication Download PDF

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Publication number
WO2008071719A1
WO2008071719A1 PCT/EP2007/063744 EP2007063744W WO2008071719A1 WO 2008071719 A1 WO2008071719 A1 WO 2008071719A1 EP 2007063744 W EP2007063744 W EP 2007063744W WO 2008071719 A1 WO2008071719 A1 WO 2008071719A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
resin
hardener component
resistant polyamide
present
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/EP2007/063744
Other languages
German (de)
English (en)
Inventor
Dieter Lehmann
Frank Taeger
Anett MÜLLER
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.)
Leibniz Institut fuer Polymerforschung Dresden eV
Original Assignee
Leibniz Institut fuer Polymerforschung Dresden eV
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 Leibniz Institut fuer Polymerforschung Dresden eV filed Critical Leibniz Institut fuer Polymerforschung Dresden eV
Publication of WO2008071719A1 publication Critical patent/WO2008071719A1/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5377—Phosphinous compounds, e.g. R2=P—OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • the invention relates to the fields of chemistry and safety technology and relates to a flame-resistant polyamide, which can be used for example in the plastics processing and plastics industry as a component for housing, as fibers or as an electronic component and a method for its preparation.
  • polyamides In addition to good mechanical, thermal and electrical properties, polyamides have a considerable fire potential.
  • the fire cycle consists of thermal decomposition, diffusion of the pyrolysis gases, oxidation and heat release with simultaneous realization of the "Thermal Feedback". To break the fire cycle different mechanisms and groups of flame retardants for plastics are distinguished.
  • halogen-containing systems which may sometimes also contain two halogens in combination [US Pat. No. 4,111,134, US Pat. No. 4,388,429, US Pat. No. 5,358,991] and frequently synergistically reinforced with antimony trioxide, zinc borate, zinc oxide or other compounds [DE 2141036, DE 2114235], suppress combustion in the gas phase by initiating rapid radical reactions by emission of chemical species, which reduce the oxygen content in the immediate vicinity of the burning plastic.
  • intumescent flame retardants which are multicomponent systems and, besides compounds which tend to char, such as polyalcohols [G. Camino, L. Costa, G. Martinasso, Polym. Degr. Rod. 23 (1989) 359; 28 (1990) 17; US 2106938], from gas-forming blowing agents, such as melamine or melamine compounds [A. Mukherjee, Plast. Eng., (2001) 57, 42-46; SV Levchik, AI Balabanovich, GF Levchik, G. Camino, L. Costa, Polym. Degr. Rod.
  • the intumescent systems are closely related to flame retardants which act exclusively on the basis of phosphorus or phosphorus compounds.
  • the most important representatives are red phosphorus, ammonium polyphosphate or ammonium phosphates and organophosphinates [J.R.A. Broadbent, M.M. Hirschler, European Polymer Journal 11 (1987) 1087; J.E. Stevenson, R. Guest, Fire Safety Proceedings, Fire Retardant Chemicals Association, New La 1987, 141; DE 4015490; DE 2646218], which can sometimes be nanoscale (DE 10 2004 035517 A1).
  • polyols carbonise, but the polymeric substrates themselves and the insulating surface layer of carbon and polyphosphoric acid is not foamed by specially added propellant.
  • layer-forming systems are pyrolytic processes that, with the participation of anhydride and esterified phosphorus-oxygen compounds and elimination of water, result in relatively branched, highly condensed, carbon-rich organic structures to which the formation of the charred crust decreases significantly.
  • a disadvantage of these systems is a less effective flame retardancy compared to the halogen-containing materials, which requires high amounts of additive to meet given ratings. This negatively affects the mechanical parameters of the plastics. Furthermore, it is possible that decomposition reactions of flame retardant components occur during processing or in the application phase. As a result, both degradation processes on the polymeric matrix can be initiated and the electrical characteristics (insulation) of the materials can be changed.
  • Flame retardant solutions must always be tailored to specific plastics and optimized for the specific application, qualitatively and quantitatively.
  • Object of the present invention is to provide a flame-resistant polyamide, which has improved properties over conventional flame-retardant polyamides due to the low addition of a reactive resin-hardener system, and a simple and inexpensive process for its preparation.
  • the flameproof polyamide according to the invention consists of a polyamide matrix, from 0.1 to 30 Ma. -% of a flame retardant and from 0.1 to 20 Ma. % of a reactive resin-hardener component, wherein the resin-hardener component contains at least one resin and at least one hardener in the ratio of 100: 1 to 1:10, and the resin-hardener component is reactivated under fire conditions and at the Surface and forms a network in the near-surface regions of the polymer matrix.
  • the polyamides PA 6, PA 12, PA 6,6 are present.
  • a flame retardant layer-forming flame retardants are present, which are more advantageously hydroquinone Dehvate of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide.
  • the flame retardants are present in proportions of 0.1 to 30%.
  • phenol-formaldehyde condensates of the novolak type with phenol or cresol as aromatic structural units or melamine-formaldehyde resins are present.
  • polyoxymethylene is present as a hardener of the resin-hardener component.
  • the resin-hardener component, a catalyst or a catalyst mixture are added, which are still advantageously present as catalysts acid and / or base-splitting compounds such as decabromodiphenyl ether, ammonium polyphosphate or melamine cyanurate.
  • a resin and a curing agent which form a network as a resin hardener component under fire conditions on the surface and in the near-surface regions of the polymer matrix are mixed and in a proportion of 0.1 until 20 Ma. -% together with 0.1 to 30 Ma. - Compounded% of a flame retardant in a polymer matrix and a molding processed.
  • the mixture of the resin-hardener component is carried out at temperatures below the melting points of both materials.
  • a proportion of 0.1 to 5% of a catalyst or a catalyst mixture is added to the mixture.
  • the solution according to the invention is based on the compounding of a reactive resin-hardener component of varying composition, which substantially enhances the flame retardant effect of intumescent and non-intumescent layer-forming conventional flame retardants or of analogously acting additives.
  • the reactive resin-hardener component which is contained in a proportion of 0.1 to 20 Ma. % of the polyamide plastic is added, consists of a resin and a curing agent, wherein the reactive resin-hardener component, and in particular the curing agent, a catalyst or a catalyst mixture may be added.
  • the reactive resin-hardener component is activated and crosslinked immediately at the burning phase boundary on the surface and in the near-surface zones of the plastic. As a result, a region of high network density is formed on the surface of the thermoplastic polyamide matrix.
  • this hybrid layer acts as a particularly effective barrier to progression or re-flaring the fire process and thus has a pronounced potential for sustainable flame retardance. It is particularly advantageous if the flame retardant present in the polyamide or the analogously acting additive can be reactively integrated into the network formation of the reactive resin hardener component.
  • the chemical and physical stability of the reactive resin-hardener component ensures easy compounding into the thermoplastic polyamide matrix or further processing of the compounds.
  • novolak type phenol-formaldehyde condensates having phenol or cresol as aromatic structural units and melamine-formaldehyde resins are preferably used.
  • a hardener or a hardener-catalyst system is compounded, which remains under the processing conditions, however, in a deactivated, passive state and is activated only at the combustion temperatures under fire conditions and then leads to rapid crosslinking of the resin component.
  • the following substances or mixtures are used as hardeners or hardener catalyst systems.
  • the proportions between resin and hardener or hardener mixture vary from 100: 1 to 1:10 and depend on the specific polyamide, the attached compounded flame retardant and the desired classification in the fire behavior.
  • the crosslinking mechanisms proceed in the cases of use of the curing agents a), b) and c) via hydroxymethylation of the resin component by formaldehyde, the formaldehyde being released in upstream thermal decomposition processes of the polyoxymethylene and followed by condensation reactions between the oligomeric aromatics.
  • acidic pyrolysis of the DBDE under HBr formation
  • alkaline thermal decomposition of melamine cyanurate or ammonium polyphosphate with liberation of ammonia
  • the reactive resin-hardener component consists of inexpensive basic materials, a significant cost reduction results for the fulfillment of certain specified fire test criteria. Furthermore, a considerable reduction of the ecological and ecotoxicological risks is achieved. The reduction of the required additive concentration makes it possible to better maintain the property profiles of the polyamide plastics or to adjust the mechanical, electrical and thermal characteristics of the materials more independently of the flame retardant content. Since the reactive resin-hardener component is stable under processing conditions, the problems that partially occur during the compounding of the flame retardants or in the phase of the thermal shaping are avoided or weakened in their effect.
  • polyamide 12 In 500 g of polyamide 12 are mixed 40 g of the terephthalaldehyde Dehvates of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (DOPT) as a flame retardant additive and 10 g of a resin-hardener component, wherein the resin Hardener component of 67% by mass Kresolnovolak and 33% by mass of melamine cyanurate. Test specimens made from this material were extinguished 1 second after removing the Burner flame.
  • DOPT 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide

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

L'invention concerne le domaine de la chimie et notamment un polyamide résistant aux flammes pouvant par exemple être utilisé en tant que composant de construction, ainsi que son procédé de fabrication. L'objectif de la présente invention est de proposer un polyamide résistant aux flammes présentant des propriétés améliorées en comparaison des polyamides résistant aux flammes classiques. L'invention concerne donc un polyamide résistant aux flammes constitué d'une matrice polyamide, de 0,1 à 30 % en masse d'un agent ignifuge et de 0,1 à 20 % en masse d'un composant réactif durcisseur de résine, ledit composant durcisseur de résine formant un réseau à la surface et à proximité de la surface de la matrice polymère. L'invention concerne également un procédé selon lequel une résine et un agent de durcissement dans une proportion totale de 0,1 à 20 % en masse sont mélangés avec 0,1 à 30 % en masse d'un agent ignifuge dans une matrice polymère et travaillés pour former un élément moulé.
PCT/EP2007/063744 2006-12-13 2007-12-11 Polyamide résistant aux flammes et son procédé de fabrication Ceased WO2008071719A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610060339 DE102006060339A1 (de) 2006-12-13 2006-12-13 Flammfestes Polyamid und Verfahren zu seiner Herstellung
DE102006060339.7 2006-12-13

Publications (1)

Publication Number Publication Date
WO2008071719A1 true WO2008071719A1 (fr) 2008-06-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/063744 Ceased WO2008071719A1 (fr) 2006-12-13 2007-12-11 Polyamide résistant aux flammes et son procédé de fabrication

Country Status (2)

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DE (1) DE102006060339A1 (fr)
WO (1) WO2008071719A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110615882A (zh) * 2019-09-24 2019-12-27 浙江华峰热塑性聚氨酯有限公司 多羟基氮磷协同阻燃剂、阻燃pu热熔胶及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2978793B1 (fr) 2013-03-28 2017-05-10 Deutsche Institute für Textil- und Faserforschung Denkendorf Polyamide ininflammable, un procédé pour sa fabrication ainsi que son utilisation
DE102014109993A1 (de) 2013-07-16 2015-01-22 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Verfahren zur Herstellung von flammgeschützten Copolyamiden, die danach erhältlichen Polyamidgarne sowie deren Verwendung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0473032A1 (fr) * 1990-08-30 1992-03-04 Bayer Ag Utilisation de novolaques spécifiques dans des polyamides
EP0561548A1 (fr) * 1992-03-16 1993-09-22 Kyowa Chemical Industry Co., Ltd. Polyamide résistant à la flamme contenant un composant de résine et du pare flamme
JP2005132695A (ja) * 2003-10-31 2005-05-26 Dainippon Ink & Chem Inc 耐火物用組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2810549A1 (de) * 1978-03-10 1979-09-13 Bayer Ag Flammfeste polyamidformmassen
US6166114A (en) * 1998-08-13 2000-12-26 E. I. Du Pont De Nemours And Company Fire and electrical resistant compositions
US7022265B2 (en) * 2001-12-19 2006-04-04 E. I. Du Pont De Nemours And Company Polyamide resin compositions with electromagnetic interference shielding properties and articles formed therefrom

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0473032A1 (fr) * 1990-08-30 1992-03-04 Bayer Ag Utilisation de novolaques spécifiques dans des polyamides
EP0561548A1 (fr) * 1992-03-16 1993-09-22 Kyowa Chemical Industry Co., Ltd. Polyamide résistant à la flamme contenant un composant de résine et du pare flamme
JP2005132695A (ja) * 2003-10-31 2005-05-26 Dainippon Ink & Chem Inc 耐火物用組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110615882A (zh) * 2019-09-24 2019-12-27 浙江华峰热塑性聚氨酯有限公司 多羟基氮磷协同阻燃剂、阻燃pu热熔胶及其制备方法
CN110615882B (zh) * 2019-09-24 2022-09-02 浙江华峰热塑性聚氨酯有限公司 多羟基氮磷协同阻燃剂、阻燃pu热熔胶及其制备方法

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Publication number Publication date
DE102006060339A1 (de) 2008-06-19

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