EP0408627A1 - Matiere ignifuge combinee a du latex - Google Patents

Matiere ignifuge combinee a du latex

Info

Publication number
EP0408627A1
EP0408627A1 EP89904068A EP89904068A EP0408627A1 EP 0408627 A1 EP0408627 A1 EP 0408627A1 EP 89904068 A EP89904068 A EP 89904068A EP 89904068 A EP89904068 A EP 89904068A EP 0408627 A1 EP0408627 A1 EP 0408627A1
Authority
EP
European Patent Office
Prior art keywords
fire protection
fire
latex
event
protection 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.)
Pending
Application number
EP89904068A
Other languages
German (de)
English (en)
Inventor
Heinz Horacek
Hermann Wudy
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.)
Chemie Linz GmbH
Original Assignee
Chemie Linz GmbH
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 Chemie Linz GmbH filed Critical Chemie Linz GmbH
Publication of EP0408627A1 publication Critical patent/EP0408627A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials

Definitions

  • the invention relates to thermally expandable fire protection compositions or fire protection laminates which contain expanded graphite, a chloroprene latex containing carboxyl groups and substances which form a paracrystalline carbon structure in the event of fire, and a process for their production.
  • Thermally expandable fire protection compositions which consist of expanded graphite, chloroprene rubber, a phenolic resin, an organic solvent and optionally also aluminum hydroxide and inorganic fibers, are described in AT-PS 360.130, for example. They are particularly effective in preventive fire protection due to their excellent resistance to moisture, frost, warmth, light and industrial climate, as well as their high inflation pressure. When exposed to heat and fire, they expand in the opening to be protected in the event of a fire with a relatively low flowability. As a result, the expanding mass does not avoid obstacles even in an opening that is not completely closed, and due to its high inflation or expansion pressure, which is usually above 2 bar, forms a tightly sealing barrier layer, which prevents further spreading of heat, fire and smoke gases or delayed or completely prevented.
  • This sealing material has high mechanical strength even when expanded.
  • a disadvantage of the production, processing and use of such compositions is their brittleness and low flexibility.
  • a further disadvantage lies in the fact that organic solvents are used in their production, which require increased equipment and labor for solvent recovery and for minimizing environmental pollution and health hazards which may be caused by solvents.
  • the polymeric binder is either a flexible binder, e.g. B. polyvinyl acetate elastomeric binder, e.g. B. a chloroprene polymer, a thermosetting binder, e.g. B. a formaldehyde resin or a thermosetting binder with the addition of a flexible binder possible.
  • a flexible binder e.g. B. polyvinyl acetate elastomeric binder, e.g. B. a chloroprene polymer
  • a thermosetting binder e.g. B. a formaldehyde resin or a thermosetting binder with the addition of a flexible binder possible.
  • the object of the invention was to eliminate these disadvantages which occur with the known fire protection compositions and, above all, to obtain less brittle compositions which form a sufficiently stable and hard barrier layer in the event of a fire and in whose production no organic solvents are required.
  • the task was solved with a fire protection compound obtained by combining three specific components.
  • the present invention accordingly relates to a thermally expandable fire protection composition which is characterized in that it contains expanded graphite, a chloroprene latex with at least 0.3 moles of carboxyl groups per 1 kg of latex solid, in the event of fire a paracrystalline carbon structure, and, if appropriate, further additives.
  • the fire protection compositions do not contain organic solvents, but if aqueous latex dispersions are used in the production. Due to the existing residual water content, these fire protection compounds show a more favorable fire behavior than when using organic solvents. Because of the absence of organic solvents, they can be manufactured and processed much more simply and in a much more environmentally friendly manner.
  • the fire protection compositions according to the invention show good elasticity and flexibility primarily because of the content of elastomeric chloroprene polymer, so that they or from them produced laminates or sheets are easy to use, process and handle.
  • very high expansion pressures preferably above 5 bar, can be achieved in the event of a fire, and thus a particularly effective seal can be achieved.
  • the barrier layer formed after inflation is characterized by its strength, hardness and stability, so that it does not form cracks and is not destroyed by the thermal, mechanical and aerodynamic stresses and fire turbulence in the event of a fire.
  • the bio graphite used can be produced, for example, by acid treatment of a natural graphite with fuming nitric acid, as described in US Pat. No. 3,574,644 or in H. Spatzek, Carbon 86 (1986).
  • the chloroprene latex is usually made by copolymerizing chloroprene with acrylic acid or methacrylic acid.
  • latices are Skyprene (R) (Toyo Soda), Bayprene (R) (Bayer), Butaclor (R) (Distugil), Denka Chloroprene (R) (Druki Kagaku Kogyo), Nairit (R) (USSR) or Neoprene (R) (Du Pont) in stores.
  • the fire protection composition usually contains 25 to 60% by weight of expanded graphite, 5 to 25% by weight, calculated as a solid, of a chloroprene latex, 5 to 25% by weight of substances which form a paracrystalline carbon structure in the event of fire, and optionally additives.
  • Suitable substances that form a paracrystalline carbon structure in the event of fire are, for example, polyacrylonitrile, cellulose or their derivatives, phenol-formaldehyde resins, polyfurfuryl alcohol or polyimides. When heated in the event of a fire, these substances initially crosslink, the strong intermolecular bonds also being retained during further thermal stress, which leads to pyrolytic decomposition and ultimately to the formation of the paracrystalline carbon skeleton. (Chemie-Ing.-Techn. 42 No. 9/10 (1970), pp. 659-669). Three-dimensional cross-linked thermosets, such as phenolic resins, have proven to be particularly suitable. Phenolic resins with tertiary butyl groups, such as. B.
  • p-tert-butylphenol formaldehyde resin 7520E or 7522E from Rousselot show particularly good results.
  • Additives that modify the fire behavior are, for example, melamine and its derivatives, various graphite salts, cyanuric acid derivatives, dicyandiamide, halogenated hydrocarbons, polyammonium phosphates and guanidine salts. These substances also swell when decomposed when exposed to heat. Since they have a decomposition temperature that is different from expandable graphite, the expansion pressure also increases in the event of a fire, which means that the opening is firmer sealed.
  • additives that primarily improve the strength of the sealant in the expanded state, solidify the crust and increase cohesion, such as.
  • B. inorganic fibers such as mineral or glass fibers, glass powder, vermiculite, bentonite, silica, silicates, borax, starch, sugar, chlorinated paraffins, aluminum sulfate, aluminum hydroxide or magnesium hydroxide.
  • Flame retardants can also be added, for example halogenated or phosphorus-containing hydrocarbons, such as.
  • Additives that help increase foam formation in the event of flaming are also suitable. Examples include salicylic acid, p-hydroxybenzoic acid, PVC, and nitrogen or sulfohydrazides, triazoles, urea dicarboxylic anhydride and ammonium carbonate.
  • the fire protection composition according to the invention can be used both as a paste and in the form of plates, strips, tapes or moldings.
  • Fire protection laminates in which the fire protection composition is laminated onto a carrier web are particularly advantageous and simple to use.
  • the laminates or plates can be covered with a covering layer, for example a plastic film, e.g. B. a PVC film, paper or aluminum sheet, be covered on one or both sides. It is also possible to equip the fire protection laminates or panels with an adhesive layer, which is then advantageously covered with a separating film.
  • the fire protection compositions according to the invention are produced by mixing and homogenizing expanded graphite, a preferably aqueous latex dispersion containing carboxyl groups, and a paracrystalline dispersion in the event of fire Carbon skeletal substance, e.g. B. a phenol-formaldehyde resin or polyimide resin, and optionally other additives which modify the fire behavior, for example in a kneader, dissolver or mixer.
  • the mass obtained in this way can either be used as such, or it can be applied to a carrier web, for example to a film or a nonwoven (for example with the aid of a doctor blade. After drying, the laminate can be applied to a calender, possibly with Embossing roller are compressed, possibly with simultaneous lamination with a cover layer, for example made of PVC or aluminum.
  • the fire protection compositions according to the invention are used for fire protection sealing or sealing off openings in components forming a fire compartment, such as. B. joints between walls, cavities or spaces, wall openings, cable ducts or the like used. Door seals, window seals or other seals that foam up in the event of a fire and seal the upstream slot or opening can also be produced.
  • the connection between glass and frame in fire protection glazing with the aid of the fire protection compositions or laminates according to the invention also results in optimal fire protection. It is also possible to manufacture entire bricks with which openings for cables or pipes are lined and which form a barrier when exposed to fire. In the event of a fire, these materials foam up due to the effects of heat and seal the opening so that the further passage of fire and smoke and thus the further spread of the fire is prevented.
  • the starting materials listed in Tables 1 and 2 were added in a stirred tank in the following order: additives, Al (OH) 3 , phenolic resin, 50% aqueous chloroprene latex dispersion, expandable graphite, mineral fibers (Inorphil (R) 061- 60, GM Langer, FRG).
  • the mass was homogenized for 1 hour in a dissolver with a toothed disc at 30 ° C. and a pH of 10 (adjusted using KOH).
  • the viscosity was about 4 Pas, measured at 30 ° C in a Brookfield viscometer (spindle 7, 20 rpm).
  • the fire protection composition obtained was then knife-coated onto a glass fleece with a basis weight of 50 g / m 2 and dried at 190.degree.
  • the expanded graphite was obtained by acid treatment of a natural graphite with smoking the nitric acid.
  • Neoprene (R) 115 Du Pont: 0.33 mol COOH per 1 kg of 1 solid
  • Neoprene (R) 750 and Neoprene (R) 824A no COOH content
  • ayprene (R) 4R (Bayer) 0.23 Moles of COOH per 1 kg of latex solids.
  • Comparative Example V 16 a 10% chloroprene solution in toluene was used instead of the aqueous latex dispersion under otherwise identical conditions.
  • the properties of the fire protection laminates are also shown in Tables 1 and 2.
  • the expansion pressure was measured at 250 ° C. on samples with a diameter of 113 mm, which were placed between two heatable metal plates.
  • the pressure created during inflation was transferred from the lower plate to a force transducer with a pressure display.
  • the inflating material was not delimited on the side and could spread freely in the plane.
  • the head height was measured on samples with a diameter of 50 mm, which were placed in a metal cylinder with a height of 100 mm and an inner diameter of 50 mm.
  • the cylinder with the sample that is over a Stamp was preloaded with 100 g, was heated in an oven at 300 ° C for 10 minutes.
  • Latex solids 0.33 0.17 0 0.23 0.33 0.33 0.23 0
  • the lightweight concrete slab was then installed in a small fire chamber based on DIN 4102 and flamed from one side up to a temperature of around 1000 ° C according to the standard temperature curve.
  • the fire protection compounds began to expand after about 4 minutes due to the heat, whereby all 4 PVC pipes were softened and compressed.
  • the partitions with the laminates according to Example 13 were completely closed after 13 and 14 minutes, those with the laminates according to Comparative Example V 16 after 13 and 17 minutes, respectively, so that no more smoke, fire or soot escaped to the outside.
  • the outwardly protruding pipe stubs of the partitioning according to the invention began to break apart, while the pipe ends of the partitioning began to melt in accordance with the comparative example.
  • Example 13 After 60 minutes, the pipe stumps were completely broken off or melted off, the temperature of the expanded foam according to Example 13 was 290 ° C., that of the expanded foam according to Comparative Example V 16 at 310 and 370 ° C. The experiment was stopped after 80 minutes without flame or flue gas breakthroughs being ascertainable. It was also found that when the fire protection composition according to Example 13 was used on the side facing away from the fire, the temperature during the fire test was 20-80 ° C. lower than when the conventional fire protection composition according to Comparison Example V 16 was used.
  • the hardness of the expanded foam according to Example 13 was measured after cooling by means of a compressive strength test on a 4045 lasting device in accordance with DIN 53421 and was 0.2 N / mm 2 (60% compression).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Laminated Bodies (AREA)
  • Building Environments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Ceramic Products (AREA)
  • Inorganic Insulating Materials (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)

Abstract

Matière ignifuge thermiquement expansible comprenant du graphite expansé, un chloroprènelatex aqueux contenant des groupes carboxyles ainsi que des substances qui forment un squelette carboné paracristallin en cas d'incendie.
EP89904068A 1988-04-07 1989-04-07 Matiere ignifuge combinee a du latex Pending EP0408627A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT889/88 1988-04-07
AT0088988A AT392078B (de) 1988-04-07 1988-04-07 Latexgebundene brandschutzmasse

Publications (1)

Publication Number Publication Date
EP0408627A1 true EP0408627A1 (fr) 1991-01-23

Family

ID=3502167

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89904068A Pending EP0408627A1 (fr) 1988-04-07 1989-04-07 Matiere ignifuge combinee a du latex
EP89106154A Expired - Lifetime EP0338347B1 (fr) 1988-04-07 1989-04-07 Masse ignifugeante liée au latex

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89106154A Expired - Lifetime EP0338347B1 (fr) 1988-04-07 1989-04-07 Masse ignifugeante liée au latex

Country Status (14)

Country Link
EP (2) EP0408627A1 (fr)
JP (1) JP2775184B2 (fr)
KR (1) KR0139292B1 (fr)
AT (2) AT392078B (fr)
AU (1) AU615293B2 (fr)
DE (2) DE3813252A1 (fr)
DK (1) DK241890A (fr)
ES (1) ES2038361T3 (fr)
FI (1) FI99021C (fr)
GR (1) GR3003890T3 (fr)
HU (1) HU206739B (fr)
NO (1) NO300223B1 (fr)
RU (1) RU1838372C (fr)
WO (1) WO1989009808A1 (fr)

Families Citing this family (19)

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Publication number Priority date Publication date Assignee Title
DE69022570T2 (de) * 1990-01-10 1996-05-02 Minnesota Mining & Mfg Wässriges intumeszierendes Feuerschutz-Dichtungsmittel.
JPH0465443A (ja) * 1990-07-06 1992-03-02 Sanwa Kako Kk 不燃性架橋ポリオレフイン連続気泡体およびその製造方法
DE4135678A1 (de) * 1991-10-30 1993-05-06 Chemie Linz (Deutschland) Gmbh, 6200 Wiesbaden, De Thermisch expandierbare brandschutzmasse
AT403885B (de) * 1993-07-20 1998-06-25 Chemie Linz Gmbh Verfahren und vorrichtung zum verschliessen von wand- oder deckenöffnungen im brandfall
FR2736919A1 (fr) * 1995-07-04 1997-01-24 Lande Claude De Materiau composite ignifuge
DE19524373A1 (de) * 1995-07-04 1997-01-09 Schill & Seilacher Verfahren zur flammhemmenden Ausrüstung von Fasermatten und nach diesem Verfahren ausgerüstete Fasermatte
DE19653503A1 (de) * 1996-12-20 1998-06-25 Hilti Ag Intumeszierendes Material
DE19705736C1 (de) * 1997-02-14 1998-10-01 Kuhn Ag Dr Kombiniertes Dichtungs/Brandschutzprofil und Verfahren zu dessen Herstellung durch Koextrusion
DE19718876A1 (de) * 1997-05-03 1998-11-05 Kapp Chemie Gmbh Textile Feuer- und Thermosperren
DE29905167U1 (de) * 1999-03-20 1999-06-02 Gebrüder Trox, GmbH, 47506 Neukirchen-Vluyn Brandschutzklappe
US6747074B1 (en) 1999-03-26 2004-06-08 3M Innovative Properties Company Intumescent fire sealing composition
DE10009914A1 (de) * 2000-03-01 2001-09-06 Niemann Hans Dieter Fugenabdichtung eines Bauwerks und Verfahren zu deren Herstellung
DE102005003295A1 (de) * 2005-01-24 2006-07-27 Henkel Kgaa Abdichtfolie für den Bautenschutz
DE102011105304B4 (de) * 2011-06-22 2017-09-28 Diehl Defence Gmbh & Co. Kg Sperrelement zum Verschließen einer Öffnung
PL2885362T3 (pl) 2012-08-16 2017-04-28 Clariant International Ltd Trudnozapalna powłoka spodnia do dywanów
US9228093B2 (en) 2013-10-18 2016-01-05 Weyerhaeuser Nr Company Colored water-repellant and crocking-resistant compositions
WO2016013951A1 (fr) * 2014-07-21 2016-01-28 Общество С Ограниченной Ответственностью "Делси" Article d'extinction d'incendie pour la protection à titre préventif d'un objet contre le feu
EP3228366A4 (fr) * 2014-12-04 2018-03-07 Limited Liability Company "Rusintech" Micro-capsules, procédé de production, et agents, matériaux, revêtements et articles d'extinction d'incendie les comprenant
US20220275190A1 (en) * 2019-08-26 2022-09-01 Sekisui Chemical Co., Ltd. Heat-expanding fire retardant

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DE3515097C1 (de) * 1985-04-26 1986-09-18 Fa. Carl Freudenberg, 6940 Weinheim Selbsthaftende Beschichtung fuer Polypropylen-Schaumstoffe
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Also Published As

Publication number Publication date
DK241890D0 (da) 1990-10-05
EP0338347B1 (fr) 1992-02-26
EP0338347A1 (fr) 1989-10-25
AU3411989A (en) 1989-11-03
FI99021C (fi) 1997-09-25
KR0139292B1 (ko) 1998-04-28
KR900700578A (ko) 1990-08-16
FI904906A0 (fi) 1990-10-05
HUT55823A (en) 1991-06-28
HU206739B (en) 1992-12-28
FI99021B (fi) 1997-06-13
JP2775184B2 (ja) 1998-07-16
JPH03503654A (ja) 1991-08-15
WO1989009808A1 (fr) 1989-10-19
NO904231L (no) 1990-09-28
AU615293B2 (en) 1991-09-26
AT392078B (de) 1991-01-25
ES2038361T3 (es) 1993-07-16
GR3003890T3 (fr) 1993-03-16
ATE72824T1 (de) 1992-03-15
NO904231D0 (no) 1990-09-28
NO300223B1 (no) 1997-04-28
RU1838372C (ru) 1993-08-30
DE3813252A1 (de) 1989-11-09
DE58900844D1 (de) 1992-04-02
DK241890A (da) 1990-10-05
HU892232D0 (en) 1991-03-28
ATA88988A (de) 1990-07-15

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