EP1032729A1 - Flame-retardant materials - Google Patents
Flame-retardant materialsInfo
- Publication number
- EP1032729A1 EP1032729A1 EP98956905A EP98956905A EP1032729A1 EP 1032729 A1 EP1032729 A1 EP 1032729A1 EP 98956905 A EP98956905 A EP 98956905A EP 98956905 A EP98956905 A EP 98956905A EP 1032729 A1 EP1032729 A1 EP 1032729A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- flame
- polymer
- pipd
- retardant
- polymers
- 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.)
- Granted
Links
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 flame-retardant materials, and to the use of said 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.
- 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 pyridobis- oxazole.
- 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 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 2 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 mVmin 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.
- Example 3 Between 10.3 g and 11.5 g of a sample of AS-PIPD (PIPD as spun, hydrated PIPD), PIPD (non-hydrated PIPD), PBO-HM (high-modulus PBO), Twaron® (poly(p-phenyleneterephthalamide)), Nomex® (poly(m-phenylene- terephthalamide)), or PVC (polyvinylchloride with the stabilizers Phosflex 41 and zinc borate) was brought into a Cone calorimeter having a heat release of 75 kW/m 2 . The calorimeter has a heating mantle for constant heat transfer to a sample of standard size. A spark plug was used to generate sparks.
- AS-PIPD PIPD as spun, hydrated PIPD
- PIPD non-hydrated PIPD
- PBO-HM high-modulus PBO
- Twaron® poly(p-phenyleneterephthalamide)
- Nomex® poly(m-phenylene-
- 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 -ma)/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
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98956905A EP1032729B1 (en) | 1997-11-21 | 1998-10-26 | Flame-retardant materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97203642 | 1997-11-21 | ||
EP97203642 | 1997-11-21 | ||
PCT/EP1998/007007 WO1999027169A1 (en) | 1997-11-21 | 1998-10-26 | Flame-retardant materials |
EP98956905A EP1032729B1 (en) | 1997-11-21 | 1998-10-26 | Flame-retardant materials |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1032729A1 true EP1032729A1 (en) | 2000-09-06 |
EP1032729B1 EP1032729B1 (en) | 2005-04-13 |
Family
ID=26070334
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98956905A Expired - Lifetime EP1032729B1 (en) | 1997-11-21 | 1998-10-26 | Flame-retardant materials |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP1032729B1 (en) |
WO (1) | WO1999027169A1 (en) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006105228A1 (en) * | 2005-03-28 | 2006-10-05 | E. I. Du Pont De Nemours And Company | High inherent viscosity polymers and fibers therefrom |
CN101287865B (en) | 2005-03-28 | 2012-06-13 | 纳幕尔杜邦公司 | Fusion-free hydrolysis of polyphosphoric acid in spun multifilament yarns |
JP4769294B2 (en) | 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 | Method for subjecting polyphosphoric acid in a spun yarn to hydrolysis on a hot surface |
JP4769289B2 (en) | 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 | Method for subjecting polyphosphoric acid in molded articles to hydrolysis |
DE602006019570D1 (en) | 2005-03-28 | 2011-02-24 | Du Pont | PROCESS FOR REMOVING CATION FROM POLYARENAZOLE FIBERS |
EP1866467B1 (en) | 2005-03-28 | 2008-12-17 | E.I. Du Pont De Nemours And Company | Process for the production of polyarenazole yarn |
WO2006105226A1 (en) | 2005-03-28 | 2006-10-05 | E. I. Du Pont De Nemours And Company | Process for hydrolyzing polyphosphoric acid in a spun yarn |
US7683122B2 (en) | 2005-03-28 | 2010-03-23 | E. I. Du Pont De Nemours And Company | Processes for increasing polymer inherent viscosity |
KR101337050B1 (en) | 2005-03-28 | 2013-12-05 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Process for the production of polyareneazole polymer |
WO2006105227A1 (en) * | 2005-03-28 | 2006-10-05 | E. I. Du Pont De Nemours And Company | Thermal processes for increasing polyareneazole inherent viscosities |
CN101203638B (en) | 2005-03-28 | 2011-01-12 | 纳幕尔杜邦公司 | Processes for hydrolysis of polyphosphoric acid in polyareneazole filaments |
WO2006105076A2 (en) | 2005-03-28 | 2006-10-05 | E.I. Du Pont De Nemours And Company | Processes for preparing monomer complexes |
WO2006105229A1 (en) | 2005-03-28 | 2006-10-05 | E.I. Du Pont De Nemours And Company | Processes for preparing high inherent viscosity polyareneazoles using metal powders |
WO2006105230A1 (en) * | 2005-03-28 | 2006-10-05 | E. I. Du Pont De Nemours And Company | Process for the production of polyareneazole polymer |
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 |
KR20080075219A (en) * | 2005-12-08 | 2008-08-14 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Matrix free non-woven layer of polypyridazle short fiber |
US7829481B2 (en) * | 2005-12-16 | 2010-11-09 | E. I. Du Pont De Nemours And Company | Garments comprising high strength extreme thermal performance outer shell fabric of polybenzimidazole and polypyridobisimidazole fibers |
CN101466282A (en) * | 2005-12-16 | 2009-06-24 | 纳幕尔杜邦公司 | PIPD comfort fabrics and articles made therefrom |
DE602006012090D1 (en) * | 2005-12-16 | 2010-03-18 | Du Pont | HEATING CLOTHES WITH A UV-LIGHT TOLERANT OUTER TUBE OF POLYPYRIDOBISIMIDAZOL AND POLYBENZOBISOXAZOLE FIBERS |
CN101331182B (en) * | 2005-12-16 | 2011-06-08 | 纳幕尔杜邦公司 | Fabrics made from a blend of polypyridobisimidazole/flame-retardant treated cellulose fibers and articles made therefrom |
CN101330843B (en) * | 2005-12-16 | 2014-10-22 | 纳幕尔杜邦公司 | Garments comprising a flexible high thermal performance outer shell fabric of polybenzimidazole and polypyridobisimidazole fibers |
EP1968407B1 (en) * | 2005-12-16 | 2012-03-14 | E.I. Du Pont De Nemours And Company | Thermal performance garments comprising a bleach tolerant outer shell fabric of polypyridobisimidazole and polybenzobisoxazole fibers |
WO2007073539A1 (en) * | 2005-12-16 | 2007-06-28 | E.I. Du Pont De Nemours And Company | Thermal performance garments comprising an outer shell fabric of pipd and aramid fibers |
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 |
CN101341295B (en) | 2005-12-21 | 2011-01-26 | 纳幕尔杜邦公司 | Fibrillated polypyridobisimidazole floc |
KR101380526B1 (en) * | 2005-12-21 | 2014-04-11 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Polypyridobisimidazole pulp and a process for making same |
KR20080083168A (en) | 2005-12-21 | 2008-09-16 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Paper comprising pipd pulp and a process for making same |
CN101331271B (en) * | 2005-12-21 | 2011-08-03 | 纳幕尔杜邦公司 | Paper comprising pipd pulp and a process for making same |
CN101341294A (en) * | 2005-12-21 | 2009-01-07 | 纳幕尔杜邦公司 | Friction papers containing pipd fibers |
CN103588703B (en) * | 2013-11-29 | 2015-08-05 | 中蓝晨光化工研究设计院有限公司 | A kind of 2,3,5,6-4-aminopyridine method for production of phosphate salt |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69412250T2 (en) * | 1993-04-28 | 1999-02-11 | Akzo Nobel N.V., Arnheim/Arnhem | Rigid-rod polymer containing pyridobismidazoles |
-
1998
- 1998-10-26 WO PCT/EP1998/007007 patent/WO1999027169A1/en active IP Right Grant
- 1998-10-26 EP EP98956905A patent/EP1032729B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9927169A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1999027169A1 (en) | 1999-06-03 |
EP1032729B1 (en) | 2005-04-13 |
WO1999027169A8 (en) | 2000-09-14 |
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