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EP1032729B1 - Materiaux retardateurs de flamme - Google Patents

Materiaux retardateurs de flamme Download PDF

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Publication number
EP1032729B1
EP1032729B1 EP98956905A EP98956905A EP1032729B1 EP 1032729 B1 EP1032729 B1 EP 1032729B1 EP 98956905 A EP98956905 A EP 98956905A EP 98956905 A EP98956905 A EP 98956905A EP 1032729 B1 EP1032729 B1 EP 1032729B1
Authority
EP
European Patent Office
Prior art keywords
polymer
flame
pipd
hydrated
use according
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.)
Expired - Lifetime
Application number
EP98956905A
Other languages
German (de)
English (en)
Other versions
EP1032729A1 (fr
Inventor
Maurits Gerhard Northolt
Doetze Jakob Sikkema
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.)
Magellan Systems International LLC
Original Assignee
Magellan Systems International LLC
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 Magellan Systems International LLC filed Critical Magellan Systems International LLC
Priority to EP98956905A priority Critical patent/EP1032729B1/fr
Publication of EP1032729A1 publication Critical patent/EP1032729A1/fr
Application granted granted Critical
Publication of EP1032729B1 publication Critical patent/EP1032729B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Definitions

  • the invention pertains to the use of flame-retardant materials for the manufacture of flame-retardant composite material, non-woven material, fabric, film, foam, or paper.
  • spun fibers, films, foams, and injection-molded articles prepared from hydrates of polymers can be used for the manufacture of flame-retardant materials with a significant improvement over non-hydrated fibers, films, foams, or articles.
  • the fibers, films, foams, or injection-molded articles are preferably made of hydrates of hydroxy-containing polymers, more preferably hydroxy-containing rigid rod polymers, and, even more preferably, of hydrates of PIPD.
  • Rigid rod polymers based on pyridobisimidazole have been described, int.al., in US-A-4,533,692.
  • PIPD rigid rod polymers have been described in WO 94/25506.
  • At least 50% of the rigid rod polymers according to the present invention is composed of recurring groups of pyridobisimidazole-2,6-diyl(2,5-dihydroxy-p-phenylene), while in the remaining groups the 2,5-dihydroxy-p-phenylene is replaced by an arylene which may be substituted or not and/or the pyridobisimidazole is replaced by benzobisimidazole, benzobisthiazole, benzobisoxazole, pyridobisthiazole, and/or pyridobisoxazole.
  • arylene dicarboxylic acid such as isophthalic acid, terephthalic acid, 2,5-pyridine dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 2,6-quinoline dicarboxylic acid, and 2,6-bis(4-carboxyphenyl)pyridobisimidazole.
  • the polymer of the present invention is brought to the form of its hydrate by spinning of a solution of the polymer in a suitable solvent (for instance, polyphosphoric acid) into water or dilute phosphoric acid, made into a film or foam in the presence of water by methods common in the art, or brought to the form of its hydrate by injection-molding the polymer into water.
  • a suitable solvent for instance, polyphosphoric acid
  • the fibers are not or only partially dehydrated and, preferably, are used as such without undergoing any dehydrating heat treatment at all.
  • the hydrate content of the fiber, film, foam, or injection-molded article is >10 wt.%, preferably >20 wt.%, at 21 °C and 65% RH (relative humidity).
  • the polymer can maximally contain one molecule water per hydroxy group (for PIPD 21.4 wt.%), and for fibers, films, and foams usually somewhat more because of water contained in the voids (for PIPD the maximum total water content is up to 25 wt.%).
  • the hydrated fibers, films, foams, and articles are not heat treated and are used as such for the manufacture of composites, fabrics, non-wovens, papers, and the like. Products obtainable from the polymers preferably are made with 100% hydrated polymers.
  • the preparation of the PIPD homopolymer can be carried out by the incorporation, with vigorous stirring, of the salt of 2,5-dihydroxyterephthalic acid and tetraaminopyridine into strong polyphosphoric acid followed by heating (see WO 94/25506).
  • the polymer is then precipitated in water using a spinning arrangement, and washed with an alkaline solution, such as ammonia.
  • the mixture obtained from the polymerization reaction can be used directly for spinning or extrusion into fibers, films, foams, or tapes without any further measures or additions to the mixture being required, and thereafter used in composites, fabrics, and the like.
  • the polymer is prepared and spun or extruded in one continuous process
  • films, foams, or tapes can be made directly from the composition, which is obtained from the solution resulting from the polymerization reaction.
  • These objects such as fibers, tapes, foams, or films can be applied either as such and, hence, consist of the polymer of the present invention, or they can be used in combination with similar objects made of another material.
  • products can be made which comprise the objects of the present invention in combination with other materials.
  • the products may be applied as reinforcement material in products which are used at high temperatures, or where the temperature can increase and where flame-retardancy is a required property.
  • the fibers may be cut and used as staple fiber or, when fibrillated, as pulp, for instance, in paper making.
  • the thermal stability and the flame-retardancy of the polymer of the present invention were found to be very good, with very low loss of the mechanical characteristics of the fibers made thereof.
  • the materials of this invention can be applied in fire barrier articles (materials), such as suits worn by firemen and boundarymen aboard ships, battle helmets, flak vests, fire protection blankets, and the like.
  • fibers of the material of the present invention were tested using a Cone calorimeter. This test provides a good indication of several different characteristics, e.g., the peak heat release rate (PHRR), the time to ignition (TTI), the total specific extinction area (SEA), and the fire performance index (FPI).
  • PHRR peak heat release rate
  • TTI time to ignition
  • SEA total specific extinction area
  • FPI fire performance index
  • the polymer obtained from Example 1 with a polymer concentration of 14 wt.% was fed at a temperature of 195°C to a 0.6 m 1 metering pump by means of a 19 mm single screw extruder.
  • the polymer was passed through a 25 ⁇ m filter package and subsequently extruded at a throughput of 6.5 m 1 /min and a temperature of 205°C through a spinneret containing 40 spinning holes of a diameter of 100 ⁇ m.
  • Fibers were produced by a dry-jet-wet spinning technique, with water being used as the coagulation medium.
  • the air gap length was 20 mm, the draw ratio in the air gap 4.65.
  • the fibers were wound onto a bobbin, and washed with water for 48 hours, neutralized with ammonia, and washed again. These undried fibers (AS-PIPD) were used as such.
  • the PHRR which gives the maximum heat release
  • the TTI which is the time the sample needs from the start of the test to continuously burn
  • the SEA which is the total extinction of light measured by a laser and a receiver during the test
  • the FPI which is the fire performance index obtained by the quotient of TTI/PHRR
  • the heat absorption of various PIPD samples was measured with a Setaram C80D calorimeter.
  • An open cell using 1 g of material and a scan rate of 0.2 °C/min yielded scans from 30 to 200°C.
  • the scans show the specific heat as a function of temperature and the absorption of heat due to the evaporation of water from the open cell.
  • the test samples contained AS-PIPD (hydrated PIPD as spun), ASd-PIPD (dried PIPD as spun), HT-PIPD (heat treated partially hydrated PIPD), or HTd-PIPD (heat treated dried PIPD).
  • AS-PIPD hydrated PIPD as spun
  • ASd-PIPD dried PIPD as spun
  • HT-PIPD heat treated partially hydrated PIPD
  • HTd-PIPD heat treated dried PIPD
  • the water content of the hydrate of the hydroxy-containing rigid rod polymer was determined as follows: The mass (m b ) of a sample of the material is determined. The sample is then dried at 150°C at ⁇ 0.133 kPa during 16 to 20 h, after which the dry mass (m a ) of the sample is determined immediately. The water content is then calculated to be 100.(m b -m a )/m b %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un matériau retardateur de flamme préparé à partir d'hydrates de polymères pouvant s'utiliser pour la fabrication de matériaux retardateurs de flamme, tels que des composites, des tissus, des non-tissés, des films, des mousses, et du papier, avec une amélioration notable par rapport aux matériaux non hydratés. On utilisera de préférence des hydrates de polymères contenant hydroxy, et idéalement des polymères baguette rigides entièrement hydratés, notamment des fibres de PIPD entièrement hydratés.

Claims (7)

  1. Utilisation de fibres filées, de film, de mousse ou d'articles moulés par injection contenant un hydrate d'un polymère pouvant être obtenu par
    filage d'une solution d'un polymère contenant des hydroxyles dans l'eau ou l'acide phosphorique dilué en un article hydraté choisi parmi une fibre, un film et une mousse ou moulage par injection d'une solution d'un polymère contenant des hydroxyles dans l'eau en un article moulé par injection hydraté ; et
    facultativement, déshydratation de l'article hydraté en un article partiellement déshydraté avec une teneur en hydrate de plus de 10 % en poids à 21°C et 65 % H.R. ;
       pour la fabrication d'un matériau ignifuge.
  2. Utilisation selon la revendication 1 dans laquelle le polymère est un polymère contenant des hydroxyles.
  3. Utilisation selon la revendication 2 dans laquelle le polymère est un polymère en bâtonnet rigide contenant des hydroxyles.
  4. Utilisation selon la revendication 3 dans laquelle le polymère est le poly(2,6-diimidazo(4,5-b:4',5'-e]pyridinylène-1,4-(2,5-dihydroxy)phénylène (PIPD).
  5. Utilisation selon l'une quelconque des revendications 1 à 4 dans laquelle la teneur en hydrate est supérieure à 20 % en poids à 21°C et 65 % H.R.
  6. Utilisation selon l'une quelconque des revendications 1 à 5 dans laquelle le matériau ignifuge est un matériau composite, un matériau non-tissé, un tissu, un film, une mousse ou un papier.
  7. Utilisation selon l'une quelconque des revendications 1 à 5 appliquant des fibres filées pour la fabrication d'un article ignifuge.
EP98956905A 1997-11-21 1998-10-26 Materiaux retardateurs de flamme Expired - Lifetime EP1032729B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98956905A EP1032729B1 (fr) 1997-11-21 1998-10-26 Materiaux retardateurs de flamme

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP97203642 1997-11-21
EP97203642 1997-11-21
EP98956905A EP1032729B1 (fr) 1997-11-21 1998-10-26 Materiaux retardateurs de flamme
PCT/EP1998/007007 WO1999027169A1 (fr) 1997-11-21 1998-10-26 Materiaux retardateurs de flamme

Publications (2)

Publication Number Publication Date
EP1032729A1 EP1032729A1 (fr) 2000-09-06
EP1032729B1 true EP1032729B1 (fr) 2005-04-13

Family

ID=26070334

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98956905A Expired - Lifetime EP1032729B1 (fr) 1997-11-21 1998-10-26 Materiaux retardateurs de flamme

Country Status (2)

Country Link
EP (1) EP1032729B1 (fr)
WO (1) WO1999027169A1 (fr)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263221B2 (en) 2005-03-28 2012-09-11 Magellan Systems International, Llc High inherent viscosity polymers and fibers therefrom
WO2006105227A1 (fr) * 2005-03-28 2006-10-05 E. I. Du Pont De Nemours And Company Procede thermique destine a augmenter les viscosites inherentes des polyarene-azole
JP5036700B2 (ja) 2005-03-28 2012-09-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアレーンアゾール重合体の製造方法
JP4769293B2 (ja) 2005-03-28 2011-09-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリアレーンアゾールヤーンの製造方法
CN101203638B (zh) 2005-03-28 2011-01-12 纳幕尔杜邦公司 用于水解聚芳烃唑长丝中的多磷酸的方法
JP4769295B2 (ja) 2005-03-28 2011-09-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 紡績マルチフィラメントヤーン中のポリ燐酸に加水分解を融合無しに受けさせる方法
EP1863957B1 (fr) 2005-03-28 2012-06-13 E.I. Du Pont De Nemours And Company Procede d'hydrolyse d'acide polyphosphorique dans un file
US7851584B2 (en) 2005-03-28 2010-12-14 E. I. Du Pont De Nemours And Company Process for preparing monomer complexes
JP4769294B2 (ja) 2005-03-28 2011-09-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 紡績ヤーン中のポリ燐酸に熱表面上で加水分解を受けさせる方法
WO2006105230A1 (fr) * 2005-03-28 2006-10-05 E. I. Du Pont De Nemours And Company Procede de production de fil de polyarene-azole
US7683122B2 (en) 2005-03-28 2010-03-23 E. I. Du Pont De Nemours And Company Processes for increasing polymer inherent viscosity
ATE440980T1 (de) 2005-03-28 2009-09-15 Du Pont Verfahren zur hydrolyse von polyphosphorsäure in geformten artikeln
WO2006105078A1 (fr) 2005-03-28 2006-10-05 E.I. Du Pont De Nemours And Company Procede d’elimination des cations dans une fibre polyareneazole
DE602006004037D1 (de) 2005-03-28 2009-01-15 Du Pont Verfahren zur herstellung von polyarenazolen mit höher inhärenter viskosität unter verwendung von metallpulvern
US7888457B2 (en) 2005-04-01 2011-02-15 E. I. Du Pont De Nemours And Company Process for removing phosphorous from a fiber or yarn
JP2009520113A (ja) * 2005-12-08 2009-05-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー マトリックスを含まないポリピリダゾール短繊維の不織層
JP5219831B2 (ja) * 2005-12-16 2013-06-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリピリドビスイミダゾール／難燃処理されたセルロース繊維の配合物から作られた布帛およびそれから作られた物品
EP1973434B1 (fr) * 2005-12-16 2010-07-28 E.I. Du Pont De Nemours And Company Tissu confortable en pipd et articles fabriques a partir de ce tissu
WO2007076259A2 (fr) * 2005-12-16 2007-07-05 E.I. Du Pont De Nemours And Company Vetements comprenant un tissus d'enveloppe exterieure souple de tres haut rendement thermique en fibres de polybenzimidazole et de polypyridobisimidazole
DE602006011955D1 (de) * 2005-12-16 2010-03-11 Du Pont Kleidungsstücke aus einem hochfesten aussenschalengewebe mit extremer thermaler leistung aus polybenzimidazol- und polypyridobisimidazolfasern
EP1959773B1 (fr) * 2005-12-16 2009-11-11 E.I. Du Pont De Nemours And Company Vêtements présentant des propriétés thermiques composés d'un tissu de revêtement extérieur comprenant des fibres pipd et aramides
US7825049B2 (en) * 2005-12-16 2010-11-02 E.I. Du Pont De Nemours And Company Thermal performance garments comprising a bleach tolerant outer shell fabric of polypyridobisimidazole and polybenzobisoxazole fibers
EP1960575B1 (fr) * 2005-12-16 2010-01-27 E.I. Du Pont De Nemours And Company Vêtements présentant des propriétés thermiques composés d'un tissu de revêtement extérieur tolérant aux rayonnements uv comprenant des fibres de polypyridobisimidazole et de polybenzobisoxazole
JP5171638B2 (ja) * 2005-12-21 2013-03-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フィブリル化ポリピリドビスイミダゾールフロック
WO2007076335A2 (fr) * 2005-12-21 2007-07-05 E. I. Du Pont De Nemours And Company Papiers a friction contenant des fibres pipd
US7727358B2 (en) * 2005-12-21 2010-06-01 E.I. Du Pont De Nemours And Company Pulp comprising polypyridobisimidazole and other polymers and methods of making same
JP2009521621A (ja) * 2005-12-21 2009-06-04 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Ｐｉｐｄフロックを含んでなる紙およびその製造方法
US8137506B2 (en) 2005-12-21 2012-03-20 E. I. Du Pont De Nemours And Company Paper comprising PIPD pulp and process for making same
KR101380526B1 (ko) * 2005-12-21 2014-04-11 이 아이 듀폰 디 네모아 앤드 캄파니 폴리피리도비스이미다졸 펄프 및 이의 제조 방법
CN103588703B (zh) * 2013-11-29 2015-08-05 中蓝晨光化工研究设计院有限公司 一种2,3,5,6-四氨基吡啶磷酸盐的制备方法

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
CN1041208C (zh) * 1993-04-28 1998-12-16 阿克佐诺贝尔公司 吡啶并双咪唑基刚性棒形聚合物

Also Published As

Publication number Publication date
EP1032729A1 (fr) 2000-09-06
WO1999027169A1 (fr) 1999-06-03
WO1999027169A8 (fr) 2000-09-14

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