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    invention patent: "hardeners for epoxy resins". the present invention relates to new mixtures, containing cyanamide and a urea derivative, liquid hardeners for curing polymeric resins, in particular epoxide resins, as well as epoxy resin compositions comprising liquid hardeners for the production of fiber reinforced composites .
    公开号:BR112013013450B1
    申请号:R112013013450
    申请日:2012-02-23
    公开日:2020-05-05
    发明作者:Krimmer Hans-Peter；Ebner Martin；Huber Michaela；Strobel Sylvia
    申请人:Alzchem Ag；Alzchem Trostberg Gmbh；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for HARDENERS FOR EPOXIDE RESINS, COMPOSITIONS UNDERSTANDING THE SAME AND THEIR USES.
    Description [001] The present invention relates to new mixtures, containing cyanamide and at least one urea derivative, liquid hardeners for curing epoxide resins, as well as epoxy resin compositions comprising liquid hardeners for the production of fiber reinforced composites .
    [002] The use of duraplastic epoxy resins, based on their good resistance to chemicals, their very good thermal and dynamic-mechanical properties, as well as their high electrical insulating power, is widely publicized. In addition, epoxide resins show good adhesion on many substrates and, therefore, are the most suitable for use in fiber reinforced composites (composites). For use in fiber reinforced composites, good wetting of the fibers is desirable, that is, a low viscosity of the resinous formulation selected for the production of the composite, as well as high mechanical properties after curing.
    [003] To produce molded parts of fiber reinforced composites, different processes are used, such as, for example, the pre-impregnation process, different infusion or injection processes, here, in particular, the RTM process (Resin Transfer Molding). Of these processes, especially the infusion or injection process have gained importance in recent years. Thus, for example, in the infusion processes, the dry reinforcement materials found in an open tool, such as, for example, fiber blankets, nonwovens, fabrics or knits, are covered with a hermetically sealed vacuum film and after vacuum application are impregnated through
    Petition 870190128709, of 12/05/2019, p. 8/68
    2/29 through distribution channels with resin formulations. These processes have the advantage that large elements with complicated geometries can be shaped in a short time.
    [004] The epoxy resin formulation for an infusion process or RTM process must have a low viscosity, to allow the impregnation of fiber materials in a vacuum in a corresponding time. If resin formulations with very high viscosities are used or resin formulations are used, which during the injection period produce too high viscosities too quickly, non-impregnated parts and other defects in the resulting composite are obtained.
    [005] The curing of epoxide resins can take place by different mechanisms. In addition to curing with phenols or anhydrides, curing is often done with amines. These substances are mostly liquid and can be mixed well with epoxide resins. Due to the high reactivity and, therefore, very low latency, such compositions of epoxide resins are made with two components. This means that the resin (component A) and the hardener (component B) are stored separately and only shortly before use are mixed in the correct proportion. Here, latent means that a mixture of the individual components is present in a stable manner under storage conditions. These two-component resin formulations are also referred to as so-called cold cure resin formulations, in which the hardeners used for this purpose are selected from the majority of the group of amines or amidoamines.
    [006] One-component epoxy resin formulations, hot curing, on the contrary, are usable ready for use, that is, the epoxy resin and the hardener are present mixed at the factory. Mixing defects of individual components when used in
    Petition 870190128709, of 12/05/2019, p. 9/68
    3/29 location are therefore excluded. Latent hardener systems form the condition for this, which do not react with epoxy resin at room temperature (they are storable), however, under heating, depending on the energy input, they react promptly. For such one-component epoxy resin formulations, for example, dicyandiamide is a particularly suitable and also cheaper hardener. Under environmental conditions, the corresponding hardening resin mixtures can be stored and usable for up to twelve (12) months.
    [007] Unfortunately, these mixtures of epoxy resin with highly latent dicyandiamide or other highly latent hardeners have the advantage that the hardeners in epoxide resins are only slightly soluble and in the process of infusion or injection for the production of fiber reinforced composites these they are retained by the fiber blankets at the resin entry points and are removed by filtration. In this way, a homogeneous mixture of the hardener before use in the composite resins is avoided. Hereby, a cure of the entire composite is prevented.
    [008] The purpose of the present invention is based on making new substances or mixtures available for the curing of curable polymeric resins, especially epoxide resins, which can be used for the production of fiber reinforced composites and matrices. In that case, it was still a necessity, that such hardeners combine the advantages of the known amine hardeners and the known dicyandiamide powder hardeners, without assuming their disadvantages, such as low latency or particle filtration. These new hardeners must have a sufficiently high latency in a temperature range of 15 o C to 30 o C and must allow for entirely crosslinking of the epoxide resin, be soluble in epoxide resins or be entirely miscible and compliant 870190128709, 05/12/12 2019, p. 10/68
    4/29 suitable for use in infusion, injection or RTM processes.
    [009] These objectives are solved by liquid hardeners according to claim 1 and liquid mixtures according to claim 7. Thus, it is a liquid mixture as a hardener for curing polymeric resins, in particular, curable polymeric resins, in particular, epoxide resins containing a) cyanamide and b) at least one urea derivative of formula (I) or formula (II)
    Formula (I) Formula (II) [0010] in which it applies to the radicals in each case simultaneously or independently of each other and at least one radical R 1 , R 2 , R 3 is different from hydrogen:
    [0011] R 1 , R 2 are simultaneously or independently of each other, hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl or together, forming a C3- to C10-alkylene ring;
    [0012] R 3 is hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, aryl, arylalkyl, [0013] C1- to C15-alkyl substituted with -NHC (O) NR 1 R 2 , [0014] C3- to C15-cycloalkyl substituted with -NHC (O) NR 1 R 2 , [0015] aryl substituted with -NHC (O) NR 1 R 2 or [0016] arylalkyl substituted with -NHC (O) NR 1 R 2 ;
    [0017] R 4 , R 5 , R 6 , R 7 , R 8 are simultaneously or independently of each other, hydrogen, halogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, aryl, arylalkyl, -CF3, -NHC (O) NR 1 R 2 , [0018] C1- to C15-alkyl substituted with -NHC (O) NR 1 R 2 ,
    Petition 870190128709, of 12/05/2019, p. 11/68
    5/29 [0019] aryl substituted with -NHC (O) NR1R 2 or [0020] arylalkyl substituted with -NHC (O) NR1R 2 ;
    [0021] The purpose of the present invention is that cyanamide and at least one urea derivative of formula (I) or formula (II) in a molar ratio contains cyanamide: urea derivative from 1: 1 to 4: 1.
    [0022] In this case, it is essential to the invention, that cyanamide is always present in equimolar amount or in an excess of at most 4: 1 in relation to the total amount of all urea derivatives. Only in this proportional range are there liquid mixtures, which are suitable for use as a hardener for curing curable polymeric resins, in particular epoxide resins.
    [0023] It is essential to the invention, that the composition according to the invention is liquid, since the components form a eutectic mixture in the indicated quantitative proportions. The composition, therefore, is not present in solid form and, in particular, not as powder. Just because the composition according to the invention is present in liquid form, it can be used for the infusion process or for the injection process. Surprisingly, it was found that a eutectic mixture and, thus, a liquid composition is obtained exclusively, when cyanamide and the urea derivative are present in a molar ratio of 1: 1 to 4: 1. For example, dicyanamide instead of cyanamide, no liquid mixture is obtained.
    [0024] As a urea derivative of formula (I) or (II), methylurea and / or dimethylurea is preferably used. The use of urea, therefore, compounds, in which R 1 , R 2 and R 3 represent each hydrogen, is, in fact, possible, but little preferred according to the invention.
    [0025] Furthermore, mixtures or hardeners are preferred, which do not contain any urea, therefore, a compound of formula (I), in which R1 = R2 = R3 contain H.
    Petition 870190128709, of 12/05/2019, p. 12/68
    6/29 [0026] Surprisingly, it has been found that intense mixtures of cyanamide with urea derivatives according to formula (I) or formula (II) with the meanings given above, provide liquid to semi-liquid mixtures with low melting points ( compared to the starting materials), which at room temperature dissolve completely in epoxy resin or mix completely. Although analytically, as before, there are separate substances, DSC analyzes show endothermic melting peaks of systems of a substance. Its mode of action on epoxy resin is comparable to the curing properties of accelerated dicyandiamide with imidazoles and is found at <100 ° C. Despite this, at room temperature a latency of several days to several weeks remains. In addition, the viscosity of epoxide resins decreases considerably, so these mixtures are excellently suitable for use in infusion resins.
    [0027] Thus, liquid hardeners for curing polymeric resins, in particular, curable polymeric resins, in particular, epoxide resins are also those comprising a) cyanamide and
    b) at least one urea derivative of formula (I) or formula (II) R 5
    Formula (I) Formula (II) [0028] in which, for radicals, they apply in each case simultaneously or independently of each other:
    [0029] R 1 , R 2 are simultaneously or independently of each other, hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl or together, forming a C3- to C10-alkylene ring;
    Petition 870190128709, of 12/05/2019, p. 13/68
    7/29 [0030] R 3 is hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, aryl, arylalkyl, [0031] C1- to C15-alkyl substituted with -NHC (O) NR1R 2 , [0032 ] C3- to C15-cycloalkyl substituted with -NHC (O) NR1R 2 , [0033] aryl substituted with -NHC (O) NR 1 R 2 or [0034] arylalkyl substituted with -NHC (O) NR1R 2 ;
    [0035] R 4 , R 5 , R 6 , R 7 , R8 are simultaneously or independently of each other, hydrogen, halogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, aryl, arylalkyl, -CF3, - NHC (O) NR1R 2 , [0036] C1- to C15-alkyl substituted with -NHC (O) NR1R 2 , [0037] aryl substituted with -NHC (O) NR 1 R 2 or [0038] arylalkyl substituted with -NHC (O) NR1R 2 .
    [0039] The object of the present invention comprises cyanamide and at least one urea derivative of formula (I) or formula (II) in a molar ratio of cyanamide: urea derivative from 1: 1 to 4: 1.
    [0040] In this case, it is essential to the invention, that cyanamide is always present in equimolar amount or even an excess of at most 4: 1 in relation to the total amount of all urea derivatives. Only in this proportional range are liquid hardeners present for curing curable polymeric resins, in particular epoxide resins, which are particularly suitable for use in composites.
    [0041] Particularly according to the present invention, it is predicted that the molar ratio of cyanamide: urea derivative matters from 1: 1 to 3: 1 and, moreover, preferably from 1: 1 to 2: 1 and particularly preferred in 2: 1 to 4: 1.
    [0042] In that case, by a liquid mixture or by a liquid hardener according to the present invention, a mixture or a hardener, which has a Sm melting point with Sm <20 o C (normal pressure) or which is present in liquid form
    Petition 870190128709, of 12/05/2019, p. 14/68
    8/29 at a temperature of 20 o C (normal pressure) and has a viscosity of less than 1 Pa * s. The liquid mixtures or liquid hardeners according to the invention preferably have a viscosity of <100 mPa * s, more preferably <20 mPa * if even more preferably <12 mPa * s at 25 o C. Particularly preferred, however, are those liquid mixtures or those liquid hardeners, which have a Sm melting point with Sm <10 o C (normal pressure), particularly a Sm melting point with Sm <0 o C (normal pressure) or that are present in form liquid at a temperature of 10 o C (normal pressure), particularly preferably at a temperature of 0 o C (normal pressure) and have a viscosity of less than 1 Pa * s.
    [0043] It should be noted here that these hardeners or mixtures are liquid as such and, in particular, in addition to cyanamide and at least one urea derivative, they do not comprise any solvent or dissolution promoter and are thus free solvents or free of dissolution promoters. In that case, in the context of the present invention, a solvent or dissolution promoter should be understood as any inorganic or organic solvent or dissolution promoter or mixtures thereof, which is used in chemical synthesis or analysis for the preparation of a solution. In the context of the present invention, a mixture or hardener, which is essentially free of solvents or dissolution promoters and due to the preparation, contains at most 1.0% by weight, in particular, not more than 0.7% by weight, in particular not more than 0.5% by weight, of solvent or dissolution promoter and particularly preferably less than 0.1% by weight and most particularly preferred, no solvent or dissolution promoter.
    [0044] Furthermore, in the context of the present invention, by C1
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    9/29 to C15-alkyl should be understood as a straight or branched alkyl radical, which has the general formula CnH2n + 1, where n represents 1 to
    15. In this case, it is predicted, in particular, that C1- to C15-alkyl represents methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decila, and these alkyl radicals, moreover, preferably also also they may be unbranched, branched once, branched several times or substituted by alkyl.
    [0045] C1- to C15-alkyl radicals are preferred, which in turn are replaced one or more times with C1- to C5-alkyl. C1- to C5-alkyl according to the present invention, can represent methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl , 2-methylbutyl, 3methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl or 1ethylpropyl. Thus, alkyl according to the present invention can also represent, in particular, 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl,
    1-methylnonyl, 1-methylldanilane, -ethylpropyl, 1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethylocyl, 1-ethylnonyl, 1-ethylldecanyl, 2-methylpropyl, 2-methylbutyl, 2-methylpentyl , 2-methylhexyl, 2-methylheptyl,
    2-methyloctyl, 2-methylnonyl, 2-methylldecanyl, 2-ethylpropyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethylheptyl, 2-ethyloctyl, 2-ethylnonyl, 2ethylethylanyl, 1,1-dimethylethyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1dimethylpentyl, 1,1-dimethylhexyl, 1,1-dimethylheptyl, 1,1-dimethyloctyl,
    1.1-dimethylnonyl, 1,1-dimethyldecanyl, 1,2-dimethylpropyl, 1,2-dimethylbutyl, 1,2-dimethylpentyl, 1,2-dimethylhexyl, 1,2-dimethylheptyl,
    1.2-dimethyloctyl, 1,2-dimethylnonyl, 1,2-dimethyldecanyl, 2-ethyl-1-methylbutyl, 2-ethyl-1-methylpentyl, 2-ethyl-1-methylhexyl, 2-ethyl-1-methylheptyla, 2-ethyl-1-methyloctyl, 2-ethyl-1-methylnonyl, 2-ethyl-1-methylldecanyl, 1ethyl-2-methylpropyl, 1-ethyl-2-methylbutyl, 1-ethyl-2-methylpentyl, 1-ethyl- 2-methylhexyl, 1-ethyl-2-methylheptyl, 1-ethyl-2-methyloctyl, 1-ethyl-2-methylpropyl or
    Petition 870190128709, of 12/05/2019, p. 16/68
    10/29
    1-ethyl-2-methyldecanil.
    [0046] Furthermore, preferably, a C1- to C15alkyl radical, in particular methyl, ethyl, propyl, butyl in turn, can also be substituted with a C3- to C15-cycloalkyl radical, where C3- to C15- cycloalkyl has the meaning described below. Thus, C1- to C15-alkyl may, in particular, also represent C3- to C15cycloalkyl-methyl, 1- (C3- to C15-cycloalkyl) -1-ethyl, 2- (C3- to C15cycloalkyl) -1-ethyl, 1- (3- to C15-cycloalkyl) -1-propyl, 2- (C3- to C15cycloalkyl) -1-propyl or 3- (C3- to C15-cycloalkyl) -1-propyl, with C3- to C15- cycloalkyl has the meaning described below.
    [0047] In the context of the present invention, C3- to C15cycloalkyl should be understood as a monocyclic or bicyclic cycloalkyl radical with 3 to 15 carbon atoms, in particular, a cycloalkyl radical, which presents the general formula CnH2n-1 with n = 3 to 15. Furthermore, preferably, C3- to C15-cycloalkyl can represent cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, and these cycloalkyl radicals, in turn, can be substituted, moreover, preferably one or more times with C1- to C5-alkyl radicals of the above-described meaning. In addition, preferably, with this, C3- to C15-cycloalkyl can also represent 1-methyl1-cyclopropyl, 1-methyl-1-cyclobutyl, 1-methyl-1-cyclopentyl, 1-methyl-1cyclohexyl, 1-methyl -1-cycloheptyl, 2-methyl-1-cyclopropyl, 2-methyl-1cyclobutyl, 2-methyl-1-cyclopentyl, 2-methyl-1-cyclohexyl, 2-methyl-1-cycloheptyl, 3-methyl -1-cyclobutyl, 3-methyl-1-cyclopentyl, 3-methyl-1-cyclohexyl, 3-methyl-1-cycloheptyl, 4-methyl-1-cyclohexyl, 4-methyl-1-cycloheptyl, 1 , 2-dimethyl-1-cyclopropyl, 2,2-dimethyl-1-cyclopropyl, 2,3-dimethyl1-cyclopropyl, 1,2-dimethyl-1-cyclobutyl, 1,3-dimethyl-1-cyclobutyl, 2,2dimethyl -1-cyclobutyl, 2,3-dimethyl-1-cyclobutyl, 2,4-dimethyl-1-cyclobutyl,
    3,3-dimethyl-1-cyclobutyl, 1,2-dimethyl-1-cyclopentyl, 1,3-dimethyl-1-cyclopentyl, 2,2-dimethyl-1-cyclopentyl, 2,3-dimethyl-1-cyclopentyl, 2.4 Petition 870190128709, of 12/05/2019, p. 17/68
    11/29 dimethyl-1-cyclopentyl, 2,5-dimethyl-1-cyclopentyl, 3,3-dimethyl-1cyclopentyl, 3,4-dimethyl-1-cyclopentyl, 1,2-dimethyl-1-cyclohexyl, 1 , 3dimethyl-1-cyclohexyl, 1,4-dimethyl-1-cyclohexyl, 1,5-dimethyl-1-cyclohexyl, 1,6-dimethyl-1-cyclohexyl, 2,2-dimethyl-1 -cyclohexyl, 2,3-dimethyl1-cyclohexyl, 2,4-dimethyl-1-cyclohexyl, 2,5-dimethyl-1-cyclohexyl, 2,6dimethyl-1-cyclohexyl, 3 , 3-dimethyl-1-cyclohexyl, 3,4-dimethyl-1-cyclohexyl, 3,5-dimethyl-1-cyclohexyl, 3,6-dimethyl-1-cyclohexyl, 4,4-dimethyl1 -cyclohexyl, 1,2,2-trimethyl-1-cyclopropyl, 1,2,3-trimethyl-1-cyclopropyl,
    1.2.2- trimethyl-1-cyclobutyl, 1,3,3-trimethyl-1-cyclobutyl, 1,2,3-trimethyl-1cyclobutyl, 2,2,3-trimethyl-1-cyclobutyl, 2,2,4- trimethyl-1-cyclobutyl, 1,2,2trimethyl-1-cyclopentyl, 1,2,3-trimethyl-1-cyclopentyl, 1,2,4-trimethyl-1cyclopentyl, 1,2,5-trimethyl-1-cyclopentyl, 1,3,3-trimethyl-1-cyclopentyl,
    1.3.4- trimethyl-1-cyclopentyl, 1,3,5-trimethyl-1-cyclopentyl, 2,2,3-trimethyl-1-cyclopentyl, 2,2,4-trimethyl-1-cyclopentyl, 2,2, 5-trimethyl-1-cyclopentyl,
    2.3.3- trimethyl-1-cyclopentyl, 2,3,4-trimethyl-1-cyclopentyl, 2,3,5-trimethyl-1-cyclopentyl, 2,3,3-trimethyl-1-cyclopentyl, 2,4, 4-trimethyl-1-cyclopentyl,
    2.4.5- trimethyl-1-cyclopentyl, 2,5,5-trimethyl-1-cyclopentyl, 3,3,4-trimethyl-1-cyclopentyl, 3,3,5-trimethyl-1-cyclopentyl, 3,4, 5-trimethyl-1-cyclopentyl,
    3.4.4- trimethyl-1-cyclopentyl, 1,2,2-trimethyl-1-cyclohexyl, 1,2,3-trimethyl-1-cyclohexyl, 1,2,4-trimethyl-1-cyclohexyl hexyl, 1,2,5-trimethyl-1-cyclohexyl,
    1.2.6- trimethyl-1-cyclohexyl, 1,3,3-trimethyl-1-cyclohexyl, 1,3,4-trimethyl-1-cyclohexyl, 1,3,5-trimethyl-1- cyclohexyl, 1,3,6-trimethyl-1-cyclohexyl,
    1.4.4- trimethyl-1-cyclohexyl, 2,2,3-trimethyl-1-cyclohexyl, 2,2,4-trimethyl-1-cyclohexyl, 2,2,5-trimethyl-1- cyclohexyl, 2,2,6-trimethyl-1-cyclohexyl,
    2.3.3- trimethyl-1-cyclohexyl, 2,3,4-trimethyl-1-cyclohexyl, 2,3,5-trimethyl-1 - cyclohexyl, 2,3,6-trimethyl-1- cyclohexyl, 2,4,4-trimethyl-1-cyclohexyl,
    2.4.5- trimethyl-1-cyclohexyl, 2,4,6-trimethyl-1-cyclohexyl, 2,5,5-trimethyl-1 - cyclohexyl, 2,5,6-trimethyl-1- cyclohexyl, 2,6,6-trimethyl-1-cyclohexyl,
    3.3.4- trimethyl-1-cyclohexyl, 3,3,5-trimethyl-1-cyclohexyl, 3,3,6-trimethyl-1 - cyclohexyl, 3,4,4-trimethyl-1- cyclohexyl, 3,4,5-trimethyl-1-cyclohexyl,
    Petition 870190128709, of 12/05/2019, p. 18/68
    12/29
    3,5,6-trimethyl-1-cyclohexyl,
    2.2.3.3- tetramethyl-1-cyclopropyl,
    1,2, 2,3-tetramethyl-1-cyclobutyl,
    2.2.3.3- tetramethyl-1-cyclobutyl,
    1,2,2,3-tetramethyl-1-cyclopentyl,
    1,2,2,5-tetramethyl-1-cyclopentyl, 1,2,3,3-tetra1,2,3,31,2,2,31,2,3,32,3,3,41,2, 2,43,4,6-trimethyl-1-cyclohexyl, tetramethyl-1-cyclopropyl, tetramethyl-1-cyclopropyl, tetramethyl-1-cyclobutyl, tetramethyl-1-cyclobutyl, tetramethyl-1-cyclopentyl, methyl-1- cyclopentyl, 1,2,3,4-tetramethyl-1-cyclopentyl, 1,2,3,5-tetramethyl1-cyclopentyl, 1,2,5,5-tetramethyl-1-cyclopentyl, 2,2,3,3- tetramethyl-1cyclopentyl, 2,2,3,3-tetramethyl-1-cyclohexyl, 2,2,4,4-tetramethyl-1-cyclohexyl, 2,2,5,5-tetramethyl-1-cyclohexyl, 3,3,4,4-tetramethyl-1-cyclohexyl,
    3,3,5,5-tetramethyl-1-cyclohexyl, 1-ethyl-1-cyclopropyl, 1-ethyl-1-cyclobutyl, 1ethyl-1-cyclopentyl, 1-ethyl-1-cyclohexyl), 1 -ethyl-1-cycloheptyl, 2-ethyl-1cyclopropyl, 2-ethyl-1-cyclobutyl, 2-ethyl-1-cyclopentyl, 2-ethyl-1-cyclohexyl, 2-ethyl-1-cycloheptyl , 3-ethyl-1-cyclobutyl, 3-ethyl-1-cyclopentyl, 3-ethyl-1cyclohexyl, 3-ethyl-1-cycloheptyl, 4-ethyl-1-cyclohexyl or 4-ethyl-1 -cycloheptila.
    [0048] According to the present invention, R 1 and R 2 together can also represent C3- to C10-alkylene, where R 1 and R 2 together with the nitrogen of the urea derivative form a nitrogenous ring. In this case, in particular, it can be predicted that R 1 and R 2 together represent ethylene, propylene, butylene, pentylene or hexylene, and these alkylene radicals, in turn, can optionally be replaced one or more times with alkyl radicals. In this case, R 1 and R 2 together with the nitrogen of the urea derivative form an aziridine, azetidine, azolidine, azinan or azepan which, in turn, can optionally be replaced one or more times with radicals C1- to C5alkyl of the above meaning described.
    [0049] According to the present invention, -NHC (O) NR1R 2 represents a 1-ureayl radical, which in N3 is replaced with R 1 and R 2 , where R 1 and R 2 have the meaning described above.
    Petition 870190128709, of 12/05/2019, p. 19/68
    According to the present invention, halogen represents, in particular, fluorine, chlorine or bromine.
    [0051] In accordance with the present invention, aryl represents, in particular, an aromatic aryl radical with 3 to 20 carbon atoms, which, moreover, preferably in turn, can be replaced (one or more times) with a radical C1- to C5-alkyl of the meaning described above. In a particularly preferred way, it can be envisaged that as the aryl radical a benzene radical, a naphthalene radical, anthracene radical or a perylene radical can be used which, in turn, can be replaced one or more times with a C1- to C5-alkyl radical of the meaning described above. Thus, aryl represents, in particular, toluyl, xylenyl, pseudocumolyl or mesitylenyl.
    [0052] According to the present invention, arylalkyl represents a C1- to C5-alkyl radical of the above described meaning, which is replaced with an aryl radical of the above described meaning. Arylalkyl may represent, in particular, a benzyl radical.
    [0053] Particularly preferably, the hardeners or liquid mixtures according to the invention comprise at least one aliphatic urea derivative according to formula (I). In those aliphatic urea derivatives according to formula (I), R 1 and R 2 have the meaning indicated above and R 3 has the meaning of hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, C1- a C15-alkyl substituted with -NHC (O) NR1R 2 or C1- to C15-cycloalkyl substituted with NHC (O) NR 1 R 2 .
    [0054] Particularly preferably, the liquid hardeners or liquid mixtures according to the invention comprise at least one urea derivative of formula (I), in which at least one of the radicals R 1 and R 2 represents a methyl radical. Particularly preferred is methylurea or N, N-dimethylurea (therefore, R 1 = R 2 = methyl and R 3 = H).
    Petition 870190128709, of 12/05/2019, p. 20/68
    14/29 [0055] In addition, aliphatic urea derivatives according to formula (I) are preferred, in which R 1 and R 2 have the above meaning, in particular hydrogen, methyl, ethyl and R 3 represents C1 - C15-cycloalkyl substituted with -NHC (O) NR 1 R 2 .
    [0056] In addition, hardeners or liquid mixtures comprising aliphatic urea derivatives of formula (III) are preferred
    Q / V rL. The A- r7
    HR 8 '(III) [0057] in which R 1 , R 2 , R 4 , R 4 ', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 'and R 8 , R 8 'have the meanings indicated above and, in particular, simultaneously or independently of each other, represent:
    [0058] R 1 , R 2 = simultaneously or independently of each other, hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl or together forming a C3- to C10-alkylene ring;
    [0059] R 4 , R 4 ', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 '= simultaneously or independently of each other, C1- to C15- alkyl, C3- to C15cycloalkyl, -NHC (O) NR 1 R 2 or C1- to C15-alkyl substituted with NHC (O) NR 1 R 2 .
    [0060] In addition, liquid hardeners or mixtures comprising aliphatic urea derivatives of formula (III), in which R 1 and R 2 simultaneously or independently of each other, represent hydrogen or methyl and R 4 , R 4 ', R are preferred 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 ' simultaneously or independently of each other, represent hydrogen, methyl, ethyl, -NHC (O) NR 1 R 2 or methyl or ethyl substituted with -NHC (O) NR 1 R 2 . Particularly preferred is 1- (N, N dimethylurea) -3- (N, N-dimethylureamethyl) -3,5,5-trimethyl-cyclohexane (therefore, R 1 = R 2 = R 5 = R 5 '= R 7 = methyl and R 7 '= -CH 2 -NHC (O) N (CH 3 ) 2 and
    Petition 870190128709, of 12/05/2019, p. 21/68
    15/29
    R 4 = R 4 '= R6 = R6' = r8 = R 8 ' = hydrogen).
    [0061] However, it can also be envisaged that hardeners or liquid mixtures of the present invention comprise aromatic urea derivatives of formula (II). Of those aromatic urea derivatives, urea derivatives are particularly preferred, in which the radicals R 4 , R 5 , R 6 , R 7 and R 8 simultaneously or independently of each other, represent hydrogen, C1- to C15-alkyl, - NHC (O) NR 1 R 2 , C1- to C15-aryl substituted with -NHC (O) NR 1 R 2 or C1- to C15arylalkyl substituted with -NHC (O) NR 1 R 2 .
    [0062] In addition, hardeners or liquid mixtures comprising urea derivatives of formula (IV) are preferred
    [0063] in which R 1 , R 2 , R 4 and R 5 have the above meaning and, in particular, simultaneously or independently of each other, represent hydrogen, C1-C15-alkyl. Preferably, the radicals R 1 and R 2 in the context of formula (IV), represent a methyl radical. Particularly preferred is 1,1 '- (4-methyl-m-phenylen) bis- (3,3-dimethylurea) and 1,1' - (2-methyl-m-phenylen) -bis- (3,3- dimethylurea) (therefore, R 1 = R 2 = R 5 represent methyl and R 4 represents hydrogen).
    [0064] According to another embodiment, it can be provided, in particular, that the liquid hardeners according to the invention, for curing epoxide resins, contain a) cyanamide and b) at least one urea derivative of the formula (I) or formula (II) with the radicals described above, with these hardeners containing cyanamide and at least one urea derivative of formula (I) or formula (II) in a molar proportion of cyanamide: urea derivative
    Petition 870190128709, of 12/05/2019, p. 22/68
    16/29 from 1: 1 to 4: 1. In particular, liquid hardeners are preferred, which contain cyanamide and two different urea derivatives of formula (I), formula (II) or formula (II) and formula (II), in which these hardeners contain cyanamide and two urea derivatives different from each other of formula (I), formula (II) or formula (I) and formula (II) in a molar proportion of cyanamide: urea derivative from 1: 1 to 4: 1.
    [0065] Particularly preferred are those liquid hardeners, which comprise a urea derivative of formula (I) or formula (II), wherein the radicals R 1 , R 2 , simultaneously or independently of each other, represent methyl or ethyl.
    [0066] Particularly preferred are those liquid hardeners, which comprise a urea derivative of formula (I), in which they are applied to the radicals, simultaneously or independently of each other:
    [0067] R 1 , R 2 = simultaneously or independently of each other, hydrogen, C1- to C15-alkyl;
    [0068] R3 = hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl, [0069] C1- to C15-alkyl substituted with -NHC (O) NR1R 2 , [0070] C3- to substituted C15-cycloalkyl with -NHC (O) NR1R 2 or [0071] aryl substituted with -NHC (O) NR1 R 2 .
    [0072] According to another particularly preferred embodiment of the invention, those liquid hardeners, comprising cyanamide and at least one urea derivative selected from the urea group, 1,1-dimethylurea, 3- (3-chloro- 4-methylphenyl) -1,1-dimethylurea, 3- (p-chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 1 , 1 '- (methylendip-phenylen) -bis- (3,3-dimethylurea), 3- (3-trifluormethylphenyl) 1,1-dimethylurea, 1,1' - (2-methyl-m-phenylen) -bis- (3,3-dimethylurea) and / or 1,1 '- (4-methyl-phenylen) -bis- (3,3-dimethylurea) in a molar ratio of cyanamide
    Petition 870190128709, of 12/05/2019, p. 23/68
    17/29 for urea derivative from 1: 1 to 4: 1, preferably from 1: 1 to 3: 1 and even more preferably, from 2: 1 to 3: 1. Very particularly preferred are those liquid hardeners, which contain cyanamide and at least one urea derivative from that group.
    [0073] Especially those hardeners or mixtures have been shown to be particularly suitable, which comprise, in particular, contain 40 - 70% by weight of cyanamide and 30 to 60% by weight of at least one urea derivative of formula (I) and / or the formula (II) described above or the selection.
    In that case, those hardeners or mixtures, which comprise or contain 45 - 70% by weight, in particular 45 - 60% by weight, and particularly preferably 45 to 55% by weight, of cyanamide are particularly preferred.
    [0075] Simultaneously or independently thereof, the mixtures or hardeners according to the invention may comprise, in particular, containing 35 - 60% by weight, in particular, 35 - 55% by weight and particularly preferably 45 to 55% by weight of at least one urea derivative of the formulas (I) and / or the formula (II) described above or the selection.
    [0076] In the improvement of the present invention, likewise epoxy resin compositions comprising a) at least one epoxy resin and b) at least one liquid hardener according to the type described above, are the object of the present invention.
    [0077] With respect to the epoxy resins to be cured, the present invention is not subject to any restrictions. All commercially available products are included, which generally have more than one 1,2-epoxide group (oxirane) and, in this case, can be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic. In addition, epoxide resins may contain substituents, such as halogens, phosphorus and hydroxyl groups. Re
    Petition 870190128709, of 12/05/2019, p. 24/68
    18/29 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) glycidyl polyether epoxides, as well as the bromine-substituted derivative (tetrabromobisphenol), 2,2-bis (4) glycidyl polyether -hydroxyphenyl) methane (bisphenol F) and novolaca glycidyl polyether, as well as based on aniline or substituted anilines, such as, for example, p-aminophenol or 4,4'-diaminodiphenylmethane, can be hardened particularly well using hardeners according to the invention.
    [0078] The amount of application of liquid hardeners according to the invention is not subject to any restrictions. Preferably, however, for 100 parts of resin 0.01 to 15 parts are used, preferably 0.1 to 15 parts, preferably 0.1 to 10 parts and particularly preferably, 0.1 to 7 parts. Also a combination of several liquid hardeners according to the invention or a combination of liquid hardeners according to the invention with other co-hardeners is covered by that invention.
    [0079] The curing of epoxy resins with the help of the hardeners used according to the invention, is carried out, as a rule, at temperatures from 10 to 120 o C. The selection of the curing temperature depends on the specific processing and product requirement and it can vary through the formulation mainly by regulating the amounts of hardener, as well as by adding additives. In this case, it is insignificant, how energy is fed to resin formulations. For example, this can occur in the form of heat through an oven or heating elements, but, likewise, by means of infrared rays or stimulation by means of microwaves or other radiation.
    [0080] By adding other commercially available additives, such as are known to the technician for curing epoxide resins, the curing profile of the formulations according to the invention
    Petition 870190128709, of 12/05/2019, p. 25/68
    19/29 may vary.
    [0081] Additives to improve the processability of uncured epoxy resin compositions or to adapt the thermal-mechanical properties of the duraplastic products to the requirements profile comprise, for example, reactive diluents, fillers, rheology additives, such as thixotropy or dispersion additives, defoamers, dyes, pigments, impact modifiers, impact resistance improvers or fire protection additives.
    [0082] A particular class of additives are the so-called stabilizers, which improve the storage stability, in this way, the latency of the hardeners according to the invention. Surprisingly, it has been found that the stability of epoxy resin compositions on storage can be improved by adding organic acids. As stabilizers in this case, especially carboxylic acids, dicarboxylic acids or aromatic and non-aromatic tricarboxylic acids have been shown to be particularly suitable.
    [0083] Thus, according to an improvement, a liquid hardener is also the objective of the present invention, which comprises a) cyanamide, b) at least one urea derivative of formula (I) or formula (II) and c) least one stabilizer selected from the group of organic carboxylic acids.
    [0084] In addition, an epoxy resin composition is an object of the present invention, which comprises a) an epoxy resin, b) at least one liquid hardener according to the type described above and c) a stabilizer selected from the group of carboxylic acids organic.
    [0085] Surprisingly it was found, that liquid hardeners according to the invention compared to mixtures in
    Petition 870190128709, of 12/05/2019, p. 26/68
    20/29 powder of the same composition always starts curing polymeric resins at lower temperatures and, thus, allows a shorter time for the production of molded parts. In addition, through the liquid hardeners according to the invention, the viscosity of ready-made formulated resins decreases, which also allows for considerable time savings for the production of molded parts. It should be noted, in this case, that the usual disadvantages of other liquid hardeners, such as very low latency and, therefore, very high reactivity, are not observed.
    [0086] In addition, resins cured with the hardener according to the invention can be produced with cured resins in comparison with amine hardeners at high glass transition temperatures. Conventional amine hardeners have a low latency, in particular, a low processing time in resin mixes of only about 3 minutes maximum.
    [0087] Epoxy resin formulations with the hardeners according to the invention are suitable for both manual and mechanical processing methods and particularly for the production of impregnated reinforced fibers and composites, as described in the publications by GW Ehrenstein , Faserverbund-Kunststoffe, 2006, 2nd edition, Carl Hanser Verlag, Munich, chapter 5, page 148 et seq and M. Reyne, Composite Solutions, in 2006, JEC Publications, chapter 5, page 51 and following. In addition to the use in pre-impregnation processes, in particular, handling in infusion and injection processes is a preferred form of processing. In this case, the generally very good miscibilities of the liquid hardeners according to the invention in these epoxide resins are advantageous, since for the impregnation process they are necessaryPetition 870190128709, from 05/12/2019, pg. 27/68
    21/29 holiday flowable infusion resin with low viscosity (compare, among others, Reyne, Composite Solutions, in 2006, JEC Publications, chapter 5, page 65, and GW Ehrenstein, Faserverbund-Kunststoffe, 2006, 2nd edition, Carl Hanser Verlag , Munich, chapter 5, page 166). [0088] Due to the liquid state of the hardeners according to the invention, they can be used in infusion and injection processes.
    [0089] Thus, likewise, the use of liquid hardeners or liquid mixtures of the type described above for curing curable compositions, are the object of the present invention. In particular, this is intended for use in compositions, which comprise at least one epoxy resin and / or a polyurethane resin.
    [0090] In addition, the present invention also includes the use of liquid mixtures or liquid hardeners of the type described above, for the curing of impregnated fiber materials or impregnated woven, knitted or interwoven materials.
    [0091] Based on the favorable application properties of the hardeners according to the invention, as well as their production at low costs and associated with an advantageous cost-benefit ratio, these are particularly well suited for a technical application.
    [0092] The following examples illustrate the advantages of the present invention.
    Examples
    I. Mixtures and hardeners according to the invention
    1) Preparation of mixtures and hardeners according to the invention
    Instrument:
    [0093] Laboratory dissolver (DISPERMAT type AE03-C1),
    500 ml metal dispersion reservoir, dissolving disc with 0
    Petition 870190128709, of 12/05/2019, p. 28/68
    22/29 of 60 mm, metallic spatula.
    Execution:
    [0094] In a 500 ml dispersion reservoir, they are weighed
    100 g of individual components and quickly mixed using a spatula. The mixture is stirred in the dissolver at 100 200 revolutions / minute for so long, until a crystalline pore is formed. Then, the mixture is stirred at 500 to 2000 revolutions / min until it reaches a temperature of 40 o C. Then, the liquid is still stirred at 100 revolutions / min for so long, until it reaches a temperature of 25 o C. The residue obtained is separated by filtration. The liquid phase obtained in this way is filled and stored at room temperature (20-25 o C).
    Yield:
    [0095] The yield after each mixture is between 75 and 90%.
    Table 1: Compositions of mixtures / liquid hardeners according to the invention
    Mixtures / liquid hardeners Cyanamide Urea B1 Urea B2 Urea B3 Urea B4 Molar proportion % by weight Molar proportion % by weight Molar proportion % by weight Molar proportion % by weight Molar proportion H1 50 3 34 1 17 0.16 - - - H2 50 2 50 1 - - - - - H3 60 2 - - - - 40 1 - H4 50 2 - - 10 0.07 40 1 - H5 - 3 - - - - - - 0.4
    Raw materials used:
    Cyanamide: AlzChem Trostberg GmbH
    Urea B1: 1,1-dimethylurea - AlzChem Trostberg GmbH
    Urea B2: technical isomeric mixture 1,1 '- (4-methyl-m-phenylen) bis- (3,3-dimethylurea) and 1,1' - (2-methyl-m-phenylen) -bis (3.3 -dimethylurea) - AlzChem Trostberg GmbH
    Urea B3: urea - Merck KGaA
    Urea B4: 1- (N, N-dimethylurea) -3- (N, N-dimethylureamethyl) -3,5,5trimethylcyclohexane - CAS: 39992-90-0 - AlzChem
    Petition 870190128709, of 12/05/2019, p. 29/68
    23/29
    Trostberg GmbH
    E 828: Epikote 828 EVEL - Momentive Specialty Chemicals
    RIMR 135: epoxy resin - Momentive Specialty Chemicals
    RIMH 137: liquid amine hardener - Momentive Specialty
    Chemicals
    Vestamin IPDA: liquid amine hardener - Evonik Degussa GmbH
    2) Viscosities of mixtures and hardeners according to the invention
    Determination of viscosity:
    [0096] Measurement in HAAKE Rheostress 1 made at 25 o C in mPa * s, with 0 of 35 mm and 1 o with a shear rate of 5.0 1 / s (reciprocal).
    Table 2: Viscosity in mPa * s at the indicated temperatures
    Mixture / Hardener at 10 o C at 15 o C at 20 o C at 25 o C at 30 ° C H1 12 - 14 11 - 13 10 - 12 10 - 11 10 - 11 H2 9 - 11 7 - 9 7 - 9 6 - 8 5 - 7 H3 - 5 - 7 5 - 7 5 - 6 4 - 5 H4 8 - 10 8 - 10 7 - 9 6 - 8 5 - 7 H5 13 - 15 12 - 14 11 - 13 10 - 12 10 - 11
    3) Melting points of mixtures and hardeners according to the invention [0097] Determination of melting points using the method
    DSC.
    [0098] Measurement in Mettler Toledo DSC 822 [0099] Dyn. DSC -40 o C - 60 o C with a heating rate of
    10 o K / min
    Table 3: Melting point
    Mixer / Hardener First peak Second peak H1 12 - 16 o C - H2 -24 - -22 o C 10 - 17 o C H3 -30 - -8 o C 13 - 15 o C
    Petition 870190128709, of 12/05/2019, p. 30/68
    24/29
    Mixer / Hardener First peak Second peak H4 -30 - -28 o C 8 - 9 o C H5 13 - - 17 o C -
    II. Epoxy resin composition according to the invention
    1) Preparation of epoxy resin compositions [00100] In a 250 ml dispersion reservoir, 100 parts by weight of epoxy resin and 7 parts by weight of the mixtures according to the invention are weighed and these are mixed in the dissolver with 500 revolutions / min for 2 minutes. Then the mixture is vented in a vacuum for 10 minutes.
    2) Measurement methods o Dyn-DSC: standard 30 - 250 o C, with a heating rate of
    10 o K / min o Final Tg: standard Tg heating from 30 o C to 200 o C with 20 o Cmin maintain for 10.0 min at 200 o C cool from 200 o C to 50 o C with 20 o C / min maintain for 5.0 min at 50 o C heat from 50 o C to 200 o C with 20 o C / min keep for 10.0 min at 200 o C cool from 200 o C to 50 o C with 20 o C / min keep for 5.0 min at 50 o C heat from 50 o C to 220 o C with 20 o C / min o viscosity at 25 o C in PA * s (1 o cone) the gelation time at 140 o C o tests infusion into the heating plate at 80 o C.
    3) Usage test and latencies
    Table 4: Usage tests - composition of epoxy resin with mixtures / liquid hardeners according to the invention against individual additions (powder mixture not according to the invention) with the same mixing proportions (in each case 100 parts by weight,
    Petition 870190128709, of 12/05/2019, p. 31/68
    25/29 epoxy resin, 7 parts by weight, powder mix or liquid hardeners, if not otherwise stated)
    No. Composition of epoxy resin Peak dyn DSC [ the C] Start DSC dyn [° C] Integral heat [J / g] Gelling time at 140 o C in min: s Glassy point Tg [ o C] Viscosity at 25 o C in PA * s E1 E828: (powder mixture: cyanamide + B1 + B2) 153.3 142.0 143 3:30 119 5.7 E2 E828: H1 147.0 135.6 224 03:10 121 5.0 E3 E828: (powder mixture: cyanamide +B1) 144.7 130.0 339 04:10 122 5.5 E4 E828: H2 143.7 129.0 336 03:10 126 3.5 E5 E828: (powder mixture: cyanamide +B3) 171.4 158.1 150 53:00 138 n.m. E6 E828: H3 168.8 153.2 70 36:00 145 4.9 E7 E828: (powder mixture: cyanamide + B3 + B2) 162.7 140.9 169 10:00 am 130 n.m. E8 E282: H4 155.0 136.7 237 07:00 142 5.1 E19 E828: VESTAMINIPDA 100: 23 115.5 79.7 453 13:30 to 80 o C 99 5.3 E10 RIMR135:RIMH137 100: 30 125.9 87.9 436.0 40:00 to 80 o C 98 4.1 E11 E282: H5 139.0 147.3 296 04:50 131 5.5
    n.m. = not measurable, in the individual addition of the powders, agglomerates are formed, which prevent an accurate measurement of the viscosity in the epoxy resin.
    [00101] From table 4, the advantages of the liquid mixtures / hardeners according to the invention in curing epoxide resins compared to the individual additions of comparable hardeners and accelerators can be read as powder components.
    [00102] In liquid mixtures according to the invention, curing in comparison with powder mixtures with the same compositions always begins at low temperatures, the times until the beginning of the polymerization (gelation time at 140 o C) are shorter . The mixtures according to the invention significantly reduce the viscosity of epoxide resins up to about 50%, which recommends their use as hardeners for infusion resin systems and increase their glass transition temperatures. The ever higher amounts of integral heat (J / g) indicate a spontaneous reaction
    Petition 870190128709, of 12/05/2019, p. 32/68
    26/29 of the mixtures according to the invention compared to the individual powder components used as a hardener and accelerator. In addition, only half or a third of the amount of hardener is required (compared to known liquid amine hardeners). Hereby, a considerable cost advantage can be realized.
    [00103] In comparison to this, the known and useful liquid amine hardeners, such as, for example, RIMH 137 (company Momentive) or IPDA (company Evonik) show, in fact, lower curing temperatures, but mixtures of according to the invention they start polymerization in comparable times and reach much higher glass transition temperatures.
    Table 5: Latencies of epoxy resin compositions according to table 4 in days (d) - at room temperature (19 - 21 o C) (viscosity measured at 25 o C)
    epoxy resin composition start 1 d 2 d 3 d 4 d 5 d E1 5.7 4.8 4.9 5.8 7.2 10 E2 4.9 5.1 6.2 7.7 16 58 E3 5.5 5.6 5.7 5.8 14 14 E4 3.9 5.6 4.6 5.8 58 123 E5 n.m. n.m. n.m. n.m. n.m. n.m. E6 4.7 4.8 3.9 4.5 4.1 4.5 E7 n.m. n.m. n.m. n.m. n.m. n.m. E8 5.0 5.0 4.9 5.0 5.0 6.0 E9 5.3 solid - - - - E10 4.1 solid - - - - E11 5.5 5.5 5.5 5.5 5.5 5.5
    Continuation
    epoxy resin composition 6 d 7 d 8 d 10 d 11 d 14 d E1 21 102 > 500 solid - - E2 437 solid - - - - E3 14 21 solid - - - E4 740 solid - - - - E5 n.m. n.m. n.m. n.m. n.m. solid E6 4.5 7.9 32 73 500 solid E7 n.m. n.m. n.m. n.m. n.m. solid E8 6.0 20 27 165 solid - E9 - - - - - - E10 - -- - - E11 5.5 5.5 5.6 5.7 6.7 8.0
    Petition 870190128709, of 12/05/2019, p. 33/68
    27/29
    n.m. - not measurable, in the individual addition of the powders, agglomerates are formed, which prevent an exact measurement of the viscosity in the epoxy resin.
    [00104] The storage capacities = latencies of hardener / accelerator systems in epoxy resin are considerably characterized by the solubility of these systems in the resin. The relative insolubility of hardener / accelerator systems sprayed at temperatures <60 o C in epoxy resin allows long storage times for these mixtures, without the components reacting with each other.
    [00105] Mixtures of liquid hardeners / accelerators in the epoxy resin leave the expectation of a rapid reaction of the components with each other, which leads to very limited storage capacities = latencies. This is shown by the amine hardeners listed in table 5 (RIMH 137 from Momentive and Vestamin IPDA from Evonik).
    [00106] Surprisingly, however, the liquid mixtures / hardeners according to the invention at room temperature, do not show any rapid reactions with epoxide resins, their storage capacities = latencies in epoxide resins, therefore, are noticeably longer than systems classic liquid amine hardeners.
    Table 6: Infusion test with epoxy resin compositions according to table 4 - Epikote E828: hardener in the proportion of 100: 7.0 (comparisons)
    Composition of epoxy resin Injection time in minutes Setting time in hours at temperature C Cold tg Final Tg E2 5 1 h5 h 59 - 63 o C 69 - 74 o C 72 128 E4 12 20 h 70 o C 79 137 E6 45 6 h 80 o C 56 134 E8 45 5.5 h 75 o C-78 o C 97 140 E9 20 6 h 70 o C 93 99 E10 18 6.5 h4 pm 40 o C and then 80 o C 68 93
    Continuation
    Petition 870190128709, of 12/05/2019, p. 34/68
    28/29
    Composition of epoxy resin Comments E2 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects E4 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects E6 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects E8 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects E9 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects E10 fiber composite can be well denuclatedfiber composite looks good, is uniform, has no defects
    Table 7: Fiber composite - Structuring for infusion tests
    Component Material Basic layer sheet vacuo R & G No 390 160 Seal Tacky Tape SM5126 0.0127 m (1/2) x X0.003175 m (1/8) Separation film (bottom) Nylon Peel ply (screen connection 64 g / m 3 ) displaced Laminate (fiberglass) 3 layers of Atlas FK 144 (296 g / m 3 ) Separation film (above) Nylon Peel ply (screen connection 64 g / m 3 ) displaced separation sheet Slip Sheet R & G No 390 190 Ventilation film R & G No 390 180 Membrane Vacuum network ventilation grid 150 g / m 3 (direction - black) Vacuum sheet sheet vacuo R & G No 390 160 Pipes (feed and drain) PVC, transparent (3.0 mm 0 internal, 5.0 mm 0 external) Support glass plate
    Shape: Heating plate
    Reservoir: Beaker
    Vacuum: Standard vacuum pump (20 mbar)
    Test execution:
    [00107] E1 - E10 epoxy resin compositions are mixed in a heatable container and preheated. The supply tube is inserted into the reservoir and fixed, the drain tube (see structuring an infusion test, table 7) is connected to the vacuum pump via a safety valve, the pump is switched on. The heating plate (it simulates the heatable form) is brought to the infusion temperature. With the application of vacuum, the epoxy resin composition is aspirated through the fiber composite. After complete immersion, the supply and drain tubes are disconnected
    Petition 870190128709, of 12/05/2019, p. 35/68
    29/29 and capped, the entire structure now cures on the heating plate to form a laminate. After complete curing and cooling, the laminate is removed from the structure.
    [00108] The powder hardener / accelerator system of the individual components are unsuitable for the polymerization of epoxide resins according to the infusion process. Their mixtures with epoxy resin are separated by filtration at the absorption points (separated) and are no longer available for a cure of epoxy resins. In this way, epoxy resin compositions E1, E3, E5, E7 are not suitable for the production of composites by means of infusion processes.
    [00109] But table 6 shows that the epoxy resin compositions E2, E4, E6 and E8 according to the invention, which contain the liquid hardeners H1, H2, H3 and H4 according to the invention, such as the known systems two-component amine (RIMH 137 from Momentive, IPDA Evonik) allows the tissue fibers to be impregnated according to the infusion process at comparable time intervals. In this case, however, they usually require shorter curing times at 80 ° C and achieve significantly higher glass transition temperatures.
    [00110] In addition, compared to the two-component amine systems (RIMH 137 from Momentive, IPDA Evonik), a significantly smaller amount of hardener is required.
    [00111] The superiority of the new liquid hardeners is also verified, in which a higher glass transition temperature (final Tg) is obtained in the composite.
    权利要求:
    Claims (11)
    [1]
    1. Liquid hardeners for curing polymeric resins, in particular epoxide resins, characterized by the fact that they comprise:
    a) cyanamide and
    b) at least one urea derivative of formula (I) or formula (II) R s

    [2]
    2/4 arylalkyl substituted with -NHC (O) NR1R 2 ;
    wherein the liquid hardener comprises cyanamide and at least one urea derivative of formula (I) or formula (II) in a molar ratio of cyanamide: urea derivative from 1: 1 to 4:
    1.
    2. Liquid hardeners according to claim 1, characterized by the fact that the hardener, in addition to cyanamide and at least one urea derivative, does not comprise any solvents or dissolution promoters or is solvent-free or free of dissolution promoters .
    [3]
    Liquid hardeners according to either of claims 1 or 2, characterized in that the hardener comprises at least two different urea derivatives.
    [4]
    Liquid hardeners according to any one of claims 1 to 3, characterized by the fact that the hardener comprises a urea derivative of formula (I), in which for the radicals it is valid in each case simultaneously or independently of each other:
    R 1 , R 2 are hydrogen, C1- to C15-alkyl;
    R 3 is hydrogen, C1- to C15-alkyl, C3- to C15-cycloalkyl,
    C1- to C15-alkyl substituted with -NHC (O) NR1R 2 ,
    C3- to C15-cycloalkyl substituted with -NHC (O) NR1R 2 or aryl substituted with -NHC (O) NR1R 2 .
    [5]
    Liquid hardeners according to any of claims 1 to 4, characterized in that the hardener contains cyanamide and a urea derivative selected from the urea group, 1,1-dimethylurea, 3- (3-chloro-4-methylphenyl) ) -1,1-dimethylurea, 3- (p-chlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) 1,1-dimethylurea, 1,1 '- (methylenedi-p-phenylen) -bis- (3,3-dimethylurea), 3- (3trifluormethylphenyl) 1,1-dimethylurea, 1,1 '- (2-methyl-m-phenylen) -bis- (3,3Petition 870190128709, of 12/05/2019, page 38/68
    3/4 dimethylurea) and / or 1,1 '- (4-methyl-m-phenylen) -bis- (3,3-dimethylurea) in a molar ratio of cyanamide to urea derivative from 1: 1 to 4: 1 .
    [6]
    6. Composition of epoxy resin, characterized by the fact that it comprises:
    a) at least one epoxy resin and
    b) at least one liquid hardener as defined in at least one of claims 1 to 5.
    [7]
    7. Composition of polyurethane resin, characterized by the fact that it comprises:
    a) at least one polyurethane resin and
    b) at least one liquid hardener as defined in at least one of claims 1 to 5.
    [8]
    8. Liquid mixtures as hardeners for curing curable polymeric resins, in particular epoxide resins, characterized by the fact that they contain:
    a) cyanamide and
    b) at least one urea derivative of formula (I) or formula (II) R s

    [9]
    Use of liquid hardeners as defined in any of claims 1 to 5, characterized in that it is for curing compositions and comprises at least one epoxy resin.
    [10]
    10. Use of liquid hardeners as defined in any of claims 1 to 5, characterized in that it is for curing compositions and comprises at least one polyurethane resin.
    [11]
    11. Use of liquid hardeners as defined in any one of claims 1 to 5, characterized by the fact that they are for curing impregnated fiber materials or impregnated fabrics, meshes or interlaced.
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    同族专利:
    公开号 | 公开日
    SI2678368T1|2015-08-31|
    JP2014506622A|2014-03-17|
    KR20140061300A|2014-05-21|
    US20160083580A1|2016-03-24|
    RU2013142992A|2015-03-27|
    ES2537285T3|2015-06-05|
    WO2012113879A1|2012-08-30|
    DK2678369T3|2015-08-03|
    US9499653B2|2016-11-22|
    CA2816725A1|2012-08-30|
    US9617369B2|2017-04-11|
    RU2586687C2|2016-06-10|
    SI2678369T1|2015-09-30|
    US20130323429A1|2013-12-05|
    JP5940096B2|2016-06-29|
    EP2678368B1|2015-05-06|
    CN103261263A|2013-08-21|
    EP2678369B1|2015-05-06|
    CN103261263B|2016-03-16|
    KR20140009246A|2014-01-22|
    EP2678369A1|2014-01-01|
    CA2816725C|2018-10-23|
    CN103597004A|2014-02-19|
    US20140024741A1|2014-01-23|
    DK2678368T3|2015-08-10|
    JP2014506621A|2014-03-17|
    PL2678369T3|2015-10-30|
    HK1184479A1|2014-01-24|
    CA2827002C|2016-11-08|
    US9296855B2|2016-03-29|
    KR101923528B1|2019-02-27|
    WO2012113878A1|2012-08-30|
    KR101926757B1|2019-03-07|
    BR112013021411B1|2020-04-14|
    RU2013143000A|2015-03-27|
    CN103597004B|2016-01-20|
    CA2827002A1|2012-08-30|
    JP5976686B2|2016-08-24|
    PL2678368T3|2015-10-30|
    ES2538231T3|2015-06-18|
    RU2586118C2|2016-06-10|
    EP2678368A1|2014-01-01|
    BR112013021411A2|2016-10-25|
    BR112013013450A2|2016-10-18|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-09| B25D| Requested change of name of applicant approved|Owner name: ALZCHEM TROSTBERG GMBH (DE) |
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 23/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE201110012079|DE102011012079A1|2011-02-23|2011-02-23|Liquid hardener useful e.g. for hardening of hardenable polymer resins, preferably epoxy resins, comprises cyanamide and at least one urea derivative|
    DE102012000674|2012-01-17|
    PCT/EP2012/053092|WO2012113879A1|2011-02-23|2012-02-23|Novel curing agents for epoxy resins|
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