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EP2948493A2 - 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes - Google Patents

2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes

Info

Publication number
EP2948493A2
EP2948493A2 EP14700693.6A EP14700693A EP2948493A2 EP 2948493 A2 EP2948493 A2 EP 2948493A2 EP 14700693 A EP14700693 A EP 14700693A EP 2948493 A2 EP2948493 A2 EP 2948493A2
Authority
EP
European Patent Office
Prior art keywords
curable composition
ether
epoxy resins
tmdc
epoxy resin
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.)
Withdrawn
Application number
EP14700693.6A
Other languages
German (de)
English (en)
Inventor
Achim Kaffee
Miran Yu
Monika CHARRAK
Kirsten Dahmen
Veit Stegmann
Gerd Haderlein
Alexander Panchenko
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP14700693.6A priority Critical patent/EP2948493A2/fr
Publication of EP2948493A2 publication Critical patent/EP2948493A2/fr
Withdrawn legal-status Critical Current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
    • 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
    • C08G59/40—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 characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic

Definitions

  • the present invention relates to a curable composition of epoxy resin, epoxide group-containing reactive diluent and the curing agent 2,2 ⁇ 6,6'-tetramethyl-4,4'-methylenebis (cyclohexylamine) (2,6-TMDC), wherein this curable composition is substantially free of aromatic diamines.
  • the invention also relates to the use of 2,6-TMDC as a curing agent for epoxy resins in curable compositions containing epoxide group-containing reactive diluents.
  • the invention further relates to the curing of the curable composition and to the cured epoxy resin obtained by curing the curable composition.
  • Epoxy resins are well known and, because of their toughness, flexibility, adhesion and chemical resistance, are used as surface coating materials, as adhesives and for molding and laminating. In particular, for the production of carbon fiber reinforced or glass fiber reinforced composite materials epoxy resins are used.
  • Epoxy materials belong to the polyethers and can be prepared, for example, by condensation of epichlorohydrin with a diol, for example an aromatic diol such as bisphenol A. These epoxy resins are then cured by reaction with a hardener, typically a polyamine.
  • a hardener typically a polyamine.
  • aminic hardeners are classified according to their chemical structure into aliphatic, cycloaliphatic or aromatic types.
  • a classification based on the degree of substitution of the amino group is possible, which may be either primary, secondary or even tertiary.
  • tertiary amines however, a catalytic curing mechanism of epoxy resins is postulated, whereas for the secondary and primary amines, stoichiometric curing reactions are used to build up the polymer network.
  • the aliphatic amines show the highest reactivity in epoxy curing.
  • the cycloaliphatic amines usually react somewhat more slowly, whereas the aromatic amines (amines in which the amino groups are bonded directly to a carbon atom of the aromatic ring) exhibit by far the lowest reactivity.
  • cycloaliphatic amines such as isophorone diamine (IPDA), 4,4'-diaminodicyclohexylmethane (dicycane), 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane (dimethyldicykan), hydrogenated bisaniline A (2, 2-di (4-aminocyclohexyl) propane), hydrogenated toluenediamines (such as, for example, 2,4-diamino-1-methylcyclohexane or 2,6-diamino-1-methylcyclohexane), 1, 3-bis (aminomethyl) cyclohexane (1, 3-BAC) is used.
  • IPDA isophorone diamine
  • dicycane 4,4'-diaminodicyclohexylmethane
  • 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane dimethyldic
  • aromatic polyamines such as phenylenediamines (ortho, meta or para), bisaniline A, toluenediamines (for example 2,4-toluenediamine or 2,6-toluenediamine), diaminodiphenylmethane (DDM), diaminodiphenylsulfone ( DDS), 2,4-diamino-3,5-diethyltoluene or 2,6-diamino-3,5-diethyltoluene (DETDA 80).
  • DDM diaminodiphenylmethane
  • DDS diaminodiphenylsulfone
  • DETDA 80 2,4-diamino-3,5-diethyltoluene or 2,6-diamino-3,5-diethyltoluene
  • cycloaliphatic polyamines are in particular dimethyl dicycane and 2,2 ', 5,5'-tetramethyl-4,4'-methylenebis (cyclohexylamine) (2,5-TMDC, also referred to as
  • TMMDCHA 2,2 ', 5,5'-tetramethylmethylenedicyclohexylamine
  • DE 2945614 describes the preparation of 2,2,6,6'-tetramethyl-4,4'-methylenebis (cyclohexylamine) (2,6-TMDC) and also mentions its use as a hardener for epoxy resins, without going into details of one to enter into such use.
  • curable compositions of epoxy resin, reactive diluent and amine curing agent with even longer pot lives and thus longer processing times than those containing dimethyldicycan or 2,5-TMDC as a curing agent without these curable compositions containing aromatic diamines and without compromising structural properties. such as the glass transition temperature) of the cured epoxy resin.
  • the object underlying the invention can therefore be considered the provision of a curable composition of epoxy resin, reactive diluent and non-aromatic, amine hardener, which has particularly long pot life (or long gel times, or slow isothermal viscosity increases) and thus particularly long processing times simultaneously good structural properties (such as the glass transition temperature) allow for the cured epoxy resin.
  • the present invention relates to a curable composition of one or more epoxy resins, one or more epoxy-containing reactive diluents, and 2,2 ', 6,6'-tetramethyl-4,4'-methylenebis (cyclohexylamine) (2,6 -TMDC) as a curing agent, said curable composition being substantially free of aromatic diamines, preferably of aromatic amines.
  • a particular embodiment of the invention relates to a curable composition
  • a curable composition comprising one or more epoxy resins, one or more epoxide group-containing reactive diluents, and 2,6-TMDC, which curable composition is free of aromatic diamines, preferably aromatic amines.
  • Reactive diluents are generally compounds which lower the initial viscosity of the curable composition and chemically bond with the developing network of epoxy resin and hardener during curing of the curable composition, for example cyclic carbonates or low molecular weight aliphatic diglycidyl compounds.
  • Epoxide-containing reactive diluents for the purposes of this invention are organic, preferably aliphatic and preferably low molecular weight (Mw ⁇ 300 g / mol) compounds having one or more epoxide groups, preferably having multiple epoxide groups, more preferably having two epoxide groups.
  • Epoxide group-containing reactive diluents are preferably selected from the group consisting of 1,4-butanediol bisglycidyl ether, 1,6-hexanediol bisglycidyl ether (HDDE), glycidyl neodecanoate, glycidyl versatate, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, p-tert-butylglycidyl ether, butylglycidyl ether, Ce-C10 alkyl glycidyl ether, C12-C14 alkyl glycidyl ether, nonylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, Cresyl glycidyl ether, polyoxyprop
  • 1,4-butanediol bisglycidyl ether 1,6-hexanediol bisglycidyl ether (HDDE), 2-ethylhexyl glycidyl ether, Ce-C10 alkyl glycidyl ether, C12-C14 alkyl glycidyl ether, neopentyl glycol diglycidyl ether, p-tert-butyl glycidyl ether, butyl glycidyl ether , Nonylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, methylolpropane triglycidyl ether (TMP), glycerol triglycidyl ether, diviny
  • TMP methylolpropane
  • 1,4-butanediol bisglycidyl ether Ce-C 1-4 alkyl monoglycidyl ether, C 12 -C 14 -alkyl monoglycidyl ether, 1,6-hexanediol bisglycidyl ether (HDDE), neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether (TMP), glycerol triglycidyl ether and dicyclopentadiene diepoxide.
  • HDDE 1,6-hexanediol bisglycidyl ether
  • TMP trimethylolpropane triglycidyl ether
  • TMP glycerol triglycidyl ether
  • dicyclopentadiene diepoxide 1,4-butanediol bisglycidyl ether, Ce-C 1-4 alkyl monoglycidyl ether, C 12
  • the epoxide group-containing reactive diluents according to the invention preferably account for up to 30% by weight, more preferably up to 25% by weight, in particular from 1 to 20% by weight, based on the resin component (epoxy resin and any reactive diluents used) of the curable composition .
  • the reactive diluents according to the invention preferably account for up to 25% by weight, more preferably up to 20% by weight, in particular from 1 to 15% by weight, based on the total curable composition.
  • the curable composition according to the invention may contain, in addition to 2,6-TMDC, further aliphatic and cycloaliphatic polyamines.
  • 2,6-TMDC is at least 50% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, based on the total amount of amine hardener in the curable composition.
  • the curable composition contains no further 2,2 ', 6,6'-tetraalkyl-4,4'-methylenebis (cyclohexylamine) compounds besides 2,6-TMDC.
  • the curable composition contains no further amine hardener besides 2,6-TMDC.
  • amine hardener is understood to mean an amine having an NH functionality of> 2 (for example, a primary monoamine has an NH functionality of 2, a primary diamine has an NH functionality of 4 and an amine of 3 secondary amino groups have an NH functionality of 3).
  • Epoxy resins according to this invention have 2 to 10, preferably 2 to 6, very particularly preferably 2 to 4 and in particular 2 epoxide groups.
  • the epoxide groups are, in particular, glycidyl ether groups, as are formed in the reaction of alcohol groups with epichlorohydrin.
  • the epoxy resins may be low molecular weight compounds. which generally have an average molecular weight (Mn) of less than 1,000 g / mol or are relatively high molecular weight compounds (polymers).
  • Such polymeric epoxy resins preferably have a degree of oligomerization of from 2 to 25, more preferably from 2 to 10 units. They may be aliphatic or cycloaliphatic compounds or compounds containing aromatic groups.
  • the epoxy resins are compounds having two aromatic or aliphatic 6-membered rings or their oligomers.
  • epoxy resins which are obtainable by reacting the epichlorohydrin with compounds which have at least two reactive H atoms, in particular with polyols.
  • epoxy resins which are obtainable by reacting the epichlorohydrin with compounds which contain at least two, preferably two hydroxyl groups and two aromatic or aliphatic 6-membered rings.
  • such compounds are in particular bisphenol A and bisphenol F, and hydrogenated bisphenol A and bisphenol F called - the corresponding epoxy resins are the diglycidyl ethers of bisphenol A or bisphenol F, or hydrogenated bisphenol A or bisphenol F.
  • epoxy resin according to this invention is usually bisphenol A diglycidyl ether (DGEBA) is used.
  • Suitable epoxy resins according to this invention are also tetraglycidyl-methylenedianiline (TGMDA) and triglycidylaminophenol or mixtures thereof.
  • reaction products of epichlorohydrin with other phenols for example with cresols or phenol-aldehyde adukten, such as phenol-formaldehyde resins, in particular novolacs.
  • epoxy resins or mixtures thereof are used according to the invention, which are liquid at room temperature (25 ° C).
  • the epoxy equivalent weight (EEW) indicates the average mass of the epoxy resin in grams per mole of epoxide group.
  • the curable composition according to the invention is at least 50 wt .-% of epoxy resin.
  • epoxy compound epoxy resins including any further organic compounds having one or more epoxide groups (for example certain reactive diluents) contained in the composition
  • amine hardeners in a relative to the epoxide or the NH functionality in used about stoichiometric ratio.
  • Particularly suitable ratios of epoxide groups to NH functionality are, for example, 1: 0.8 to 1: 1, 2.
  • the curable composition of the present invention may also contain other additives such as thinners, reinforcing fibers (especially glass or carbon fibers), pigments, dyes, fillers, release agents, tougheners, flow agents, anti-foaming agents, flame retardants or thickening agents , Such additives are usually added in a functional amount, that is, for example, a pigment in an amount that leads to the desired color for the composition.
  • the compositions according to the invention contain from 0 to 50% by weight, preferably 0 to 20 wt .-%, for example. 2 to 20 wt .-% of the total of all additives based on the total curable composition.
  • additives are understood as meaning all additions to the curable composition which are neither epoxide compounds nor amine hardeners.
  • the present invention also relates to the use of 2,6-TMDC as a curing agent for epoxy resins in curable compositions with one or more epoxy-containing reactive diluents.
  • the present invention relates to the use of 2,6-TMDC as a curing agent for epoxy resins in curable compositions having one or more epoxy group-containing reactive diluents, the curable composition comprising aromatic diamines in an amount of not more than 5% by weight, preferably not more than 1% by weight, more preferably not more than 0.1% by weight, based on the total amount of all amine hardeners.
  • the present invention particularly preferably relates to the use of 2,6-TMDC as a hardener for epoxy resins in curable compositions with one or more epoxide-containing reactive diluents without the addition of aromatic amines as further hardeners to the curable composition.
  • 2,6-TMDC can be prepared, for example, by catalytic ring hydrogenation of xylidine base with hydrogen (WO 201 1/082991, Ex. 2-16 and Ex. 2-17) or according to DE 2945614.
  • Another object of the invention is a process for the preparation of cured epoxy resins from the curable composition of the invention.
  • the components epoxy resin, epoxy-containing reactive diluent, 2,6-TMDC and optionally other components such as additives, preferably excluding aromatic amines
  • the components are contacted, mixed and mixed in any order then cured at a temperature of at least 20 ° C.
  • the cured epoxy resin is still subjected to a thermal aftertreatment, for example in the context of curing or as part of an optional downstream annealing.
  • the curing can be carried out at normal pressure and at temperatures below 250 ° C., in particular at temperatures below 210 ° C., preferably at temperatures below 185 ° C., in particular in a temperature range from 40 to 210 ° C.
  • the curing is usually done in a tool until dimensional stability is achieved and the workpiece can be removed from the tool.
  • the subsequent process for reducing residual stresses of the workpiece and / or completing the crosslinking of the cured epoxy resin is called tempering.
  • the tempering process usually takes place at temperatures at the limit of the form stiffness. Usually, at temperatures of 120 to 220 ° C, preferably at temperatures of 150 to 220 ° C annealed.
  • the hardened workpiece is exposed to the annealing conditions for a period of 30 to 240 minutes. Depending on the dimensions of the workpiece, longer annealing times may be appropriate.
  • Another object of the invention is the cured epoxy resin of the curable composition of the invention.
  • cured epoxy resin obtainable or obtained by curing a curable composition of the invention is an object of the invention.
  • cured epoxy resin which is obtainable or obtained by the process according to the invention for producing cured epoxy resins is an object of the invention.
  • the epoxy resins cured in accordance with the invention have a comparatively high Tg, although the curing agent 2,6-TMDC is a cycloaliphatic diamine in which both ortho positions are substituted for the amino groups, and although the underlying curable composition contains epoxide groups Contains reactive diluents.
  • the curable compositions according to the invention are suitable as coating or impregnating agents, as adhesives, for the production of moldings and composite materials, or as casting compositions for embedding, bonding or solidification of moldings.
  • coating agents e.g. Called paints.
  • scratch-resistant protective lacquers on any substrates e.g. be obtained from metal, plastic or wood materials.
  • the curable compositions are also useful as insulating coatings in electronic applications, e.g. as insulating coating for wires and cables. Also mentioned is the use for the production of photoresists. They are also suitable as a refinish, e.g. also when repairing pipes without dismantling the pipes (your in-place pipe (CIPP) rehabilitation). They are also suitable for sealing floors. They are particularly suitable for the production of composite materials, especially of large composite components.
  • Composite materials combine different materials, eg plastics and reinforcing materials (eg glass fibers or carbon fibers).
  • materials eg plastics and reinforcing materials (eg glass fibers or carbon fibers).
  • the curing of preimpregnated fibers or fiber fabrics eg prepregs
  • VARTM vacuum infusion
  • RTM transfer molding
  • BMC wet pressing methods
  • the curable composition is particularly suitable for the production of large moldings, in particular those with reinforcing fibers (for example glass or carbon fibers), for which comparatively long pot lives are required so that the filling of the mold or the impregnation of the fibers is ensured.
  • reinforcing fibers for example glass or carbon fibers
  • the composite materials according to the invention preferably contain glass and / or carbon fibers in addition to the cured epoxy resin according to the invention.
  • the glass transition temperature (Tg) can be determined by means of dynamic mechanical analysis (DMA), for example in accordance with the standard DIN EN ISO 6721, or with a differential calorimeter (DSC), for example in accordance with the DIN 53765 standard.
  • DMA dynamic mechanical analysis
  • a rectangular specimen with a forced frequency and given deformation is subjected to torsion.
  • the temperature is increased with a defined ramp and storage and loss module recorded at fixed time intervals.
  • the former represents the stiffness of a viscoelastic material.
  • the latter is proportional to the work dissipated in the material.
  • the phase shift between the dynamic stress and the dynamic strain is characterized by the phase angle ⁇ .
  • the glass transition temperature can be determined by different methods: as the maximum of the tan ⁇ curve, as the maximum of the loss modulus or by means of the tangent method on the storage module.
  • a very small amount of sample (about 10 mg) is heated in an aluminum crucible and the heat flux measured to a reference crucible. This cycle is repeated three times.
  • the determination of the glass transition is carried out as an average value of the second and third measurement.
  • the evaluation of the Tg stage of the heat flow curve can be determined via the inflection point, after half the width or the procedure of the midpoint temperature.
  • pot life or gel time is to be understood as meaning a parameter which is usually used to compare the reactivity of various resin / hardener and / or resin / hardener mixture combinations.
  • the measurement of pot life is a method for characterizing the reactivity of laminating systems by means of a temperature measurement. Depending on the application, deviations from the parameters described there (quantity, test conditions and measuring method) have become established.
  • the pot life is determined as follows: 100 g of curable composition containing epoxy resin and hardener or hardening mixture are filled in a container (usually a paper cup). In this curable composition, a temperature sensor is immersed, which measures the temperature at certain intervals and stores.
  • the formulations to be compared were prepared by mixing stoichiometric amounts of the particular cycloaliphatic amine (IPDA (Baxxodur EC 210, BASF), DMDC (Baxxodur EC 331, BASF) or 2,6-TMDC) with a bisphenol A diglycidyl ether based on produced epoxy resin (Epilox A19-03, Leuna resins, EEW 182) and examined immediately.
  • IPDA Boxxodur EC 210, BASF
  • DMDC Baxxodur EC 331, BASF
  • 2,6-TMDC bisphenol A diglycidyl ether based on produced epoxy resin
  • the isothermal gel time is significantly higher compared to the other diamines tested. It is also significantly higher than the isothermal gel time of 73 min at 60 ° C for 2,5-TMDC disclosed in US 4,946,925. Especially at higher temperatures it can be seen that only with 2,6-TMDC a much longer gel time can be achieved. However, higher temperatures may be required in particular for achieving favorable starting viscosities in the production of moldings.
  • the pot life is considerably longer and the maximum temperature significantly lower compared to the other diamines tested.
  • the sample with 2,6-TMDC showed only a slight increase in temperature of 3 ° C and no complete cure even after more than 30 hours.
  • a temperature increase of 12 ° C observed.
  • an increase in pot life at a storage temperature of 40 ° C was found to be 213% and a decrease in the maximum temperature of 155 ° C. 2,6-TMDC is therefore particularly suitable for epoxy resin systems where a long processing time with simultaneously low temperature increase during curing is required.
  • IPDA cycloaliphatic amines
  • resin components were used which contain 10% or 20% by weight (based on the total resin component) of the reactive diluents hexanediol bisglycidyl ether (HDDE, Epilox P13). 20, Leuna resins), butanediol bisglycidyl ether (BDDE, Epilox P13-21, Leuna), C12-C14 alkyl monoglycidyl ether (Epilox P13-18, Leuna resins) or propylene carbonate (PC, Huntsman) and also determined the Tg. Table 4:
  • Exothermic profile and glass transition temperatures (the various hardening protocols underlying the Tg measurements are given in the first column in brackets for the respective Tg measurement, the abbreviation "Exo” means that an exothermic reaction was observed in this case and thus no Tg determination possible was.
  • 2,6-TMDC excellent thermal properties (eg comparatively high Tg) can be achieved with simultaneously reduced reactivity and long processing times.
  • slow cure (1 K / min to 180 ° C)
  • a significantly higher glass transition temperature can be achieved for 2,6-TMDC, which is equivalent to that achieved with DMDC.
  • thermosets without reactive diluents
  • IPDA Boxxodur EC 210, BASF
  • DMDC Baxxodur EC 331, BASF
  • 2,6-TMDC cycloaliphatic amines
  • Cure A shows a significant increase in tensile strain for 2,6-TMDC over the other cured curing agents tested.
  • the other mechanical data show either a slightly elevated or comparable value.
  • 2,6-TMDC shows a significant increase in tensile elongation over 2,5-TMDC.

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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)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

L'invention concerne une composition durcissable constituée de résine époxyde, de diluants réactifs contenant des groupes époxydes et du durcisseur 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine), le durcissement de la composition selon l'invention et la résine époxyde durcie ainsi obtenue, ainsi qu'une utilisation correspondante de 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) en tant que durcisseur pour des résines époxydes dans des compositions durcissables renfermant des diluants réactifs contenant des groupes époxydes.
EP14700693.6A 2013-01-28 2014-01-16 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes Withdrawn EP2948493A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14700693.6A EP2948493A2 (fr) 2013-01-28 2014-01-16 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13152879 2013-01-28
PCT/EP2014/050814 WO2014114556A2 (fr) 2013-01-28 2014-01-16 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes
EP14700693.6A EP2948493A2 (fr) 2013-01-28 2014-01-16 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes

Publications (1)

Publication Number Publication Date
EP2948493A2 true EP2948493A2 (fr) 2015-12-02

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EP14700693.6A Withdrawn EP2948493A2 (fr) 2013-01-28 2014-01-16 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes

Country Status (6)

Country Link
EP (1) EP2948493A2 (fr)
JP (1) JP2016504476A (fr)
KR (1) KR20150110758A (fr)
CN (1) CN104955867A (fr)
RU (1) RU2015136364A (fr)
WO (1) WO2014114556A2 (fr)

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Publication number Priority date Publication date Assignee Title
CN105073712B (zh) 2013-01-30 2017-09-22 巴斯夫欧洲公司 2,6‑双(氨基甲基)哌啶衍生物
JP6505913B1 (ja) 2018-05-17 2019-04-24 株式会社Ｔ＆Ｋ Ｔｏｋａ 硬化性エポキシド組成物
KR102083444B1 (ko) * 2018-05-30 2020-03-02 주식회사 나노폴리켐 발전소 세정 및 내시경용 고내열성 복합소재
RU2740241C1 (ru) * 2020-03-16 2021-01-12 Максим Викторович Кулагин Способ ремонта и герметизации оборудования и трубопроводов, наполненных нефтью или нефтепродуктами
EP3882294A1 (fr) * 2020-03-18 2021-09-22 Hilti Aktiengesellschaft Composition de durcisseur à base de diaminométhylcyclohexane et de 1,3-cyclo-hexane-bis(méthylamine) pour une masse de résine époxy, masse de résine époxy et système de résine époxy multicomposant
KR102765200B1 (ko) 2021-10-15 2025-02-07 주식회사 네패스 우수한 접착 및 속경화 특성을 가지는 에폭시 접착제 조성

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US4798761A (en) * 1987-11-03 1989-01-17 The Dow Chemical Company Epoxy resin compositions for use in low temperature curing applications
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Publication number Publication date
KR20150110758A (ko) 2015-10-02
JP2016504476A (ja) 2016-02-12
WO2014114556A3 (fr) 2014-11-20
WO2014114556A2 (fr) 2014-07-31
RU2015136364A (ru) 2017-03-06
CN104955867A (zh) 2015-09-30

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