WO2002070622A1 - Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations - Google Patents

Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations Download PDF

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Publication number
WO2002070622A1
WO2002070622A1 PCT/US2002/006186 US0206186W WO02070622A1 WO 2002070622 A1 WO2002070622 A1 WO 2002070622A1 US 0206186 W US0206186 W US 0206186W WO 02070622 A1 WO02070622 A1 WO 02070622A1
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WO
WIPO (PCT)
Prior art keywords
composition
article
substrate
sheet
epoxy resin
Prior art date
Application number
PCT/US2002/006186
Other languages
English (en)
Inventor
Rubin Feldman
Edward W. Taylor, Jr.
Robert L. Bryant
Original Assignee
Nu-Chem, Inc.
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 Nu-Chem, Inc. filed Critical Nu-Chem, Inc.
Priority to US10/469,677 priority Critical patent/US20040147184A1/en
Priority to EP02725039A priority patent/EP1377645A4/fr
Priority to CA002439950A priority patent/CA2439950A1/fr
Publication of WO2002070622A1 publication Critical patent/WO2002070622A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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

  • This invention relates to thermal protective compositions which form chars when exposed to fire or other thermal extremes.
  • the invention is particularly well suited to use in epoxy resin, intumescent coatings for substrates and as novel intumescent sheets, but its usefulness is not limited thereto.
  • Background Art Various compositions are known which provide protection against fire and other thermal extremes, such as temperatures above about 300° C. Some of the compositions are foamed inorganic passive insulative compositions which protect merely by their low thermal conductivity and their thickness as applied. These include, for example, foamed cement or intumesced silicates.
  • the present invention is not concerned with such systems, but with systems which include a polymeric binder and which form a char when exposed to fire or hyperthermal conditions.
  • the char-forming compositions may operate by various modalities.
  • the compositions may be used in various forms, including thick film (mastic) coatings, thin film coatings, castings, extrusions, and others.
  • the compositions may include organic or inorganic binders and various additives.
  • Upon exposure to heat the compositions slowly lose weight as portions of the composition are volatilized, and a char is formed which provides a measure of protection against the transfer of heat energy.
  • the char is consumed by physical erosion and by chemical processes, primarily oxidation by oxygen in the air and by free radicals produced by the coating or otherwise in a fire environment, and protection is lost.
  • the length of time required for a given temperature rise across a predetermined thickness of the composition, under specified heat flux, environmental, and temperature conditions, is a measure of the effectiveness of the composition in providing thermal protection. When subjected to fire or other hyperthemnal conditions, different coatings behave differently.
  • Ablative coatings swell to less than twice their original thickness. They provide limited passive thermal protection, but they tend to produce dense chars having good physical and chemical resistance. Intumescent coatings swell to produce a char more than five times the original thickness of the coating. This char provides an insulative blanket which provides superior thermal efficiency, but at the cost of some of the physical and chemical properties of the ablative coatings.
  • the char of the intumescent materials tends to form coarse and irregular cell structures, cracks, and fissures as it expands, and the char may not expand uniformly at corners, leaving areas where the char provides far less protection than the average thermal protection of the underlying structure.
  • intumescent systems examples include silicate solutions or ammonium phosphate paints or mastic compositions such as those disclosed in Nielsen et al., U.S. Patent 2,680,077, Kaplan, U.S. Patent 3,284,216, Ward et al., U.S. Patent 4,529,467, or Deogon, U.S. Patent No. 5,591 ,791.
  • a third type of char-forming coating is a subliming coating disclosed in Feldman, U.S. Patent 3,849,178. When subjected to thermal extremes, these compositions both undergo an endothermic phase change and expand two to five times their original thickness to form a continuous porosity matrix. These coatings tend to be tougher than intumescent coatings. They provide far longer thermal protection than ablative coatings, frequently. longer than intumescent coatings, in part because the gasses formed by the endothermic phase change provide active cooling as they work their way through the open-cell matrix. These coatings may also have a tendency to crack and form voids and fissures.
  • the present invention relates primarily to the Feldman-type subliming compositions which undergo an endothermic phase change and swell two to five times their original thickness. Some aspects of the invention are also applicable to intumescent char-forming coatings.
  • thermal protective systems have long been formed as self-supporting shapes formed, for example, by molding or extruding a protective material similar to, or identical with, the foregoing coating materials.
  • Such free-standing systems are described, for example, in Feldman, United States Patent No. 4,493,945.
  • Such systems suffer from the considerable expense of casting, molding, or extruding the shapes, and from the fact that the shapes and sizes of each system must be determined prior to forming the shape.
  • mesh In both the coating systems and the free-standing systems, it is often useful to incorporate a mesh of some sort to strengthen the system.
  • Examples of such mesh are metal mesh and cloth mesh such as fiberglass or graphite mesh.
  • the mesh may be formed in many known ways, such as weaving and knitting.
  • the term "mesh” is used broadly herein to include any perforate material.
  • the materials are first applied to a reinforcing structure such as a flexible tape or flexible wire mesh, and the combined structure is applied to the substrate.
  • a reinforcing structure such as a flexible tape or flexible wire mesh
  • Examples of this approach are found in Feldman, U.S. Pat. No. 3,022,190, Pedlow, U.S. Pat. No. 4,018,962,
  • the purpose of the reinforcing structure may be both to strengthen the resulting composite and to permit its application to a substrate without directly spraying, troweling or painting the uncured coating materials onto the substrate.
  • multiple layers are frequently applied to the substrate to provide additional protection.
  • a thermal protective composition which when exposed to flame or thermal extreme exhibits a volume increase through the formation of an expanded char, the composition comprising a flexible epoxy resin, the resin being internally flexibilized with soft resin segments contributing to the overall flexibility of the resin.
  • the composition preferably includes a component which volatilizes at fixed temperatures to absorb and block heat.
  • the composition responds to hyperthermal conditions with a small volume increase of two to five times its initial thickness to form an open cell matrix.
  • the internally flexibilized epoxy resins which are useful in the present invention are widely available.
  • the resins have sufficient flexibility that a flat 175 mil (4.5 mm) sheet of the material can be rolled by hand around a one inch (25.4 mm) pipe at room temperature (23° C).
  • Internally flexibilized epoxy resins have been known for many years, as evidenced by Sellers, et al, United States Patent 3,522,210.
  • the internally flexibilized epoxy resin's soft resin segments are preferably alkylene or oxyalkylene units. Representative of such resins are a butyl glycidyl ether-modified bisphenol A diglycidyl ether epoxy resin having an epoxy equivalent of about 310 to about 390 sold by Ciba Geigy Ltd.
  • the preferred compositions of the invention comprise a part A including the internally flexibilized epoxy resin and a part B including a polysulfide, most preferably a polymer of bis-(ethylene oxy)methane containing disulfide linkages and curable terminal thiol groups.
  • the two part system of the preferred compositions includes a curing agent.
  • An amine curing agent is preferred.
  • the preferred compositions also include gas formers such as polyol spumifics, amine blowing agents, and phosphate acid producers.
  • the composition includes from about 20% to about 65% polysulfide-modified flexible epoxy resin, more preferably about 40% to about 60% polysulfide-modified flexible epoxy resin.
  • the composition is in the form of a sheet of material about two to about thirty millimeters thick, more preferably about 3-15 mm thick, most preferably about 3-10 mm thick.
  • Other additives may be included in the composition for their known properties.
  • boron or zinc may be included in the composition or incorporated in a surface layer.
  • Fillers may be included for their known properties.
  • a lower layer in accordance with the invention may be of a different composition, but it is preferred that the ablative material includes an internally flexibilized epoxy resin.
  • the upper layer in these embodiments, forms an open cell matrix when exposed to a jet fire to permit passage of gasses from the lower layer to ambient.
  • compositions of the present invention have outstanding adhesive qualities. They are therefore well adapted to direct application to a substrate by standard methods such as spraying, troweling, or rolling. In accordance with preferred embodiments of the invention, they can also be formed into sheets by applying them to a surface having a mold release agent applied to it. Because the cured compositions of the present invention, unlike conventional epoxy resins, can be wrapped around a small pipe, having a diameter of 1" (25.4 mm) or less, the sheets can be wrapped around almost any substrate, particularly structural substrates. The sheets can therefore be easily adapted to protecting structures of almost any size or shape. They can be used with standoffs, or they can be adhered to the substrate with a contact cement, or preferably with a thin layer of the uncured composition itself.
  • the sheet When wrapped around a substrate, the sheet is preferably adhered to the substrate and the ends of the sheet are held to each other by overlapping and securing with a mechanical fastener as by stapling.
  • the flexible properties of the sheets also make the sheets useable by themselves as free standing structural elements. They can, for example, be bent into substantially rectangular cross sections and used without little or no underlying structure as cable trays.
  • the ability of the sheets of the present invention to bend around relatively sharp corners greatly reduces the labor required to install fire- protective sheets around columns, beams, cable trays, and other structural elements.
  • ordinary fire protective sheets or boards When ordinary fire protective sheets or boards are bent around corners, they must be scored before they are bent, and the scored edges filled with additional material.
  • the sheets of the present invention do not require scoring to be bent around corners and thus eliminate the need to fill the edges.
  • the coatings and structures of the present invention may include a mesh reinforcing layer, preferably embedded in the composition.
  • a mesh reinforcing layer preferably embedded in the composition.
  • Fiberglass and graphite fabrics are presently favored as the mesh, although flexible ceramic fabrics, metal mesh and other types of mesh may also be used.
  • a flexible sheet having a thickness of 0.175" (4.5 mm) wrapped around a 1.5" (38.1 mm) solid rod provides over 51 minutes of protection against a 900° C standard fire (maximum temperature rise to 400° C in a furnace rising to 500° C in five minutes, 700° C in ten minutes, 800° C in twenty minutes, and 900° in forty-six minutes).
  • Figure 1 is a graph showing average furnace temperature and average sample temperature of a 1.5" (38.1 mm) diameter solid metal rod protected by a 0.175" (4.5 mm) sheet of the present invention, wrapped around the rod.
  • a composition of the present invention was prepared containing a two-component epoxy.
  • the composition is formulated to be thermally activated by flame or thermal extreme; it volatilizes at fixed temperatures, exhibiting a small volume increase through the formation of an open cell matrix, and absorbs and blocks heat to protect the substrate material.
  • the composition included a polyfunctional alcohol, a 1 ,3,5-triazine-2,4,6-triamine, an internally flexibilized epoxy resin and a polymer of bis-(ethylene oxy)methane containing disulfide linkages and curable terminal thiol groups (a polysulfide).
  • the composition had a nominal formula as follows:
  • Catalyst 5 The composition was spread on a plate (previously coated with a standard release agent) to a nominal thickness of 0.175" (4.5 mm). A graphite fabric was pressed into the layer of material before it set. The layer was allowed to cure at 30° C. for one month.
  • a test article was prepared by coating a solid 1.5" (38.1 mm) diameter metal rod with a contact adhesive.
  • the sheet of EXAMPLE 1 was wrapped around the rod, and the excess was cut off, leaving a small overlap.
  • the overlap was stapled to the underlying sheet, and the stapled area was filled with uncured composition of EXAMPLE 1.
  • the test article was cured for about sixteen hours.
  • test article prepared in accordance with EXAMPLE 2 was exposed to a simulated fire in accordance with the conditions of ASTM E-119. The actual conditions are shown in FIGURE 1. The test showed that the system provided approximately fifty-one minutes of protection under the conditions of the test.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une préparation intumescente souple de protection d'un substrat contre le feu et les extrêmes thermiques comportant un liant époxydique assoupli de manière interne, un agent de carbonification, un agent de formation de mousse, un catalyseur et des additifs de préférence. Ces préparations peuvent servir de revêtements ou être mises en forme, de préférence des feuilles qui sont appliquées à ou enveloppées autour du substrat. Les feuilles peuvent adhérer au substrat et les extrémités des feuilles enveloppées peuvent être agrafées ou alors fixées les unes aux autres.
PCT/US2002/006186 2001-03-02 2002-03-01 Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations WO2002070622A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/469,677 US20040147184A1 (en) 2002-03-01 2002-03-01 Flexible thermal protective compositions and coatings and structures formed with them
EP02725039A EP1377645A4 (fr) 2001-03-02 2002-03-01 Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations
CA002439950A CA2439950A1 (fr) 2001-03-02 2002-03-01 Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27318401P 2001-03-02 2001-03-02
US60/273,184 2001-03-02

Publications (1)

Publication Number Publication Date
WO2002070622A1 true WO2002070622A1 (fr) 2002-09-12

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PCT/US2002/006186 WO2002070622A1 (fr) 2001-03-02 2002-03-01 Preparations protectrices thermiques souples, revetements et structures composees a partir desdites preparations

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EP (1) EP1377645A4 (fr)
CA (1) CA2439950A1 (fr)
WO (1) WO2002070622A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014095502A1 (fr) * 2012-12-18 2014-06-26 Hilti Aktiengesellschaft Composition formant une couche isolante et utilisation de ladite composition
US10138421B2 (en) 2013-11-12 2018-11-27 3M Innovative Properties Company Hot melt intumescent materials for fire protection

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2796032A1 (fr) * 2010-04-13 2011-10-20 3M Innovative Properties Company Bandes fibreuses inorganiques et procedes de fabrication et d'utilisation
AU2022260108A1 (en) * 2021-04-20 2023-11-16 Akzo Nobel Coatings International B.V. Heat resistant coating composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529467A (en) * 1983-10-25 1985-07-16 Ppg Industries, Inc. Fire protective intumescent mastic composition and method employing same
US5404687A (en) * 1991-04-24 1995-04-11 Avco Corporation Intumescent fireproofing panel system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108832A (en) * 1990-09-28 1992-04-28 Ppg Industries, Inc. Flexible intumescent coating composition
EP0682732B1 (fr) * 1993-02-08 2001-03-14 Thermal Science, Inc. Systeme de protection thermique renforcee
US5372846A (en) * 1993-05-05 1994-12-13 Nu-Chem, Inc. Heat blocking materials and methods
EP0956323B1 (fr) * 1996-07-08 2003-10-29 Nu-Chem, Inc. Compositions de protection thermique contenant du platine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529467A (en) * 1983-10-25 1985-07-16 Ppg Industries, Inc. Fire protective intumescent mastic composition and method employing same
US5404687A (en) * 1991-04-24 1995-04-11 Avco Corporation Intumescent fireproofing panel system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1377645A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014095502A1 (fr) * 2012-12-18 2014-06-26 Hilti Aktiengesellschaft Composition formant une couche isolante et utilisation de ladite composition
RU2650148C2 (ru) * 2012-12-18 2018-04-09 Хильти Акциенгезельшафт Образующая изоляционный слой композиция и ее применение
US10000659B2 (en) 2012-12-18 2018-06-19 Hilti Aktiengesellschaft Insulating layer-forming composition and use thereof
US10138421B2 (en) 2013-11-12 2018-11-27 3M Innovative Properties Company Hot melt intumescent materials for fire protection
US10683457B2 (en) 2013-11-12 2020-06-16 3M Innovative Properties Company Solid composite intumescent structures for fire protection

Also Published As

Publication number Publication date
EP1377645A4 (fr) 2006-05-31
EP1377645A1 (fr) 2004-01-07
CA2439950A1 (fr) 2002-09-12

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