EP2731978A2

EP2731978A2 - Polyetheramines used as accelerating agents in epoxy systems

Info

Publication number: EP2731978A2
Application number: EP12733670.9A
Authority: EP
Inventors: Jean-Francois Stumbe; Anna MÜLLER-CRISTADORO; Günter Scherr; Michael Henningsen; Bernd Bruchmann; Miran Yu; Chunhong YIN; Achim Kaffee
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2011-07-15
Filing date: 2012-07-03
Publication date: 2014-05-21
Also published as: US20130184379A1; WO2013010788A2; US20160083518A1; JP2014520937A; WO2013010788A3; CN103687889A

Abstract

The invention relates to the acceleration of the hardening of compositions of epoxy compounds and amino or anhydrid hardeners by adding highly-branched polyetheramines. Said highly branched polyetheramines can comprise terminal hydroxy groups (polyols) and/or amino groups (amino-modified). Said amino-modified highly branched polyetheramines can be obtained by subsequent modification of the terminal hydroxy groups of highly branched polyetheramine polyols.

Description

Polyetheramines as accelerators in epoxy systems

Description This application includes, by reference, US Provisional Application 61 / 508,096 filed Jul. 15, 2011.

The present invention relates to a curable composition comprising an epoxy compound, an amino or anhydride curing agent and a highly branched polyetheramine. The highly branched polyetheramine may terminally have hydroxyl groups (polyol) and / or amino groups (a-mino-modified).

The invention also relates to amino-modified hyperbranched polyetheramines which have an average of at least 1%, preferably at least 5%, amino groups as terminal groups, and to a process for preparing such amino-modified highly branched polyetheramines.

Further objects of the invention are the process for the preparation of cured epoxy resins from the curable composition, the use of highly branched polyethers as accelerators for the curing of epoxy resins, as well as cured epoxy resin of the curable composition and moldings produced therefrom. In addition, the curable composition can also be used in adhesive or paint applications.

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 composites epoxy resins are used. The use of epoxy resins in casting, potting and encapsulation is well known in the electrical and tool industries.

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. The epoxy resins are then cured by reaction with a hardener, typically a polyamine (US 4,447,586, US 2,817,644, US 3,629,181, DE 1006101, US 3,321,438).

There are different ways to cure known. Starting from epoxide compounds having at least two epoxide groups, hardening by a polyaddition reaction (chain extension) can be carried out, for example, with an amino compound having two amino groups. High reactivity amino compounds are generally added only shortly before the desired cure. They are therefore so-called two-component (2K) systems. Alternatively, so-called latent hardeners, for example dicyandiamide or various anhydrides, can be used which are only active at high temperatures, so that An undesirable early cure is avoided and one-component (1K) systems are possible.

There is a great need for compositions which make it possible to precisely control and adjust the curing of the epoxy resin for the desired requirements. Thus, especially during the production of large components, the viscosity should not increase so much during the processing time that full filling of the mold or adequate wetting of the composite fibers is no longer guaranteed. At the same time, the cycle time, ie the time for processing and curing, should not be adversely affected.

The rate of stoichiometric curing of epoxide compounds with amino hardeners can be increased by adding tertiary amines to the composition which act as accelerators. Examples of such accelerators are triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and tetramethylguanidine (US 4,948,700). However, US Pat. No. 6,743,375 teaches the person skilled in the art that tetramethylguanidine is a comparatively weak accelerator. A disadvantage of using these accelerators is that they can migrate after curing in the cured epoxy resin. Unwanted aging processes and poorer material properties due to the then unevenly distributed in the finished cured epoxy resin accelerator, as well as unwanted release of these chemicals from the cured epoxy resin are the result. Even during processing, the use of these compounds is problematic because it can come because of their slight volatility to odorous, health-impairing and / or combustible emissions. This is a problem especially when using toxic or regulatory regulated compounds such as triethanolamine.

It is therefore an object of the present invention to provide additives for compositions of epoxy compounds and amino or anhydride curing agents which can accelerate curing in a controlled manner without the disadvantages of known accelerators.

Accordingly, the present invention relates to curable compositions comprising one or more epoxy compounds, one or more amino or anhydride curing agents and an addition of one or more highly branched polyetheramines. The highly branched polyetheramines according to the invention are highly branched polyetheramine polyols having terminal hydroxy groups or derivatives thereof in which the terminal hydroxyl groups are completely or partially modified. The terminal hydroxy groups of the derivatives are preferably modified in such a way that the corresponding polyetheramine has terminal primary and / or secondary amino groups. The derivatives of the highly branched polyetheramine polyols according to the invention are preferably amino-modified highly branched polyetheramines. The invention also relates to processes for the preparation of cured epoxy resins from the curable composition of the invention by curing the composition. The curing is preferably carried out thermally by heating the composition to at least a temperature at which the amino groups or the anhydride groups of the curing agent and the epoxy groups of the epoxy compound react with each other. 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 of moldings is usually done in a tool until dimensional stability is achieved and the workpiece can be removed from the tool. The degree of curing can be determined by DSC (differential scanning calorimetry) by measuring the released reaction energy. Alternatively, theological analyzes, pot life measurements or viscosity determinations may also be used to determine the extent of cure. The curing can also be done by non-thermal methods, such as by microwave treatment.

The invention further relates to the use of highly branched polyetheramines as an additive in a curable composition of one or more epoxy compounds and one or more amino or anhydride hardeners to accelerate the cure. Unexpectedly, the macromolecular highly branched polyetheramines cause a significant acceleration of the curing process. Compared with the curable composition without the addition of highly branched polyetheramines, the time until complete curing or until a fixed viscosity is reached (eg 10,000 mPas) is reduced by at least 5%, preferably by at least 10%, more preferably under otherwise identical curing conditions at least 20%.

Furthermore, the invention relates to cured epoxy resins preparable by complete or partial curing of the curable composition of the invention. The curing is preferably carried out until a viscosity of at least 10,000 mPas or until dimensional stability has been reached. The invention relates to cured epoxy resins from the curable composition according to the invention. The cured epoxy resins may be in the form of shaped bodies, possibly as composite materials with glass or carbon fibers.

The highly branched polyetheramine polyols according to the invention, which carry a multiplicity of functional groups, are optionally obtained from trialkanolamines also in a mixture with mono- or dialkanolamines. For this purpose, these monomers are catalytically etherified (acidic or basic catalysis) with elimination of water. The preparation of these polymers is described for example in US 2,178,173, US 2,290,415, US 2,407,895 and DE 40 03 243. The polymerization can be carried out either statistically or block structures can be prepared from individual alkanolamines which are linked together in a further reaction (US Pat. No. 4,404,362). As starting material for the synthesis of highly branched polyetheramine polyols trialkanolamines such as triethanolamine, tripropanolamine, triisopropanolamine or tributanolamine are used, optionally in combination with dialkanolamines such as diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, Ν, Ν ^' -Dialkanolpiperidin, or in combination with di- or higher-functional polyetherols based on ethylene oxide and / or propylene oxide. Preferably, however, triethanolamine and triisopropanolamine or their mixture is used as the starting material. The highly functional highly branched polyetheramine polyols are terminated with hydroxy groups after the reaction, ie without further modification.

Terminal groups in the sense of this invention are free, reactive groups (terminal or pendant), such as, for example, hydroxyl groups, primary or secondary amino groups, terminal monomer units or reagents of highly branched polyetheramine coupled to terminal monomer units.

Alkanol groups in the context of this invention are aliphatic radicals, preferably having 1 to 8 C atoms, a hydroxyl group and without further heteroatoms. The radicals can be linear, branched or cyclic and saturated or unsaturated. In the context of this invention, a hyperbranched polyetheramine polyol is to be understood as meaning a product which, in addition to the ether groups and the amino groups which form the polymer backbone, furthermore has at least three, preferably at least six, more preferably at least ten, more preferably at least 20 hydroxyl groups. The number of terminal hydroxy groups is in principle not limited to the top, but products with a very high number of hydroxyl groups may have undesirable properties, such as high viscosity or poor solubility. The highly branched polyetheramine polyols of the present invention generally have not more than 500, preferably not more than 150, terminal hydroxy groups. The polyetheramine polyols are prepared either in solution or preferably without solvent. Possible solvents are aromatic and / or aliphatic (including cycloaliphatic) hydrocarbons and mixtures thereof, halogenated hydrocarbons, ketones, esters and ethers. The temperature in the preparation should be sufficient for the reaction of the alkanolamine. In general, the reaction is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 to 300 ° C, more preferably 180 to 280 ° C and especially 200 to 250 ° C.

The liberated in the reaction water or low molecular weight reaction products can be removed to accelerate and to complete the reaction from the reaction equilibrium, for example by distillation, optionally at reduced pressure. The separation of the water or of the low molecular weight reaction products can also be supported. by passing a substantially inert gas stream under the reaction conditions (stripping), such as nitrogen or noble gases such as helium, neon or argon.

To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze etherification or conversion reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, preferably of sodium, potassium or cesium, and acidic compounds such as iron chloride or zinc chloride, formic acid, oxalic acid or phosphorus-containing acidic compounds, such as phosphoric acid, polyphosphoric acid, phosphorous acid or hypophosphorous acid. Preference is given to using phosphoric acid, phosphorous acid or hypophosphorous acid, if appropriate in a form diluted with water.

The addition of the catalyst is generally carried out in an amount of 0.001 to 10 mol%, preferably from 0.005 to 7 mol%, particularly preferably 0.01 to 5 mol%, based on the amount of the alkanolamine or alkanolamine mixture used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, the average molecular weight of the polymers can be adjusted via the composition of the starting components and over the residence time.

The polymers prepared at elevated temperature are usually stable over a longer period of time, for example for at least 6 weeks, at room temperature, without turbidity, precipitation and / or viscosity increase.

There are various possibilities for stopping the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the polycondensation product is storage-stable. For this purpose, the temperature is usually lowered to below 60 ° C., preferably below 50 ° C., more preferably below 40 ° C. and most preferably to room temperature.

Alternatively, one can deactivate the catalyst for stopping the polycondensation reaction. This is carried out in the case of basic catalysts, for example by adding an acidic component, such as a Lewis acid or an organic or inorganic protic acid. For acidic catalysts, this is done, for example, by adding a basic component, such as a Lewis base or an organic or inorganic base.

Further, it is possible to stop the reaction by dilution with a pre-cooled solvent. This is particularly preferred if it is necessary to adjust the viscosity of the reaction mixture by adding solvent. The high-functionality highly branched polyetheramine polyols according to the invention generally have a glass transition temperature of less than 50 ° C., preferably less than 30 ° C. and more preferably less than 10 ° C. The OH number of the highly branched polyetheramine polyols according to the invention is usually 50 mg KOH / g or more, preferably 150 mg KOH / g or more. The OH number indicates the amount of potassium hydroxide in milligrams, which is equivalent to the amount of acetic acid bound upon acetylation of one gram of the substance. It is typically determined according to regulation DIN 53240, part 2.

The invention also relates to amino-modified hyperbranched polyetheramines which are obtainable starting from highly branched polyetheramine polyols by reacting an average of at least 1%, preferably at least 5%, of the terminal hydroxyl groups with reagents containing at least one primary or secondary amino group and at least one have a reactive group suitable for coupling to the terminal hydroxy groups. The reactive group is, for example, an alcohol, carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, amine or amide group, preferably an alcohol, carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride group, more preferably an alcohol group , The coupling may be, for example, a cure, an esterification, a transamination or a reaction with cyclic amides such as e.g. Caprolactam act. Preferred couplings are etherifications.

The invention also relates to a process for the preparation of amino-modified polyetheramines, which is characterized in that a highly branched polyetheramine polyol is reacted with a reagent which has at least one primary or secondary amino group and at least one to covalent coupling with suitable reactive group for the terminal hydroxy groups of the hyperbranched polyetheramine polyol. The reactive group is, for example, an alcohol, carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride, amine or amide group, preferably an alcohol, carboxylic acid, carboxylic acid anhydride, carboxylic acid chloride group, more preferably an alcohol group.

Suitable reagents for the reaction of the terminal hydroxyl groups of highly branched polyetheramine polyols are, for example, monohydric or polyhydric amino alcohols, preferably monohydric aminoalcohols which can form ether bonds with the terminal hydroxy groups of the highly branched polyetheramine polyol. Such amino alcohols are, for example, linear or branched, aliphatic or aromatic alcohols. Such amino alcohols which are used to introduce secondary or primary amino groups are preferably aliphatic amino alcohols having 2 to 40 carbon atoms and aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols having 6 to 20 carbon atoms and aromatic structures having heterocyclic or isocyclic ring systems. Examples of suitable aliphatic amino alcohols are N- (2-hydroxyethyl) ethylenediamine, ethanolamine, propanolamine, butanolamine, diethanolamine, dipropanolamine, dibutanolamine, 1-amino-3,3-dimethylpentan-5 ol, 2-aminohexane-2 ', 2 "-diethanolamine, 1-amino-2,5-dimethylcyclohexan-4-ol, 2-aminopropanol, 2-aminobutanol, 3-aminopropanol, 1-amino-2-propanol, 2 -Amino-2-methyl-1-propanol, 5-aminopentanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 1-amino-1-cyclopentan-methanol, 2-amino-2-ethyl-1,3-propanediol Examples of suitable aromatic-aliphatic or aromatic-cycloaliphatic amino alcohols are naphthalene or in particular benzene derivatives such as 2-aminobenzyl alcohol, 3- (hydroxymethyl) aniline, 2-amino-3-phenyl-1-propanol, 2-amino-1-phenylethanol, 2-phenylglycinol or 2-amino-1-phenyl-1,3-propanediol In the context of this invention, an amino-modified hyperbranched polyetheramine is to be understood as meaning a product which, in addition to the ether groups and the amino groups , which form the polymer backbone, terminally further at least three, preferably at least six, more preferably at least ten, particularly preferably at least 20 functional Gr uppen. These functional groups are hydroxy groups to which an average of at least 1%, preferably at least 5%, of a reagent which has at least one primary or secondary amino group is coupled. The reagent is preferably coupled via an ether bridge. In principle, the number of terminal functional groups is not limited to the above, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The amino-modified hyperbranched polyetheramines of the present invention generally have not more than 500, preferably not more than 150, terminal functional groups.

The weight-average molecular weight (M w) of the highly branched polyether amines is generally from 1 to 500 000 g / mol, preferably from 2000 to 300 000 g / mol.

The highly branched polyetheramines have trialkanolamines as monomer units, for example triethanolamine, tripropanolamine, triisopropanolamine or tributanolamine, if appropriate in combination with dialkanolamines and / or polyetherols, the monomer units in the hyperbranched polyetheramine being linked to one another via their hydroxyl groups to form ether bridges.

Highly branched polyetheramine is described, for example, for use in coating surfaces (WO 2009/047269) or for producing nanocomposites (WO 2009/1 15535).

The curable composition according to the invention preferably has a content of from 0.1 to 20% by weight, particularly preferably from 1 to 10% by weight, of the hyperbranched polyetheramine. Epoxy compounds 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 used in the reaction of alcohol groups with Epichlorohydrin arise. The epoxide compounds 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). The epoxy compounds typically have a degree of oligomerization of 1 to 25 monomer units. They may be aliphatic or cycloaliphatic compounds or compounds containing aromatic groups. In particular, the epoxy compounds are compounds having two aromatic or aliphatic 6-membered rings or their oligomers. Of technical importance are epoxide compounds which are obtainable by reacting the epichlorohydrin with compounds which have at least two reactive H atoms, in particular with polyols. Of particular importance are epoxide compounds obtainable by reacting the epichlorohydrin with compounds containing at least two, preferably two, hydroxy groups and two aromatic or aliphatic 6-membered rings. As such compounds, in particular bisphenol A and bisphenol F, and hydrogenated bisphenol A and bisphenol F may be mentioned. As the epoxy compounds according to this invention, for example, bisphenol A diglycidyl ether (DGEBA) is used. Also suitable are reaction products of epichlorohydrin with other phenols, for example with cresols or phenol-aldehyde adukten, such as phenol-formaldehyde resins, in particular novolacs. Also suitable are epoxide compounds which are not derived from epichlorohydrin. Suitable examples are epoxide compounds which contain epoxide groups by reaction with glycidyl (meth) acrylate.

Amino hardeners for the purposes of the present invention are compounds having at least one primary or at least two secondary amino groups. Starting from epoxide compounds having at least two epoxide groups, hardening by a polyaddition reaction (chain extension) can be carried out with an amino compound having at least two amino functions. The functionality of an amino compound corresponds to their number of NH bonds. A primary amino group thus has a functionality of 2 while a secondary amino group has a functionality of 1. By linking the amino groups of the amino hardener with the epoxide groups of the epoxide compound, oligomers of the amino hardener and the epoxide compound are formed, wherein the epoxide groups are converted to free OH groups. Preference is given to using amino hardeners having a functionality of at least 3 (for example at least 3 secondary amino groups or at least one primary and one secondary amino group), especially those having two primary amino groups (functionality of 4). Preferred amino hardeners are isophoronediamine (IPDA), dicyandiamide (DICY), diethylenetriamine (DETA), triethylenetetramine (TETA), bis (p-aminocyclohexyl) methane (PACM), polyetheramine D230, dimethyldicykan (DMDC), diaminodiphenylmethane (DDM) , Diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene and mixture thereof. Particularly preferred amino hardeners for the curable composition of the present invention are isophoronediamine (IPDA), dicyandiamide (DICY) and polyetheramine D230.

Preferably, in the case of the curable composition according to the invention, epoxy compound and amino hardener are used in an approximately stoichiometric ratio the number of epoxide groups or the amino functionality. Particularly suitable ratios are, for example, 1: 0.8 to 1: 1, 2.

Anhydridhärter in the context of the present invention are organic compounds having at least one, preferably with exactly one intramolecular carboxylic acid anhydride group. Preferred anhydride hardeners are succinic anhydride (SCCA), phthalic anhydride (PSA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA),

Methyltetrahydrophthalic anhydride (MTHPA), methylhexahydrophthalic anhydride

(MHHPA), endo-cis-bicyclo [2.2.1] -6-methyl-5-heptene-2,3-dicarboxylic anhydride (Nadic methyl anhydride, NMA), dodecenylsuccinic anhydride (DDSA), pyromellitic dianhydride (PMDA), trimellitic anhydride (TMA) and benzophenone tetracarboxylic dianhydride (BTDA) and mixtures thereof. Particularly preferred anhydride hardeners for the curable composition of the invention are MHHPA and NMA. In the case of the curable composition according to the invention, epoxide compound and anhydride hardener are preferably used in an approximately stoichiometric ratio based on the number of epoxide or anhydride groups. Suitable ratios are, for example, 1: 0.8 to 1: 1, 2. Curable compositions according to the present invention include, for example, the combination comprising diglycidyl ethers of bisphenol A (DGEBA), isophoronediamine (IPDA) and hyperbranched polyetheramine, the combination comprising DGEBA, IPDA and highly branched amino-modified polyetheramine, the combination comprising DGEBA, polyetheramine D230 and highly branched polyetheramine, the combination comprising DGEBA, polyetheramine D230 and highly branched amino-modified polyetheramine, the combination comprising DGEBA, dicyandiamide (DICY) and hyperbranched polyetheramine, the combination comprising DGEBA, DICY and hyperbranched amino-modified polyetheramine, the combination comprising DGEBA, methylhexahydrophthalic anhydride (MHHPA) and hyperbranched polyetheramine, the combination comprising DGEBA, MHHPA and hyperbranched amino-modified polyetheramine, the combination comprising DGEBA, Nadic methyl anhydride (NMA) and hyperbranched polyetheramine and the combination comprising DGEBA , NMA and hyperbranched amino-modified polyetheramine.

The curable composition of the present invention may be both a liquid and solid epoxy compound, amino or anhydride curing agent, and hyperbranched polyetheramine composition. Preferred are liquid compositions. According to the desired use, the compositions may include liquid components (epoxy compound, amino or anhydride hardener and hyperbranched polyetheramine) or solid components. Mixtures of solid and liquid components can also be used, for example, as solutions or dispersions. For example, mixtures of solid components are used for use as powder coatings. Liquid compositions are of particular importance for the production of fiber-reinforced composite materials. The physical state of the epoxy compound can be adjusted in particular by the degree of oligomerization.

The curable composition of the invention with the addition of hyperbranched polyetheramine allows accelerated curing compared to the corresponding formulation without this additive. The curing is preferably accelerated by at least 5%, particularly preferably by at least 10%, in particular by at least 20%. The acceleration of the curing can be determined in particular by measuring the time to reach a set viscosity of 10,000 mPas composition of the invention compared with the corresponding composition without the addition of highly branched polyether under otherwise identical curing conditions. The acceleration of the curing can also be determined by measuring the time to hardening of the composition of the invention on a tempered hot plate with constant stirring compared with the corresponding composition without the addition of the highly branched polyether under otherwise identical curing conditions. Advantageously, the highly branched polyetheramine does not migrate in the cured epoxy resin due to its high molecular weight and does not migrate during processing.

Preferably, highly branched polyetheramines having a similar viscosity to the epoxy compound used in the composition are used for the curable composition of the present invention. In such a case, the usually low-viscosity hardener can first be mixed with the highly branched polyetheramine to form a pre-formulation. This pre-formulation and the similarly viscous epoxy compound can then be mixed well and uniformly with one another shortly before curing (for example, into a molding). Preferably, the viscosities of these components (preformulation and epoxide compound) at the mixing temperature differ by a maximum of a factor of 20, more preferably by a maximum of a factor of 10, in particular a maximum of a factor of 5, preferably a mixing temperature is selected which is 0 to 20 ° C, more preferably 0 to 10 ° C below the selected curing temperature. In the production of carbon fiber reinforced or glass fiber reinforced composite materials, a temperature is preferably selected for mixing the components and filling the mold with the wetting of the fibers, wherein the epoxy compound used has a viscosity of not more than 200 mPas, particularly preferably not more than 100 mPas, in particular a viscosity in a range of 20 to 100 mPas. The mixing of similarly viscous liquids usually succeeds better and more uniformly than the mixing of very different viscous liquids. Therefore, using such preformulations having a viscosity adapted to the epoxy compound, moldings of cured epoxy resin whose material property is better and more uniform can be produced.

In addition, the cured epoxy resins of the present invention have improved mechanical properties compared to the cured epoxy resins resulting from a corresponding However, without the addition of highly branched polyetheramine be prepared composition. Thus, in the case of the cured epoxy resins according to the invention, the flexural strength, the flexural modulus and the bending elongation are markedly improved. These parameters can be determined, for example, by means of a 3-point bending test according to ISO 178: 2006.

The present invention will be explained in more detail with reference to the following examples. Example 1 and 2

Preparation of the highly branched polyetheramine polyols polyTEA (Example 1) and polyTIPA (Example 2)

In a four-necked flask equipped with stirrer, distillation bridge, Gaseinleitrohr and internal thermometer, 2000 g of triethanolamine (TEA; Example 1) or triisopropanolamine (TlPA; Ex. 2) and 13.5 g of hypophosphorous acid were presented as a 50% aqueous solution and the mixture is heated to 230 ° C. At about 220 ° C began the formation of condensate. The reaction mixture was stirred at 230 ° C for the time indicated in Table 1, wherein the water of reaction formed in the reaction was removed by means of moderate IS stream as stripping gas on the distillation bridge. Towards the end of the stated reaction time, residual water of reaction was removed at a reduced pressure of 500 mbar.

After reaching the desired degree of conversion, the approach to 140 ° C.

cooled and the pressure slowly and gradually reduced to 100 mbar to remove remaining volatiles.

The product mixture was then cooled to room temperature and analyzed. Example 3

Preparation of highly branched amino-modified polyTEA

In a four-necked flask equipped with stirrer, distillation bridge, gas inlet tube and internal thermometer, 500 g of polytriethanolamine (polyTEA, Ex. 1) and 138 g of N- (2-hydroxyethyl) ethylenediamine were submitted. The mixture was then heated to 230 ° C and stirred for 4.5 h, whereby the water of reaction formed in the reaction was removed by means of moderate IS flow as stripping gas over the distillation bridge. Towards the end of the stated reaction time, residual water of reaction was removed at a reduced pressure of 500 mbar.

After reaching the desired degree of conversion, the approach to 140 ° C.

The product mixture was then cooled to room temperature and analyzed. Example 4

Preparation of highly branched amino-modified polyTIPA In a four-necked flask equipped with stirrer, distillation bridge, gas inlet tube and internal thermometer, 600 g Polytnisopropanolamin (PolyTIPA, Ex. 2) and 208 g of N- (2-hydroxyethyl) ethylenediamine were submitted. The mixture was then heated to 230 ° C and stirred at 230 ° C for 4.5 h, wherein the water of reaction formed in the reaction was removed by means of moderate IS stream as stripping gas over the distillation bridge. Towards the end of the stated reaction time, residual water of reaction was removed at a reduced pressure of 500 mbar.

After reaching the desired degree of conversion, the approach to 140 ° C.

cooled and the pressure slowly and gradually reduced to 100 mbar to remove any remaining volatile components.

The product mixture was then cooled to room temperature and analyzed.

Example 5

Analysis of the hyperbranched polyetheramines of Examples 1 to 4

The polyetheramines were analyzed by gel permeation chromatography (GPC) with a refractometer as detector. Hexafluoroisopropanol (HFIP) was used as the mobile phase, and polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)). The OH number was determined in accordance with DIN 53240, Part 2.

The amine number indicates the amount of potassium hydroxide in milligrams that corresponds to the amine basicity of one gram of the test compound. Their voting took place according to the regulation ASTM D 2074.

The results of the analysis are summarized in Table 1.

Table 1 :

Starting materials and end products

Ex. 1 2 3 4

Reaction time (h) 4 0.2

Mass of water of reaction (g) 245 36 39 50

Mw per GPC (g / mol) 6,500 4,220 13,000 5,980

Mn by GPC (g / mol) 3,800 3,560 5,500 4,290

OH number of the product 595 747 61 1 750

(mg KOH / g)

Amine number for all amino groups 410 297 555 477

(mg KOH / g)

Amine number for tert. Amino groups 406 296 436 294

(mg KOH / g) Example 6

Rheological Investigation Epoxy Compositions with Hardener Isophoronediamine and Addition of Highly Branched Polyetheramines Per 5 g of the hyperbranched polyetheramines of Ex. 1 to 4 were respectively mixed with 100 g of a bisphenol A type low viscosity and solvent free epoxy resin (Epilox A 19-03 of LEUNA-Harze GmbH) and 23.6 g of the cycloaliphatic amino hardener isophoronediamine (IPDA from BASF SE). The reference was a batch of the same amounts of epoxy resin and IPDA without the addition of a highly branched polyetheramine. The reactivity of the epoxy compositions was examined by measuring the viscosity of the

Epoxy compositions over time at 40 ° C by means of plate / plate rheometer (MCR300 from Anton Paar GmbH, Austria). Determined as a measure of the reactivity, the reaction time at which the respective epoxy composition reached a viscosity of 10,000 mPas. The results are summarized in Table 2.

Example 7

Rheological analysis Epoxy compositions with hardener Polyetheramine D230 and addition of highly branched polyetheramines Per 5 g of hyperbranched polyetheramines of Ex. 1 to 4 were each mixed with 100 g of a low viscosity and solvent-free bisphenol A type epoxy resin (Epilox A 19-03 from LEUNA-Harze GmbH) and 33.5 g of the amino hardener D230 (from BASF SE), an aliphatic linear polyetheramine. The reference was a batch of the same amounts of epoxy resin and D230 without the addition of a highly branched polyetheramine. The reactivity of the epoxy compositions was studied by measuring the viscosity of the epoxy compositions over time at 40 ° C using a plate / plate rheometer (MCR300 from Anton Paar GmbH, Austria). Determined as a measure of the reactivity, the reaction time at which the respective epoxy composition reached a viscosity of 10,000 mPas. The results are summarized in Table 2.

Example 8

Rheological analysis Epoxy compositions with hardener dicyandiamide and addition of highly branched polyetheramines Per 5 g of hyperbranched polyetheramines of Ex. 1 to 4 were respectively mixed with 100 g of a bisphenol A type low viscosity and solvent free epoxy resin (Epilox A 19-03 of LEUNA-Harze GmbH) and 6.52 g of the latent amino hardener dicyandiamide (DICY, Dyhard 100SH from AlzChem Trostberg GmbH), which is used in particular in 1-K epoxide systems. The reference was a batch of the same amounts of epoxy resin and DICY without the addition of a highly branched polyetheramine. The reactivity of the epoxy compositions was studied by measuring the viscosity of the epoxy compositions over time at 140 ° C by plate / plate rheometer (MCR300 of Anton Paar GmbH, Austria). Determined as a measure of the reactivity, the reaction time at which the respective epoxy composition reached a viscosity of 10,000 mPas. The experiment was stopped after 60 minutes. The results are summarized in Table 2.

Example 9

Determination of the Thermal Properties of Epoxy Compositions with Isophoronediamine Hardener and Addition of Highly Branched Polyetheramines by the DSC Method (Differential Scanning Calorimetry) The epoxy compositions with isophoronediamine hardener and addition of highly branched polyetheramine and the corresponding reference were prepared as described in Example 6 , The DSC analysis was performed according to ASTM 3418/82. The onset temperature (To), the peak maximum temperature (T _ma x) and the glass transition temperature (T _g ) were determined. The results are summarized in Table 2.

Table 2:

Rheologically determined reaction time and DSC analysis

Polyetheramine 5 g polyTEA 5 g polyTIPA 5 g amino-5 g amino reference

Addition from Ex. 1 from Ex. 2 Modified Modified

polyTEA made of polyTIPA

Ex. 3 Ex. 4

Reaction time for

IPDA curing 38 29 52 40 69 acc. Example 6 (min)

Reaction time for

D230 hardening 165 1 16 185 156 195 acc. Example 7 (min)

Reaction time for

DICY Hardening 6> 60 4 18> 60 acc. Ex. 8 (min)

according to Ex. 9 66.8 47.3 62.6 53.0 74.3

(° C)

according to Ex. 9 96 90.5 96.7 95.1 100.8

(° C)

T _g for IPDA curing acc. Ex. 9 146.4 143.8 149.7 145.7 158

(° C) Example 10

Determination of the Pot Life of Epoxy Compositions with Isophoronediamine Hardener and Addition of Highly Branched Polyetheramines

The epoxy compositions with isophorone diamine (IPDA) hardener and with the addition of highly branched polyetheramine according to Example 2 and Example 4 and the corresponding reference without the addition of highly branched polyetheramine were prepared as described in Example 6. For the analysis of the pot life, the reaction temperature was measured in each case for 100 g of the curable composition in thermoscanning. The pot life is the time to reach the maximum reaction temperature. It corresponds to the time during which the viscosity of the curable composition is low enough that processing of the composition is possible. The maximum temperature and pot life were determined. The corresponding epoxy compositions with the hyperbranched polyetheramine according to Example 2 has a pot life of 43 min and a maximum temperature of 226 ° C and that with the highly branched polyetheramine according to Example 4 has a pot life of 66.9 minutes and a maximum temperature of 226 ° C while the reference composition has a pot life of 137 minutes and a maximum temperature of 174 ° C. Example 1 1

Determination of the Thermal Properties of Epoxy Compositions with Dicyandiamide (DICY) Hardener and Addition of Hyperbranched Polyetheramines by DSC Method (Differential Scanning Calorimetry) The Epoxy Compositions with Dicyandiamide (DICY) Hardener and Addition of Highly Branched Polyetheramine and the Corresponding Reference without the addition of hyperbranched polyetheramine were prepared as described in Example 8. The DSC analysis was performed according to ASTM 3418/82. The onset temperature (To), the peak maximum temperature (T _ma x) and the glass transition temperature (T _g ) were determined. The results are summarized in Table 3.

Example 12

Determination of the curing time of epoxy compounds with dicyandiamide (DICY) hardener and addition of highly branched polyetheramines

Cure time determination was on a B-time plate at 160 ° C. The epoxy compositions with dicyandiamide (DICY) hardener and addition of highly branched polyetheramine and the corresponding reference without the addition of highly branched polyetheramine were prepared as described in Example 8 and dropped onto the 160 ° C hot plate. The mixture was then stirred by hand constantly with a wooden stick until it became hard. The appropriate time is the cure time. The measurements are summarized in Table 3. Compared with the cure time, the reference showed the epoxy compositions with the addition of hyperbranched polyetheramines a significantly reduced curing time. The addition of these highly branched polyetheramines thus had a curing effect significantly accelerating effect. Table 3:

Rheologically determined reaction time and DSC analysis

Example 13

Determination of mechanical properties of epoxy resin cured epoxy resins

Compositions with isophoronediamine hardener and addition of hyperbranched polyetheramines

The epoxy compositions with isophorone diamine (IPDA) hardener and with the addition of highly branched polyetheramine according to Example 1 (polyTEA) and Example 2 (polyTIPA) and the corresponding reference without the addition of highly branched polyetheramine were prepared as described in Example 6. The curing was carried out by heating to 80 ° C for 2 h and then to 125 ° C for 3 h. The flexural strength, flexural modulus and flexing elongation were examined on the cured samples. The results are summarized in Table 4. By adding the highly branched polyetheramines to the epoxy composition, it was possible to obtain cured epoxy resins which had markedly improved mechanical properties. Table 4:

Mechanical examination

Example 14

Rheological investigation and determination of the curing time of epoxy compounds with hardener methylhexahydrophthalic anhydride and addition of hyperbranched polyetheramines

5 g each of the highly branched polyetheramines of Ex. 1 to 4 were each mixed with 100 g of a low-viscosity and solvent-free epoxy resin of the bisphenol A type (Epilox A 19-03 from LEUNA-Harze GmbH) and 85 g of the anhydride curing agent methylhexahydrophthalic anhydride (MHHPA from ACROS Organics). A reference of the same amounts of epoxy resin and MHHPA without the addition of a highly branched polyetheramine served as a reference. The reactivity of the epoxy compositions was examined by measuring the viscosity of the epoxy compositions over time at 120 ° C using plate / plate rheometer (MCR300 from Anton Paar GmbH, Austria). Determined as a measure of the reactivity, the reaction time at which the respective epoxy composition reached a viscosity of 10,000 mPas. The reaction time determinations for the reference were stopped after 120 minutes. The results are summarized in Table 5.

Cure time determination was on a B-time plate at 160 ° C. The epoxy compositions with MHHPA hardener and addition of highly branched polyetheramine and the corresponding reference were dropped onto the 160 ° C hot plate. The mixture was then stirred by hand constantly with a wooden stick until it became hard. The appropriate time is the cure time. The determination of the curing time was stopped after 120 minutes for the reference or at the latest after 30 minutes for the samples with addition of hyperbranched polyetheramine. The results are summarized in Table 5

Example 15

Rheological Investigation and Determination of the Curing Time Epoxy Compositions with Hardener Nadic Methyl Anhydride and Addition of Highly Branched Polyetheramines Per 5 g of the highly branched polyetheramines of Ex. 1 to 4 were each mixed with 100 g of a bisphenol A type low-viscous and solvent-free epoxy resin ( Epilox A 19-03 from LEUNA-Harze GmbH) and 85 g of the anhydride hardener Nadic methyl hydride (NMA from Fluka). The reference was a batch of the same amounts of epoxy resin and NMA without the addition of a highly branched polyetheramine. The reactivity of the epoxy compositions was investigated by measuring the viscosity of the epoxy compositions over time at 120 ° C. using a plate / plate rheometer (MCR300 from Anton Paar GmbH, Austria). Determined as a measure of the reactivity, the reaction time at which the respective epoxy composition reached a viscosity of 10,000 mPas. The reaction time determinations for the reference were stopped after 120 minutes. The results are summarized in Table 5. Cure time determination was on a B-time plate at 160 ° C. The epoxide

Compositions with NMA hardener and addition of highly branched polyetheramine and the corresponding reference were dropped onto the 160 ° C hot plate. The mixture was then stirred by hand constantly with a wooden stick until it became hard. The appropriate time is the cure time. The determination of the curing time was stopped after 120 minutes for the reference and after 30 minutes at the latest for the samples with the addition of hyperbranched polyetheramine. The results are summarized in Table 5

Table 5:

Rheologically determined reaction time and determination of the curing time

Polyetheramine additive 5 g poly-5 g polyTI-5 g amino-5 g amino reference

TEA from PA from Ex. Modified modified

Ex. 1 2 polyTEA polyTIPA

from example 3 from example 4

Reaction time for MHH-PA Hardening at 120 ° C 6.1 39.5 9 18.4> 120 (min)

Curing time for MHHPA

1, 6> 30 1, 7 8> 120 Hardening at 160 ° C (min)

Reaction time for NMA

1 1, 6 68.7 13.3 32.4> 120 Hardening at 120 ° C (min)

Curing time for NMA

3> 30 2.9> 30> 120 Curing at 160 ° C (min)

Claims

claims

A curable composition comprising at least one epoxy compound, at least one amino or anhydride curing agent and at least one highly branched polyetheramine, wherein the epoxy compounds has 2 to 10 epoxide groups.

The curable composition of claim 1, wherein the curing agent is an amino curing agent having at least one primary or two secondary amino groups.

The curable composition of claim 1, wherein the curing agent is an anhydride curing agent having at least one intramolecular carboxylic acid anhydride group.

The curable composition of any one of claims 1 to 3, wherein the hyperbranched polyether amine is a highly branched polyether amine polyol having at least 3 terminal hydroxy groups.

The curable composition of any one of claims 1 to 3, wherein the hyperbranched polyetheramine is an amino-modified hyperbranched polyetheramine having at least three terminal hydroxy groups to which at least 1% average of a reagent is coupled, the at least one primary or secondary amino group having.

The curable composition of claim 5, wherein the reagent is a mono- or polyhydric aminoalcohol.

The curable composition according to any one of claims 1 to 6, characterized in that the hyperbranched polyether amine triethanolamine, tripropanolamine, triisopropanolamine or tributanolamine contains as a monomer unit, wherein the monomer units in the polyetheramine are linked together via their hydroxy groups to form ether bridges.

The curable composition according to any one of claims 1 to 7, characterized in that the hyperbranched polyetheramine has a weight average molecular weight of 1, 000 to 500,000 g / mol.

Process for the preparation of cured epoxy resin, characterized in that a curable composition according to any one of claims 1 to 8 is cured.

A cured epoxy resin obtainable by curing a curable composition according to any one of claims 1 to 8.

1 1. A cured epoxy resin of the curable composition according to any one of claims 1 to 8.

12. Shaped body of the cured epoxy resin according to claim 10 or 11.

13. Highly branched polyetheramine, characterized in that it has at least 3 terminal hydroxy groups, to which a proportion of on average at least

1% is coupled to a reagent which has at least one primary or secondary amino group.

Highly branched polyetheramine, characterized in that it is obtainable starting from highly branched polyetheramine polyol by reacting a proportion of on average at least 1% of the terminal hydroxy groups with a reagent having at least one primary or secondary amino group and one for coupling with the terminal hydroxy groups of the hyperbranched polyetheramine Polyols having suitable reactive group.

The hyperbranched polyetheramine of claim 13 or 14, wherein the reagent is a mono- or polyhydric aminoalcohol.

A process for preparing an amino-modified hyperbranched polyetheramine, characterized in that a highly branched polyetheramine polyol is reacted with a reagent having at least one primary or secondary amino group and a reactive group suitable for coupling to the terminal hydroxy groups of the hyperbranched polyetheramine polyol.

Use of hyperbranched polyetheramine as an additive in a curable composition of at least one epoxy compound having from 2 to 10 epoxy groups and at least one amino or anhydride curing agent to accelerate the curing of the curable composition.