EP2473559A1 - Utilisation de résines époxyde moussables à basses températures dans des structures creuses - Google Patents

Utilisation de résines époxyde moussables à basses températures dans des structures creuses

Info

Publication number
EP2473559A1
EP2473559A1 EP10740686A EP10740686A EP2473559A1 EP 2473559 A1 EP2473559 A1 EP 2473559A1 EP 10740686 A EP10740686 A EP 10740686A EP 10740686 A EP10740686 A EP 10740686A EP 2473559 A1 EP2473559 A1 EP 2473559A1
Authority
EP
European Patent Office
Prior art keywords
preparation
carbamate
weight
substrate
insert
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.)
Ceased
Application number
EP10740686A
Other languages
German (de)
English (en)
Inventor
Emilie Barriau
Dennis Bankmann
Olaf Lammerschop
Martin Renkel
Sven Wucherpfennig
Karl Braun
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2473559A1 publication Critical patent/EP2473559A1/fr
Ceased legal-status Critical Current

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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
    • 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
    • C08J9/08—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 carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1228—Joining preformed parts by the expanding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a new use of at low temperatures
  • epoxy resin monomers or prepolymers are combined under “epoxy resin prepolymers” as latent hardeners.
  • preferred ammonium carbamate salts split off at temperatures below 100 0 C CO 2 , which leads to foaming of the mass. The resulting free
  • Amine acts as a hardener for the epoxy prepolymer.
  • substrates with cavity structure are reinforced with these preparations.
  • the preparations are used to attach inserts such as sleeves with or without internal thread for fixing screws, hooks etc. or threaded rods in substrates with cavity structures.
  • a cavity structure is understood, on the one hand, to mean a structure with more or less regularly arranged cavities, such as, for example, solid foams or cellular structures, such as honeycomb structures, etc.
  • the cavity may be a volume of larger volumes. eg the interior of a pipe, a hollow carrier or a commodity.
  • the cavities have diameters in the range of 0.1 to 100 mm, especially 1 to 30 mm.
  • solid foams or cellular structures such as honeycomb structures, cells of 1 to 10 mm, in particular 1 to 5 mm in diameter may occur, but larger holes may be formed by drilling and to be filled.
  • the material for these substrates may for example consist of metal, plastic, cardboard or the like. Such substrates are used for example in transportation and in particular in ship and aircraft as lightweight materials, for example, to build the interior of aircraft or ships, especially the luggage compartments of aircraft.
  • the present invention makes use of the known effect that organic amines can reversibly attach CO 2 to form carbamic acid, the carbamic acid in a self-assimilating Neutralization with further amine reacts to an organic ammonium carbamate salt, as the following equation shows.
  • the amine that forms the carbamic acid is primary or secondary, while the neutralizing amine may be primary, secondary or tertiary.
  • the acid-base reaction can be carried out intramolecularly or intermolecularly in the case of multifunctional amines. However, only 0.5 CO 2 equivalents based on the free amine groups of the starting material can be reacted.
  • US-A-3,425,964 also describes the use of organic carbamates as foamable hardeners for resin systems. They can be used, for example, in the production of films, coatings or adhesives. Another application is the embedding of electronic components or the use as packaging material or as insulating material. For example, foamed epoxy resins can be used for this purpose.
  • the present invention extends the field of application of epoxy resins, which can be foamed and cured by means of carbamates at a temperature in the range of 20 to 100 0 C. Higher curing temperatures are possible, but then the advantage of the invention is less significant.
  • the present invention improves the anchoring of inserts in hollow structures, which has hitherto usually been carried out with the aid of conventional two-component adhesives has been.
  • the present invention it is now possible to reduce the mass of the required adhesive in terms of lightweight construction, since the foamed and cured material may have a significantly lower density than a non-foamed adhesive.
  • foamable adhesive composition is its ability to compensate for tolerances and differences in cavity size through variable expansion, whereas with a conventional non-foamable adhesive composition, the amount of adhesive must be adjusted.
  • the present invention relates to a method for reinforcing a substrate having a void structure, wherein a foaming and curable epoxy resin-based formulation is introduced into a selected part of the void structure to be reinforced, and the preparation is heated by heating to a temperature in the Range of 20 0 C to 100 0 C or above, preferably cured to 80 0 C and in particular to 65 ° C with foaming, wherein the preparation contains at least the following components: a) at least one epoxy resin prepolymer (this term, the monomers with includes, see above) with reactive epoxide groups,
  • At least one organic ammonium carbamate preferably one which at a temperature in the range of 20 to 100 0 C or above, but preferably up to 80 0 C and in particular to 65 0 C within an hour at least 25% of the carbamate splits off bound CO 2 .
  • the present invention relates to a method of securing an insert in a cavity-structured substrate, wherein a foamable and curable epoxy-based formulation is placed in a selected portion of the cavity structure in which the insert is to be secured, the insert therein Part of the cavity structure used so that the inside of the cavity structure to be fastened part of the insert immersed at least after their foaming and curing in the foamable and curable preparation, and the preparation by heating to a temperature in the range of 20 0 C to 100 0 C or above, but preferably cures to 80 0 C and in particular to 65 0 C with foaming, wherein the preparation contains at least the following components:
  • At least one organic ammonium carbamate preferably one which at a temperature in the range of 20 to 100 0 C or above, preferably up to 80 0 C and in particular up to 65 0 C within one hour at least 25% of the carbamate splits off bound CO 2 .
  • organic ammonium carbamate preferably one which at a temperature in the range of 20 to 100 0 C or above, preferably up to 80 0 C and in particular up to 65 0 C within one hour at least 25% of the carbamate splits off bound CO 2 .
  • organic ammonium carbamate is understood according to the invention to mean a compound of at least one carbamate anion and at least one organic ammonium counterion.
  • the epoxy resin prepolymer should be at least difunctional, ie have at least two reactive epoxide groups, so that a polymerization reaction can occur with the amine released from the carbamate. It can be used as a monomer or as an already prepolymerized prepolymer. Both are summarized in the context of this document under “epoxy resin prepolymers” or "epoxy resins”.
  • epoxy resin prepolymers hereinafter also referred to as "epoxy resins" may in principle be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxide compounds.
  • Suitable epoxy resins in the context of the present invention are, for example, preferably selected from bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak epoxy resins.
  • Type, epoxidized products of numerous dicyclopentadiene-modified phenolic resins obtainable by reaction of dicyclopentadiene with numerous phenols, epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, aromatic epoxy resins such as naphthalene-based epoxy resins and fluorene-based epoxy resins, aliphatic Epoxy resins such as neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether, alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexyl) adipate, and epoxy resins having a hetero ring such as triglycidyl isocyanurate.
  • aromatic epoxy resins such as naphthalene-based epoxy resins and fluorene-based epoxy resin
  • the epoxy resins include, for example, the reaction product of bisphenol A and epichlorohydrin, the reaction product of phenol and formaldehyde (novolak resins) and epichlorohydrin, glycidyl esters, and the reaction product of epichlorohydrin and p-aminophenol.
  • polyphenols which provide suitable epoxy resin prepolymers by reaction with epichlorohydrin (or epibromohydrin) are: resorcinol, 1,2-dihydroxybenzene, hydroquinone, bis (4- hydroxyphenyl) -1, 1-isobutane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane and 1, 5-hydroxynaphthalene.
  • polyglycidyl ethers of polyhydric alcohols or diamines are polyglycidyl ethers of polyhydric alcohols or diamines.
  • Such polyglycidyl ethers are derived from polyhydric alcohols, for example ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol or trimethylolpropane.
  • epoxy resins which are commercially available include, in particular, octadecyl oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ethers of bisphenol A (eg those sold under the trade names "Epon 828”, “Epon 825”, “ Epon 1004 "and” Epon 1010 "from Hexion Specialty Chemicals Inc.,” DER-331 “,” DER-332 “,” DER-334 “,” DER-732 “and” DER736 “available from Dow Chemical Co.) , Vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexene carboxylate, bis (3,4-epoxy-6-methylcyclohex
  • DEN-431 and “DEN-438” from Dow Chemical Co. as well as resorcinol diglycidyl ethers (eg, "Kopo xite” from Koppers Company Inc.), bis (3,4-epoxycyclohexyl) adipate, 2- (3 , 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, vinylcyclohexene monoxide, 1,2-epoxyhexadecane, alkyl glycidyl ethers such as C8-C10-alkyl-glycidyl ether (eg "HELOXY modifier 7").
  • Hexion Specialty Chemicals Inc. C12-C14 alkyl glycidyl ether (eg "HELOXY Modifier 8" from Hexion Specialty Chemicals Inc.), butyl glycidyl ether (eg "HELOXY Modifier 61" from Hexion Specialty Chemicals Inc.), cresyl glycidyl ether (eg " HELOXY Modifier 62 "from Hexion Specialty Chemicals Inc.), p-tert-butylphenyl glycidyl ether (eg" HELOXY Modifier 65 "from Hexion Specialty Chemicals Inc.), polyfunctional glycidyl ethers such as diglycidyl ether from 1,4-butanediol (eg" HELOXY Modifier 67 "from Hexion Specialty Chemicals Inc.), diglycidyl ether from neopentyl glycol (eg"
  • Further preferred commercially available compounds are, for. Selected from Araldite TM 6010, Araldit TM GY-281 TM, Araldit TM ECN-1273, Araldit TM ECN-1280, Araldit TM MY-720, RD-2 from Huntsman Int. LLC; DEN TM 432, DEN TM 438, DEN TM 485 from Dow Chemical Co., Epon TM 812, 826, 830, 834, 836, 871, 872,1001, 1031 etc. from Hexion Specialty Chemicals Inc.
  • HPT TM 1071 , HPT TM 1079 also from Hexion Specialty Chemicals Inc., as novolac resins further include, for example, Epi-Rez TM 5132 from Hexion Specialty Chemicals Inc., ESCN-001 from Sumitomo Chemical, Quatrex 5010 from Dow Chemical Co., RE 305S from Nippon Kay aku, Epiclon TM N673 from DaiNipon Ink Chemistry or Epicote TM 152 from Hexion Specialty Chemicals Inc.
  • polyepoxides may be used at least proportionally: polyglycidyl esters of polycarboxylic acids, for example reaction products of glycidol or epichlorohydrin with aliphatic or aromatic polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, terephthalic acid or dimer fatty acid.
  • the epoxide equivalent of suitable polyepoxides may vary between 150 and 50,000, preferably between 170 and 5,000.
  • an epoxy resin is based
  • Epichlorohydrin / bisphenol-A having an epoxide equivalent weight of 475 to 550 g / eq or an epoxide group content in the range of 1820 to 21 10 mmol / g.
  • the softening point determined according to RPM 108-C is in the range of 75 to 85 ° C.
  • reaction products of epichlorohydrin with bisphenol A or bisphenol F are preferably used.
  • these epoxy equivalent weights range from about 150 to about 480.
  • the composition to be used according to the invention can be formed as one-component or two-component.
  • one component contains the epoxy resin prepolymer
  • the other component contains the organic ammonium carbamate.
  • this does not necessarily have to be the case: if a carbat was put into a latent state by 100% loading or has a sufficiently low reactivity, it can be mixed with the epoxide in one component.
  • the second component may then contain a reactive amine and the carbamate would be decomposed by either the heat of reaction or by heating.
  • both components are preferably liquid at room temperature (22 ° C). Therefore, it is for this preferred form that the preparation contains at least one at 22 ° C liquid epoxy prepolymer.
  • the preparation according to the invention is preferably not liquid, but may have a state between soft and kneadable to plastically firm.
  • the preparation contains at least one 22 ° C liquid epoxy prepolymer.
  • the viscosity of the preparation at the foaming and curing temperature should be high enough that the CO 2 formed is at least partially and preferably as completely as possible held in the form of gas bubbles in the preparation. This can be achieved by making the preparation at least one waxy at 22 ° C
  • the preparation contains both a liquid at 22 ° C and a waxy at 22 ° C or solid epoxy prepolymer.
  • the formulation contains from 5% to 90% and more preferably from 20% to 80% by weight of epoxy prepolymer, this being a solid or waxy epoxy prepolymer at 22 ° C, than at 22 ° C liquid epoxy prepolymer or may be present as a mixture of different E- poxide prepolymers.
  • amounts in weight percent are generally understood to refer to the mass of the entire formulation, which is 100 percent by weight.
  • the data refer to the mass of the preparation after mixing the two components.
  • the carbamate anion preferably has a structure according to formula (I)
  • R1 is hydrogen or an organic radical and R2 represents an organic radical.
  • the radicals R1 and R2 may be the same or different, if R1 is not hydrogen.
  • Carbamate salts of primary amines are preferred, so that R1 is preferred. represents hydrogen.
  • R means an organic residue.
  • the nature of the radical R characterizes the reactivity of the carbamate and the corresponding free amine in two ways. On the one hand, it depends on the remainder R how easily the organic amine absorbs CO 2 under carbamate formation and, on temperature increase, splits off again to recover the amine.
  • the stability of the carbetmate salt is decisively determined by two factors. On the one hand, a high basicity of the free amine leads to a strongly exothermic neutralization reaction with the intermediate carbamic acid. According to thermodynamic principles, a high energy barrier must accordingly be overcome in order to recover the starting materials, ie the carbamate salt has a high temperature stability.
  • Suitable amines in the context of the present invention are those which split off at least 25% of the CO 2 bound as carbamate at the desired temperature within one hour.
  • the nature of the radical R controls the reactivity towards the epoxy resin prepolymer and thus the curing behavior. Preference is given to using those carbamates of the formula (II) in which the organic radical R may be:
  • alkyl radical or arylalkyl radical having 1 to 100 carbon atoms which may carry one or more further amino or alkylamino groups, which in turn may be converted into carbamate groups,
  • radical R 2 of the formula (I) preferably has the same meaning as the radical R of the formula (II).
  • Carbamate anions of the formulas (I) in which at least one of the radicals R 1 or R 2 is a radical of a polyalkylene glycol are very particularly preferred according to the invention.
  • At least a proportion of carbamates of such amines are used which have two or three amino groups. This makes it possible to control the crosslinking behavior and the mechanical properties of the cured preparation.
  • the organic ammonium counterions can in principle be formed from any organic amine. However, it has proved to be particularly advantageous according to the invention in terms of performance properties, when the ammonium counterion is formed from the same organic amine, which is involved in the formation of carbamate.
  • di- or polyamines whose amino groups have already been partially reacted with epoxides, so that only a fraction of the original amino groups is available for carbamate formation. These can be prepared as described in WO 2007/025007, page 17, line 4 to page 19, line 25. In order to However, if free amino groups are available for carbamate formation, the amines must be used in a stoichiometric excess relative to the epoxide groups.
  • the epoxide used is preferably diglycidyl ether of bisphenols, in particular of bisphenol A.
  • polyfunctional amines having molecular weights in the range of below 200 often form carbamates, which at temperatures of at most 100 0 C and in particular of maximum 65 ° C split only insignificant amount of CO2. Since a foaming and curing temperature of a maximum of 100 0 C and in particular of a maximum of 65 ° C is desirable in the present invention (although higher temperatures are not excluded), such amines for the present invention are less suitable.
  • amines which have a molecular weight in the range from about 200 to about 4000, preferably up to about 3000 and in particular up to about 1800 g per mole before the formation of the carbamate ,
  • the group includes in principle suitable amines having molecular weights in the range of about 60 to about 8000 g / mol.
  • a first carbamate which has a molecular weight in the range from about 200 to about 4000, preferably up to about 3000 and in particular up to about 1800 g per mole, is present in carbamate form and for foaming of the resin is used and for curing of the epoxy resin at a maximum temperature of 100 0 C and in particular of not more than 65 ° C suitable for curing second amine.
  • the preparation In order to ensure sufficient frothing of the preparation, it must contain a minimum content of carbamate-bound CO 2 . It is therefore preferred that the preparation contains at least 0.5% by weight, preferably at least 1% by weight, based on the total preparation, of CO 2 bound as carbamate. Depending on the molar mass of the amine on which the carbamate is based, the corresponding amount of carbamate can be determined from this.
  • the preparation preferably contains 5 to 95% by weight, more preferably 10 to 60% by weight, of organic ammonium carbamate, calculated as the complete ammonium salt.
  • the preparation may contain, in addition to the carbamate anions and the organic counterions, free amine molecules. The curing is thereby generally accelerated.
  • the content of free amine can be between 0 and 90% by weight, preferably between 1 and 60% by weight.
  • the preparation may contain so-called tougheners, as known for epoxy adhesives
  • the impact modifiers may be, for example, rubber, in particular in the form of rubber nanoparticles, thermoplastic polymers such as thermoplastic polyurethanes, core-shell particles with an organic polymer shell and an organic or inorganic core, or block copolymers. Examples for this are:
  • Solid rubbers such as styrene-butadiene rubbers and nitrile-butadiene rubbers or polystyrene polymers such as SBS block copolymers, polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, EPDM, synthetic or natural isoprene rubber, butyl rubber or polyurethane rubber.
  • partially crosslinked solid rubbers based on isoprene-acrylonitrile or butadiene-acrylonitrile copolymers, epoxy-polyurethane hybrids, polyurethanes derived from hydroxyl-terminated polyoxyalkylenes, such as, for example, polypropylene glycol or polytetrahydrofurandiol, styrene-butadiene-methyl methacrylate block Copolymers, methyl methacrylate-butadiene-methyl methacrylate block copolymers and butadiene-methyl methacrylate block copolymers, thermoplastic, non-reactive polyurethane, which is preferably selected from polyurethanes containing a polyester chain.
  • the composition of the present invention may contain rubber particles as an impact improver. These likewise contribute to improving the impact strength of the cured preparation, in particular at temperatures below 0 ° C.
  • these rubber particles have a core-shell structure. It is preferred that the rubber particles with core-shell structure have a core of a polymer material having a glass transition temperature of below 0 0 C and a shell of a polymer material having a glass transition temperature of above 25 0 C.
  • Particularly suitable rubber particles having a core-shell structure may have a core of a diene homopolymer, a diene copolymer or a polysiloxane elastomer and / or a shell of an alkyl (meth) acrylate homopolymer or copolymer.
  • composition according to the invention may contain, as an impact improver, inorganic particles which have a shell of organic polymers, where the organic niche polymers are preferably selected from polystyrene or from homo- or copolymers of acrylic acid and / or methacrylic acid ester.
  • the preparation to be used according to the invention may contain from 0 to 30% by weight, preferably from 1 to 20% by weight of inorganic fillers, for example the various ground or precipitated crayons, carbon black, calcium magnesium carbonates, barite and in particular silicate fillers of the type of the aluminum-magnesium-calcium silicate, e.g. B. wollastonite, chlorite.
  • inorganic fillers for example the various ground or precipitated crayons, carbon black, calcium magnesium carbonates, barite and in particular silicate fillers of the type of the aluminum-magnesium-calcium silicate, e.g. B. wollastonite, chlorite.
  • fumed silicas, bentones or fibrillated or pulp short fibers in the range between 0.1 and 5% can be added as rheology auxiliaries. Their addition can contribute in particular to hold the resulting CO 2 as gas bubbles in the curing preparation.
  • the compositions may contain, in addition to or instead of the aforementioned "normal" fillers, so-called light fillers, which may be selected, for example, from the group of hollow metal spheres, such as e.g. As hollow steel spheres, hollow glass spheres, fly ash (Fillite), hollow plastic spheres based on phenolic resins, epoxy resins or polyesters, expanded hollow microspheres with wall material of (meth) acrylic acid ester copolymers, polystyrene, styrene (meth) acrylate copolymers and in particular of polyvinyl idenchloride and Copolymers of vinylidene chloride with acrylonitrile and / or (meth) acrylic acid esters, ceramic hollow spheres or organic light fillers of natural origin such as ground nutshells, such as the shells of cashew nuts, coconuts or peanut shells and cork powder or coke powder.
  • light fillers which may be selected, for example, from the group of hollow metal sphere
  • excipients and agents such as flexibilizers, adhesion promoters, other fillers, pigments and flame retardants may be included, the latter being particularly important in aircraft applications.
  • foaming and / or curing can be accelerated if the preparation contains cleavage accelerators for the CO 2 from the carbamates.
  • cleavage accelerators for the CO 2 from the carbamates include acids, especially organic acids such as lactic acid, citric acid, tartaric acid, etc. Sulfonic acids or phosphonic acids are also suitable.
  • the acid is preferably used substoichiometrically in relation to the total amount of CO 2 to be split off.
  • the preparation contains the following constituents, the amounts given in wt .-% based on the total weight of the preparation: 0 wt .-% to 90 wt .-%, preferably 5 wt .-% to 80 wt .-% and in particular 20 wt .-% to 80 wt .-% at 22 0 C solid or waxy epoxy prepolymer,
  • auxiliaries and active substances in particular flexibilizers, cleavage accelerators, adhesion improvers, further fillers, pigments and flame retardants.
  • the preparation may be one-component or two-component.
  • one component contains the epoxy prepolymers
  • the other component either the ammonium carbamate, to accelerate curing, optionally in combination with free amine, or else one component contains the epoxy prepolymers and the ammonium carbamate and the other component a free amine.
  • other combinations are conceivable, e.g. an embodiment wherein epoxy prepolymers and carbamate salt (s) in one and a mixture of free amine and carbamate salt (s) are present in the second component.
  • the preparation is used as one-component or two-component, it is preferred that it be fixed at both 22 ° C. liquid epoxide prepolymer and at 22 ° C. tes or waxy epoxy prepolymer contains. Preferably, then their amounts, based on the total preparation, each in the range between 25 and 40 wt .-%.
  • a suitable preparation which is preferably one-component, may contain, for example:
  • Fillers in particular lightweight fillers, such as, for example, hollow glass spheres,
  • organic ammonium carbamate 10 to 30% by weight
  • Fillers in particular light fillers such as, for example, glass hollow spheres: 5 to 20% by weight,
  • the preparation consists exclusively of the abovementioned five components.
  • the individual quantities are to be coordinated so that they add up to 100 wt .-%.
  • the preparation additionally contains, in addition to the abovementioned five components, flame retardants, preferably an amount of from 0.1 to 60% by weight, based on the total composition. Examples are: red phosphorus, which can preferably be used in the quantitative range 0.1 to 5 wt .-%, or aluminum hydroxide with a higher amount used, for example in the range of 20 to 60 wt .-%.
  • a bore is introduced into the substrate into which the preparation (which is then preferably in waxy or kneadable form) is forced and then the insert is pressed into this preparation. Thereafter, the preparation is cured.
  • the substrate for a while after the introduction of the preparation (several hours or days, with cooling even longer) before the insert is inserted and the preparation is cured.
  • At least that part of the insert which is to be fastened in the substrate with cavity structure is surrounded at least partially with the one- or two-component preparation.
  • the preparation should be at least so strong that it is not stripped off when inserting the insert into the substrate.
  • the inserts can be equipped with the preparation already in the manufacturer and shipped in this form. It is then not necessary to manipulate at the site of insertion of the insert into the substrate with the preparation itself. In this way, time savings and process simplifications can be realized. If this is done using a two-component preparation, it may be necessary to store the coated insert at low temperature (below 0 0 C) to prevent premature curing and foaming reaction.
  • the insert is preferably a threaded sleeve with or without internal thread or a part containing it.
  • other inserts such as nuts or flanged nuts may be used. In each of these other elements can then be attached.
  • inserts such as threaded rods, hooks, screws, sleeves etc. can also be anchored directly in the preparation.
  • the present invention relates to an insert for mounting in a substrate, the part to be fixed within the substrate is at least partially surrounded by a foaming and curable epoxy resin-based preparation obtained by heating to a temperature in the range of 20 0 C to 100 0 C or above, preferably to 80 0 C and in particular to 65 0 C cures with foaming, wherein the preparation contains at least the following components:
  • the present invention comprises an article containing or consisting of a substrate having a void structure, wherein the voided structure substrate has been reinforced or provided with an insert according to the method described above.
  • this object may represent a component of a ship or an aircraft, in particular a component for luggage compartments of aircraft. However, it may also generally be parts of water, land or air vehicles or everyday objects.
  • This preparation was molded at room temperature (22 ° C) into a cylindrical part weighing 0.3 g.
  • This cylindrical member was inserted into a bore of a honeycomb sandwich phenolic resin panel coated with glass fiber phenolic resin prepreg.
  • an insert in the form of a threaded sleeve with internal thread was used.
  • the threaded sleeve consisted of a circular top with a diameter of 11 mm and a height of 1 mm, a cylindrical shaft with a height of 4 mm and a diameter of 7 mm and a substantially rectangular, rounded on the short side bottom plate with a length of 1 1 mm, a width of 7 mm and a height of 1 mm.
  • This insert was pressed into the composition up to the top of the top. Thereafter, was heated to a temperature of 60 0 C for foaming and curing for one hour. After storage for 7 days at 22 ° C, the pulling force required to pull the insert out of the substrate was measured. For this purpose, the substrate was held in place by a retaining plate having a bore slightly larger than the diameter of the top of the insert. The upper part was connected to a tensile testing machine (Zwick Z050) and at a drawing speed of 0.1 mm / sec. pulled out. A pulling force for extracting the insert from 470 N was determined. The fracture behavior was cohesive.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de renforcement d'un substrat à structure creuse ou de fixation d'un insert dans un tel substrat, selon lequel une préparation moussable et durcissable mono- ou bicomposante à base de résine époxyde est introduite dans une partie choisie de la structure creuse à renforcer, et la préparation est durcie avec moussage par chauffage à une température dans la plage allant de 20 °C à 100 °C ou plus. Selon l'invention, la préparation contient au moins les composants suivants : a) au moins un prépolymère de résine époxyde contenant des groupes époxyde réactifs, b) au moins un carbamate d'ammonium organique, de préférence tel qu'à une température dans la plage allant de 20 à 100 °C ou plus, au moins 25 % du CO2 relié en tant que carbamate soit clivé en l'espace d'une heure. L'invention concerne également un insert à fixer dans un substrat, dont la partie à fixer dans le substrat est entourée au moins en partie par une telle préparation moussable et durcissable ; un article qui contient un substrat à structure creuse ou en est constitué, le substrat étant renforcé ou muni d'un insert en utilisant cette préparation.
EP10740686A 2009-08-31 2010-08-11 Utilisation de résines époxyde moussables à basses températures dans des structures creuses Ceased EP2473559A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009029030A DE102009029030A1 (de) 2009-08-31 2009-08-31 Verwendung von bei niedrigen Temperaturen schäumbaren Epoxidharzen in Hohlraumstrukturen
PCT/EP2010/061688 WO2011023552A1 (fr) 2009-08-31 2010-08-11 Utilisation de résines époxyde moussables à basses températures dans des structures creuses

Publications (1)

Publication Number Publication Date
EP2473559A1 true EP2473559A1 (fr) 2012-07-11

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EP10740686A Ceased EP2473559A1 (fr) 2009-08-31 2010-08-11 Utilisation de résines époxyde moussables à basses températures dans des structures creuses

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US (1) US20120156412A1 (fr)
EP (1) EP2473559A1 (fr)
JP (1) JP2013503215A (fr)
KR (1) KR20120073212A (fr)
DE (1) DE102009029030A1 (fr)
WO (1) WO2011023552A1 (fr)

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US20100151253A1 (en) * 2005-07-08 2010-06-17 Henkel Kgaa Primer Compositions for Adhesive Bonding Systems
DE102011007897A1 (de) 2011-04-12 2012-10-18 Henkel Ag & Co. Kgaa Schlagzähmodifizierte Klebstoffe
DE102012205057A1 (de) 2012-03-29 2013-10-02 Henkel Ag & Co. Kgaa Thermisch expandierbare Zubereitungen
DE102013006206A1 (de) * 2013-04-04 2014-10-09 Salzgitter Mannesmann Line Pipe Gmbh Kunststoffummanteltes Rohr aus Stahl
CN103727317B (zh) * 2013-09-11 2016-01-20 太仓派欧技术咨询服务有限公司 一种铼基难熔金属混杂管的制备方法
US20150190981A1 (en) * 2014-01-08 2015-07-09 E I Du Pont De Nemours And Company Metallic core having a high compression strength and articles made from same
EP3050919A1 (fr) 2015-01-29 2016-08-03 Basf Se Matériaux contenant de la lignocellulose comprenant des mélanges de sels d'acides carbamiques n-substitués
EP3725826A1 (fr) 2019-04-16 2020-10-21 Henkel AG & Co. KGaA Préparations thermiquement durcissables et expansibles pouvant être pompées
EP3725827A1 (fr) 2019-04-16 2020-10-21 Henkel AG & Co. KGaA Préparation thermiquement expansible pouvant être pompée
KR20240066246A (ko) * 2021-09-02 2024-05-14 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 에폭시 수지계 발포체, 이산화탄소 흡수제, 에폭시 수지계 발포체의 제조방법, 다층 구조체 그리고 그의 제조방법

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Also Published As

Publication number Publication date
WO2011023552A1 (fr) 2011-03-03
DE102009029030A1 (de) 2011-03-03
JP2013503215A (ja) 2013-01-31
US20120156412A1 (en) 2012-06-21
DE102009029030A8 (de) 2011-06-01
KR20120073212A (ko) 2012-07-04

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