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
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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
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Magellan Systems International LLC
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Filing date
Publication date
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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)

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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
US7906613B2 (en) 2005-03-28 2011-03-15 Magellan Systems International, Llc Process for removing cations from polyareneazole fiber
WO2006105231A1 (fr) 2005-03-28 2006-10-05 E. I. Du Pont De Nemours And Company Processus d'hydrolyse d'acide polyphosphorique dans des filaments de polyareneazole
US7683122B2 (en) 2005-03-28 2010-03-23 E. I. Du Pont De Nemours And Company Processes for increasing polymer inherent viscosity
CN101203636B (zh) 2005-03-28 2011-10-12 纳幕尔杜邦公司 使成型制品中的多磷酸水解的方法
WO2006105230A1 (fr) * 2005-03-28 2006-10-05 E. I. Du Pont De Nemours And Company Procede de production de fil de polyarene-azole
EP1866467B1 (fr) 2005-03-28 2008-12-17 E.I. Du Pont De Nemours And Company Procede de production d'un fil de polyareneazole
KR101324822B1 (ko) 2005-03-28 2013-11-01 마젤란 시스템즈 인터내셔날, 엘엘시 높은 고유 점도 중합체 및 그로부터의 섬유
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
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
JP5302674B2 (ja) * 2005-03-28 2013-10-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 金属粉末を使用する固有粘度が高いポリアレンアゾールの製造法
KR101337050B1 (ko) * 2005-03-28 2013-12-05 이 아이 듀폰 디 네모아 앤드 캄파니 폴리아렌아졸 중합체의 제조 방법
KR101337688B1 (ko) 2005-03-28 2013-12-06 마젤란 시스템즈 인터내셔날, 엘엘시 방사된 실 중의 폴리인산의 가수분해 방법
US7851584B2 (en) 2005-03-28 2010-12-14 E. I. Du Pont De Nemours And Company Process for preparing monomer complexes
ATE495289T1 (de) 2005-03-28 2011-01-15 Du Pont Heisse oberflächen-hydrolyse von polyphosphorsäure in spun-garnen
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
US8051494B2 (en) 2005-12-08 2011-11-08 E.I. Du Pont De Nemours And Company Matrix free non-woven layer of polypyridazle short fiber
EP1960464B1 (fr) * 2005-12-16 2011-06-08 E.I. Du Pont De Nemours And Company Tissus faits à partir d'un mélange de fibres de polypyridobisimidazole et de fibres cellulosiques ignifugées, et articles ainsi obtenus
JP4881393B2 (ja) * 2005-12-16 2012-02-22 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およびポリベンゾビスオキサゾール繊維の漂白剤耐性外面シェル布帛を含んでなる熱的性能被服
WO2007076270A2 (fr) * 2005-12-16 2007-07-05 E. I. Du Pont De Nemours And Company Vetements comprenant un tissus d'enveloppe exterieure de haute resistance et de tres haut rendement thermique, fait en fibres de polybenzimidazole et de polypyridobisimidazole
CN101330845B (zh) * 2005-12-16 2010-05-19 纳幕尔杜邦公司 包含pipd和芳族聚酰胺纤维外层面料的耐热性服装
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
JP4852107B2 (ja) * 2005-12-16 2012-01-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリベンゾイミダゾールおよびポリピリドビスイミダゾール繊維の可撓性高度熱的性能外面シェル布帛を含んでなる被服
US7829483B2 (en) * 2005-12-16 2010-11-09 E. I. Du Pont De Nemours And Company PIPD comfort fabrics and articled made therefrom
CN101341294A (zh) * 2005-12-21 2009-01-07 纳幕尔杜邦公司 包含pipd纤维的摩擦纸
CN101331270B (zh) * 2005-12-21 2012-09-05 纳幕尔杜邦公司 包含pipd纸浆的纸及其制造方法
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
WO2007076334A2 (fr) * 2005-12-21 2007-07-05 E. I. Du Pont De Nemours And Company Papier comprenant un floc de pipd et procédé de fabrication de celui-ci
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
WO2007076332A2 (fr) * 2005-12-21 2007-07-05 E. I. Du Pont De Nemours And Company Pulpe de polypyridobisimidazole a liaison spontanee et processus de fabrication correspondant
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2120042T3 (es) * 1993-04-28 1998-10-16 Akzo Nobel Nv Polimero de varilla rigida a base de piridobisimidazol.

Also Published As

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

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