WO2002049836A1 - Compositions expansibles stables au stockage - Google Patents

Compositions expansibles stables au stockage Download PDF

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Publication number
WO2002049836A1
WO2002049836A1 PCT/US2001/045000 US0145000W WO0249836A1 WO 2002049836 A1 WO2002049836 A1 WO 2002049836A1 US 0145000 W US0145000 W US 0145000W WO 0249836 A1 WO0249836 A1 WO 0249836A1
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WO
WIPO (PCT)
Prior art keywords
thermosettable composition
thermosettable
composition
cavity
temperature
Prior art date
Application number
PCT/US2001/045000
Other languages
English (en)
Inventor
Bruce Lee Harrison
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU2002219981A priority Critical patent/AU2002219981A1/en
Publication of WO2002049836A1 publication Critical patent/WO2002049836A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2421/00—Characterised by the use of unspecified rubbers

Definitions

  • the invention pertains to storage-stable foamable compositions based on epoxy resins. More specifically, particular curing accelerators are utilized to obtain one-component thermosettable compositions which exhibit improved stability both at room temperature and at moderately elevated processing temperatures over prolonged periods of time, yet which can be quickly activated at surprisingly low temperatures to provide foams capable of strengthening and stiffening hollow metal parts and the like. Discussion of the Related Art
  • a foam precursor composition is placed during vehicle assembly in the portion of the hollow part where reinforcement is desired, either by pumping or by means of a carrier or support inserted into the hollow part.
  • the composition is formulated to foam and cure when the vehicle is thereafter placed in a paint cure oven.
  • foamable compositions comprise a thermosettable resin such as an epoxy resin, a blowing agent and a filler.
  • these foams have a density of about 20-40 lb/ft 3 (about 0.30-0.65 g/cc) and are able to withstand heat in excess of 175°O, more preferably in excess of 200°C.
  • Optional ingredients include accelerators, curing agents, processing aids, stabilizers, colorants, and UV absorbers.
  • Foamable thermosettable compositions such as, e.g., TEROCORE® (a product of Henkel Surface Technologies), are now used in a variety of industries.
  • thermosettable composition in accordance with WO 00/12595 which has been introduced into a hollow section near the base of a vehicle (such as, for example, a lower rail section) may not completely foam and cure within the time the vehicle remains in the paint cure oven since the oven temperature in the region where such hollow section is located may be only 120°C to 135°C.
  • thermosettable composition that not only remains stable during prolonged storage at temperatures up to 55°C but is capable of being foamed and cured within a short period of time upon being exposed to a temperature in the range of about 120°C to about 135°C. Additionally, it would be advantageous if such compositions also were stable at 80°C for at least 24 hours, as in certain applications the composition may need to be processed at such temperatures (for example, where the composition is to be applied by pumping or where the composition is to be molded or extruded and its viscosity at ambient temperatures is excessive).
  • thermosettable compositions used to prepare structural reinforcement foams may be effectively alleviated through the use of boron halide amine adducts (especially boron trichloride amine adducts) as curatives.
  • boron halide amine adducts especially boron trichloride amine adducts
  • thermosettable compositions containing such adducts are able to be quickly cured and foamed upon heating to a temperature which is only moderately elevated (120°C to 135°C).
  • curatives such as amine-epoxy adducts which are activated at temperatures of 150°C or higher.
  • thermosettable compositions comprising: (a) at least one epoxy resin;
  • At least one curative which is a boron halide amine adduct (preferably, a boron trichloride amine adduct);
  • thermosettable composition is stable at 55°C for a period of at least 1 week and at 80°C for a period of at least 1 day and is curable and foamable within about 10 minutes upon being exposed a temperature in the range of about 120°C to about 135°C.
  • stable means that the viscosity and the specific gravity do not change by more than 20% from their initial values over the applicable time period.
  • thermosettable compositions of the present invention are cured using amine adducts (also referred to as "complexes") of boron trihalides such as boron trichloride. It is critical to use the boron trihalides in adduct form, as uncomplexed boron trichloride, for example, is a corrosive gas at room temperature which would be difficult to contain within the thermosettable composition during storage and handling.
  • thermosettable compositions rather than boron t fluoride amine adducts are greatly preferred for use in the present invention due to the tendency for the latter substances to initiate more pronounced exotherms in thermosettable compositions than the boron trichloride analogues.
  • This problem is especially severe when a large mass of thermosettable composition is being utilized; burning, charring and non-uniform expansion of the thermosettable composition takes place, creating large holes or voids in the foam produced.
  • Critical physical properties such as modulus and compression strength are thereby adversely affected.
  • boron trihalide amine adducts are the only curatives present in the thermosettable compositions.
  • minor amounts of other curatives may also be utilized in combination with the boron trihalide amine adducts provided such additional curatives do not interfere with the desired storage and processing stability of the thermosettable composition.
  • about 0.05 to about 1.0 weight % of a guanidine such as dicyandiamide may be incorporated in the thermosettable composition.
  • the post-cure odor may be adversely affected by the presence of curatives other than boron trihalide amine adducts.
  • the amount of boron trihalide amine adduct must be selected to be sufficient to initiate curing and cross-linking of the thermosettable composition within a preselected period of time (typically, within about 10 minutes) when exposed to a temperature within the range of from about 120°C to about 135°C.
  • the precise amount used is otherwise not believed to be critical and will vary somewhat depending upon a number of factors, including, for example, the reactivity of the particular epoxy resin(s) and other components present in the thermosettable composition.
  • the concentration of boron trihalide amine adduct will vary from about 0.2 to about 5 weight % of the thermosettable composition (more preferably, about 0.5 to about 3.5 weight %).
  • the amine component may be a primary, secondary, or tertiary amine; combinations of different amines may also be employed.
  • the amine may be substituted with aliphatic, and/or aryl, and/or arylalkyl groups and may be a heterocyclic compound.
  • the amine component should be selected to impart the desired degree of storage and processing stability as well as the desired activation temperature and curing time to the termosettable composition.
  • thermosettable resins having an average of more than one (preferably about two or more) epoxy groups per molecule known or referred to in the art may be utilized as the epoxy resin component of the present invention.
  • Epoxy resins are described, for example, in the chapter entitled "Epoxy Resins" in the Second Edition of the Encyclopedia of Polymer Science and Engineering, Volume 6, pp. 322-382 (1986).
  • Exemplary epoxy resins include polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with haloepoxides such as epichlorohydrin; glycidylether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid or beta-hydroxy naphthoic acid with epichlorohydrin or the like; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid or terephthalic acid with epichlorohydrin or the like; epoxidated phenolic-novalac resins (sometimes also
  • epoxy resins may be used if so desired; for example, mixtures of liquid (at room temperature), semi-solid, and/or solid epoxy resins can be employed. Any of the epoxy resins available from commercial sources are suitable for use in the present invention. Preferably, the epoxy resin has an epoxide equivalent molecular weight of from about 150 to about 1000.
  • the use of epoxy resins based on glycidyl ethers of bisphenol A is especially advantageous. Such epoxy resins are commercially produced by the reaction of bisphenol A with epichlorohydrin and thus are typically mixtures of molecules having somewhat different degrees of condensation.
  • the epoxy resin preferably contains an average of about 2 epoxy groups per molecule and should be selected so as to provide the desired combination of properties in both the thermosettable composition and the final cured thermoset and composite prepared therefrom.
  • blowing agent or blowing agents to be used in the present invention is not believed to be particularly critical, although chemical blowing agents and/or encapsulated physical blowing agents rather than non- encapsulated physical blowing agents should be used if a storage-stable, ready- to-use one-part composition is desired.
  • the blowing agent should preferably be substantially inert at normal storage temperatures (e.g., up to about 55°C) but capable of being activated when exposed to temperatures within the range of about 120°C to about 135°C.
  • Any of the chemical blowing agents known in the art may be employed, with azodicarbonamide (also sometimes referred to as 1 ,1 '- azobisformamide) and sulfonyl hydrazides providing particularly good performance.
  • azodicarbonamide is used as the predominate or, more preferably, sole blowing agent; mixtures with sulfonylhydrazides may be desirable for certain purposes, however.
  • Azodicarbonamide is available from a number of commercial sources; for example, it is sold under the trademark UNICELL by Dong Jin Chemical of South Korea and under the CELOGEN trademark by Uniroyal Chemical. "Activated” or “modified” forms of azodicarbonamide may be used to advantage.
  • Suitable sulfonylhydrazide blowing agents include, but are not limited to, p,p'-oxybis
  • the particle size of the blowing agent may be adjusted so as to provide the desired foaming characteristics in the cured foam. Smaller particle sizes, for example, tend to provide foams having more uniform cell structure.
  • Expandable thermoplastic resin microspheres (which can comprise, for example, volatile physical blowing agents such as hydrocarbons or halocarbons encapsulated in thermoplastic shells) may also be employed to render the thermosettable composition foamable.
  • Particularly preferred expandable microspheres are available from Akzo Nobel AB under the trademark EXPANCEL.
  • blowing agent activators include, but are not limited to, ureas (such as the surface-coated, oil-treated urea sold by Uniroyal Chemicals under the trademark BIKOT), polyols, organic acids, amines, and lead, zinc, tin, calcium and cadmium oxides and salts (including carboxylic acid salts).
  • blowing agent activator based on the weight of the thermosettable composition
  • the optimum amount will of course vary depending upon the activator/accelerator selected, the amount of blowing agent, cure temperature and other variables. Excess activator should not be used since the storage and processing stability may thereby be adversely affected.
  • Hollow glass microspheres are added to the thermosettable composition to reduce the density and weight of the resulting thermoset while maintaining good strength and stiffness.
  • Commercially available hollow glass microspheres include the materials sold by Minnesota Mining & Manufacturing under the trademark SCOTCHLITE, with suitable grades including those available under the designations B38, C15, K20 and VS 5500.
  • the glass microspheres preferably have diameters in the range of from about 5 to 200 micrometers (preferably, no greater than 70 micrometers).
  • the crush strength of the hollow glass microspheres may be selected in accordance with the desired characteristics of the cured thermoset or composite containing such thermoset. Preferably, the crush strength is at least about 200 Kg/cm 2 to permit processing of the thermosettable composition by pumping or the like without crushing the microspheres.
  • thermosettable composition Glass fiber is a preferred type of filler, since it helps increase the strength and stiffness of the thermoset.
  • the glass fiber may be chopped, milled or in other suitable physical form.
  • Any of the conventional organic or inorganic fillers known in the thermosettable resin art may be used including, for example, fibers other than glass fibers (e.g., wollastonite fibers, carbon fibers, ceramic fibers, polyaramid fibers), calcium oxide, wollastonite (including high aspect ratio wollastonite, which chemically is comprised of calcium silicate), alumina, mica, talc, zinc oxide, clays, sand, metals (e.g., aluminum powder), microspheres and macrospheres comprised of materials such as ceramics, thermosets, carbon, and the like (all of which may be solid or hollow, expanded or expandable) and the like.
  • fibers other than glass fibers e.g., wollastonite fibers, carbon fibers, ceramic fibers, polyaramid fibers
  • One or more thixotropic agents are also included in the thermosettable composition, especially where the epoxy resins used are liquid or semi-solid at room temperature or where other liquid components such as reactive diluents and the like are present.
  • thermosettable composition is formulated to have the consistency of a pliable dough or putty which at room temperature or a slightly elevated temperature (e.g., less than about 80°C ) can be readily formed into a desired shape by extrusion, molding or the like and yet which retains that shape once the forming operation is completed.
  • a slightly elevated temperature e.g., less than about 80°C
  • thermosettable composition in another embodiment, the components of the thermosettable composition and the relative proportions of said components are selected such that the thermosettable composition is pumpable. That is, such thermosettable composition is capable of being pumped into a hollow space or cavity where reinforcement is desired (such, as for example, a pillar, joint or hydroformed part of a vehicle which is otherwise not readily accessible).
  • the thermosettable composition which has been introduced in such manner is thereafter heated (by, for example, placing the vehicle in a paint oven) to a temperature effective to cure and expand the thermosettable composition.
  • Pumping of the thermosettable composition will generally be carried out at a temperature higher than room temperature, but lower than the temperature needed to initiate curing and foaming.
  • thermosettable composition such that it is pumpable in the aforedescribed manner, yet does not continue to flow after being cooled below the pumping temperature (e.g., to room temperature) or when no longer subjected to a disturbing force such as shear stress.
  • thixotopic agents include fumed or pyrogenic silica (especially fumed silica which has been treated with silanes or siloxanes or the like to render it hydrophobic in character), calcium carbonate (especially fine particle coated and/or precipitated calcium carbonate), bentonites, thixotropic clays and the like.
  • thermosettable composition be essentially free of surfactants, as such substances tend to increase the rate at which water can penetrate the thermoset and corrode the surface of a metal substrate to which the thermoset is adhered.
  • thermosettable composition it is particularly advantageous to include one or more rubbers in the thermosettable composition, as such additives will toughen the thermoset and reduce the tendency of the thermoset to crack under stress.
  • rubbers includes both rubbers and elastomers. Suitable rubbers include thermoplastic as well as thermosettable (reactive) rubbers.
  • Illustrative types of rubber include styrene - butadiene rubbers (SBR), nitrile - butadiene rubbers, butyl rubbers, polyisoprene, natural rubber, polybutadiene, chlorobutyl rubbers (neoprene), isobutylene polymers, alpha - olefin elastomers, ethylene - propylene elastomers, chlorosulfonated polyethylenes, ethylene - propylene - diene (EPDM) rubbers, and the like.
  • SBR styrene - butadiene rubbers
  • nitrile - butadiene rubbers butyl rubbers
  • polyisoprene natural rubber
  • polybutadiene chlorobutyl rubbers (neoprene)
  • isobutylene polymers alpha - olefin elastomers
  • ethylene - propylene elastomers chloro
  • Such materials contain one or more base segments ("A") covalently bonded to one or more soft or elastomeric segments ("B").
  • the A segments may be polystyrene, poly (alpha - methylstyrene), polyethylene, polyurethane, polysulfone, polyester, polycarbonate or the like.
  • the B segments may be polybutadiene, polyisoprene, poly ( ethylene - cobutylene), polydimethylsiloxane, polyether, or the like.
  • the block copolymers may have a linear, branched, radial or star structure and may, for example, correspond to the general structure A-B-A, (A-B) n , and so forth.
  • SBS block copolymers are examples of specific types of such materials.
  • Liquid rubbers which may be functionalized with carboxy groups, amine groups, or other groups capable of reacting with other components of the thermosettable composition may also be employed.
  • the thermosettable composition may additionally include one or more coupling agents and/or metal- modified inorganic oxides.
  • Suitable coupling agents include silanes and organometallates such as organic titanates and zirconates.
  • Organic titanates and zirconates are well known in the art and are described, for example, in U.S. Pat. No. 6,103,784, which is incorporated herein by reference in its entirety.
  • Suitable metal-modified inorganic oxides include alkaline earth metal-modified silicates, for example, calcium ion exchanged amorphous silica gels such as the SHIELDEX products available from the Grace Davison Division of W.R. Grace.
  • thermosettable compositions of the present invention can be readily prepared by simply mixing the individual components in desired proportions using planetary mixers, kneaders, rollers, or the like. The various components are adjusted such that the thermosettable composition retains a workable consistency (i.e. does not cross - link or cure to an unacceptable degree) for at least 1 week at 55°C and at least 1 day at 80°C and does not expand in volume or decrease in specific gravity under such conditions to an unacceptable extent, yet foams and cures within about 10 minutes upon being exposed to a temperature within the range of about 120°C to about 135°C. It is also desirable that the composition exhibits no appreciable deterioration in performance (e.g. % expansion, cured thermoset physical properties such as lap shear or compressive strength) after being exposed to such conditions.
  • a workable consistency i.e. does not cross - link or cure to an unacceptable degree
  • the composition exhibits no appreciable deterioration in performance (e.g. % expansion, cured thermoset
  • thermosettable compositions of the present invention may be utilized in any end-use application where an adhesive, sealant or coating is required.
  • the thermosettable compositions are especially useful in the production of automobiles and other vehicles to maintain or increase the strength of structural members such as rails, rockers, torsion bars, pillars, radiator support beams, doors, reinforcing beams and the like.
  • structural reinforcement foams in such applications is described, for example, in U.S. Pat. Nos.
  • thermosettable compositions in accordance with the present invention are described in Tables I and I.
  • PEP 6134 epoxy resin a product of Peninsula Polymers 2 CELOGEN AZ 120 azodicarbonamide blowing agent, a product of Air Products

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des mousses structurales utiles pour renforcer des parties creuses de véhicules et analogues obtenues par chauffage de compositions thermodurcissables à base de résines époxy contenant des agents porogènes ainsi que des agents de durcissement d'addition à base d'amines de trihalogénure de bore. L'utilisation de ces agents de durcissement permet la formulation de compositions thermodurcissables stables au stockage et pouvant être traitées à des températures modérément élevées sans détérioration. Une activation des compositions thermodurcissables peut cependant être exécutée en une durée courte à des températures relativement basses (120 °C à 135 °C).
PCT/US2001/045000 2000-11-17 2001-11-16 Compositions expansibles stables au stockage WO2002049836A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002219981A AU2002219981A1 (en) 2000-11-17 2001-11-16 Storage-stable foamable compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71596600A 2000-11-17 2000-11-17
US09/715,966 2000-11-17

Publications (1)

Publication Number Publication Date
WO2002049836A1 true WO2002049836A1 (fr) 2002-06-27

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PCT/US2001/045000 WO2002049836A1 (fr) 2000-11-17 2001-11-16 Compositions expansibles stables au stockage

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WO (1) WO2002049836A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004065485A1 (fr) * 2003-01-22 2004-08-05 Henkel Komanditgesellschaft Auf Aktien Composition thermoexpansible et thermodurcissable presentant un haut degre d'expansion
WO2007025036A1 (fr) * 2005-08-24 2007-03-01 Dow Global Technologies, Inc. Patches de renforcement a base d’epoxy comprenant des agents gonflants physiques encapsules
CN104149404A (zh) * 2014-07-14 2014-11-19 华南理工大学 一种纤维增强泡沫梯度隔热减振层合板

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3395121A (en) * 1966-09-21 1968-07-30 Stauffer Chemical Co Curing epoxy resins with boron trichloride-tertiary amine complexes
US6103784A (en) * 1998-08-27 2000-08-15 Henkel Corporation Corrosion resistant structural foam
US6233826B1 (en) * 1997-07-21 2001-05-22 Henkel Corp Method for reinforcing structural members
US6237304B1 (en) * 1997-07-18 2001-05-29 Henkel Corporation Laminate structural bulkhead
US6332731B1 (en) * 1998-02-04 2001-12-25 Henkel Corporation Three dimensional composite joint reinforcement for an automotive vehicle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3395121A (en) * 1966-09-21 1968-07-30 Stauffer Chemical Co Curing epoxy resins with boron trichloride-tertiary amine complexes
US6237304B1 (en) * 1997-07-18 2001-05-29 Henkel Corporation Laminate structural bulkhead
US6233826B1 (en) * 1997-07-21 2001-05-22 Henkel Corp Method for reinforcing structural members
US6332731B1 (en) * 1998-02-04 2001-12-25 Henkel Corporation Three dimensional composite joint reinforcement for an automotive vehicle
US6103784A (en) * 1998-08-27 2000-08-15 Henkel Corporation Corrosion resistant structural foam

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004065485A1 (fr) * 2003-01-22 2004-08-05 Henkel Komanditgesellschaft Auf Aktien Composition thermoexpansible et thermodurcissable presentant un haut degre d'expansion
US7736743B2 (en) 2003-01-22 2010-06-15 Henkel Kgaa Heat curable, thermally expandable composition with high degree of expansion
WO2007025036A1 (fr) * 2005-08-24 2007-03-01 Dow Global Technologies, Inc. Patches de renforcement a base d’epoxy comprenant des agents gonflants physiques encapsules
CN104149404A (zh) * 2014-07-14 2014-11-19 华南理工大学 一种纤维增强泡沫梯度隔热减振层合板

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