Epoxy resins containing cycloaliphatic diamine based curing agent

FIELD: chemistry.

SUBSTANCE: invention relates to curing compositions for epoxy resin based systems. The invention discloses a curing composition for epoxy resins, containing a mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, a prepolymer curing composition for epoxy resins, containing a product of reacting epoxide with a mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, as well as a method of preparing the prepolymer curing composition, a method of gluing two substrates, an aqueous epoxy resin and versions of curing compositions and methods of applying a coating on a substrate.

EFFECT: disclosed compositions are compatible with epoxy resins, have higher rate of curing and are capable of curing at lower temperatures without deterioration of coating properties.

19 cl, 3 dwg, 11 tbl, 5 ex

Cross-reference to related applications

This application claims priority based on provisional application U.S. serial No. 60/993288, filed September 11, 2007, and 60/860128, filed November 20, 2006, each of which is incorporated herein by reference.

Background of invention

The technical field to which the invention relates

Embodiments of the invention disclosed herein relate, in General, to compositions hardener. Disclosed herein specific embodiments of the invention relate to compositions hardener for systems based on epoxy resins.

Prior

One of the areas of ongoing research in the field of chemical development is a curing agent, which would be compatible with conventional epoxy resins at low temperatures curing and which would be sufficiently reactive toward epoxy resins, so that the system utverjdala in a wide range of temperatures. Especially desirable curing agents, which will cure at low temperatures for 24 hours in the absence of external accelerators.

Typical amine curing agents, regardless of whether they are aliphatic, aromatic or adduct and epoxy resins, with the end of at least one primary amine group, often cause unwanted side effects "fading" or "turbidity" in the cured product. Fading occurs when the amount of condensation causes the migration of water-soluble compounds to the surface of the product. Discoloration or clouding most likely occurs when the curing agent is stored for a long time and used at low temperatures or under conditions of high relative humidity.

Discoloration and turbidity can to some extent be explained by the interaction of many atoms of hydrogen of the primary amine. However, the reactivity of the resulting curing agent may be reduced because the secondary amines are less reactive than primary amines. As a result, to achieve the appropriate curing times are often used accelerators, especially at a low temperature curing. In addition, many of the adducts of amine curing agents whose primary amine groups are converted to the secondary amine groups, poorly compatible with epoxy resins.

Typical curing agents based on cycloaliphatic diamines include isophorondiamine (ACCESSORIES>), 1,2-diaminocyclohexane and bis-p-aminocyclohexanone. Data cycloaliphatic diamines may is to provide the resin has good properties discoveries, but have the disadvantage that have a low rate of curing epoxy resins.

Accordingly, there is a need for hardening compositions that are compatible with the epoxy resin and having improved curing speed and improved ability to cure at lower temperatures. Preferably improved curing rate does not contradict the critical properties of coatings, including color, turbidity, chemical resistance, adhesion and hydrolytic resistance, among other things.

SUMMARY of the INVENTION

In one aspect of embodiments of the invention discussed herein relate to compositions hardener for epoxy resin, the hardener composition comprises (a) 1,3-bis(aminomethyl)cyclohexane and (b) 1,4-bis(aminomethyl)cyclohexane. The hardener composition may include CIS - and TRANS-isomers of both components (a) and (b).

In another aspect, embodiments of the invention discussed herein relate to compositions formalising hardener for epoxy resins, the composition formalising hardener includes the product of the interaction of the resin with the hardener composition containing (a) 1,3-bis(aminomethyl)cyclohexane and (b) 1,4-bis(aminomethyl)cyclohexane.

In another aspect, embodiments of izobreteny is, considered in this document, refer to the cured composition, comprising the composition of the hardener and terpolymer composition, as described above, and epoxy resin.

In another aspect, embodiments of the invention discussed herein relate to a method of bonding two substrates, the method comprises the epoxy resin and the hardener composition or compositions formalising hardener as described above, one or both of the substrates and bringing the substrates into contact.

Other aspects and advantages disclosed herein of embodiments of the invention will be apparent from the following description of the invention and the attached claims.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 provides a comparison of the reactivity of two known compounds and compositions are opened according to a variant embodiment of the invention.

Figure 2 provides a comparison of the viscosity in the destruction of two known compounds and compositions are opened according to a variant embodiment of the invention.

Figure 3 provides a comparison of the viscosity in the destruction of the compositions based on epoxy resins according to disclosed herein variants of carrying out the invention and an epoxy resin, utverzhdenii ACCESSORIES>.

DETAILED description of the INVENTION

In one aspect of the embodiments of the invention, disclosed herein are curing agents for epoxides with improved speed curing at lower temperatures. In other aspects of embodiments of the invention disclosed herein relate to compositions curing agents for epoxides comprising a mixture of amines and/or derivatives of amines. In other aspects of embodiments of the invention disclosed herein relate to compositions forprimary curing agents for epoxides obtained by the engagement amine with the epoxide.

The mixture of amines or the hardener composition obtained from a mixture of amines may be combined with the epoxy resin with the formation of the cured composition. A mixture of amine curing agents, the composition of the hardener, epoxy resin and cured compositions disclosed herein are described in more detail below.

A mixture of amine curing agents

Embodiments of the invention disclosed herein relate to compositions curing agents for epoxides comprising a mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, their isomers and their derivatives. Other embodiments of the invention disclosed herein relate to compositions formalising from the of erudites, which can be obtained by the interaction of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, their isomers and their combinations with an epoxy compound or resin. For example, 1,3 - and 1,4-bis(aminomethyl)cyclohexane may interact with this epoxide, as D.E.R. 331 education formalising hardener or also called amine adduct.

It is established that a mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexane can provide a very high curing rate as a curing agent for epoxides without deterioration in color/turbidity and chemical resistance. In other embodiments of the invention, the mixture of amines may include norbornanamine (2,5(2,6)-bis(aminomethyl)bicyclo(2.2.1)heptane (NBDA).

In some embodiments of the invention a mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexane may include CIS - and TRANS-1,3 - and 1,4-bis(aminomethyl)cyclohexanol. For example, in some embodiments of the invention the mixture of amine otorgada agents disclosed herein may include CIS - and TRANS-isomers of 1,3-bis(aminomethyl)cyclohexane. In other embodiments of the invention, the mixture may include CIS - and TRANS-isomers of 1,4-bis(aminomethyl)cyclohexane. Other embodiments of the invention may include CIS - and TRANS-isomers of both ,3 - and 1,4-bis(aminomethyl)cyclohexanol.

Unexpectedly it was found that the unique structure and the presence of four isomers, 1,3 - and 1,4-positional isomers with CIS - and transgenetics isomers for each, can lead to improved properties of epoxy resin while maintaining high reactivity, caused by a primary amine.

A mixture of amine curing agents disclosed herein may include 1,3 - and 1,4-bis(aminomethyl)cyclohexane, where the mixture comprises at least some amount of 1,4-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include at least 1 percent by weight of 1,4-bis(aminomethyl)cyclohexane, based on the total weight of 1,3 - and 1,4-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% 1,4-bis(aminomethyl)cyclohexane calculated on the total weight of 1,3 - and 1,4-bis(aminomethyl)cyclohexane.

A mixture of amine curing agents disclosed herein may include 1,3 - and 1,4-bis(aminomethyl)cyclohexane, where the mixture comprises at least some amount of 1,3-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include, at the very measures which, 1 wt.% 1,3-bis(aminomethyl)cyclohexane, based on the total weight of 1,3 - and 1,4-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% 1,3-bis(aminomethyl)cyclohexane calculated on the total weight of 1,3 - and 1,4-bis(aminomethyl)cyclohexane.

In some embodiments of the invention the mixture of amine curing agents may include an isomer mixture of 1,3-bis(aminomethyl)cyclohexane. In some embodiments of the invention the mixture of amine curing agents may include at least some amount of CIS-1,3-bis(aminomethyl)cyclohexane and at least some amount of TRANS-1,3-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include at least 1 wt.% CIS-1,3-bis(aminomethyl)cyclohexane, based on the total weight of 1,3-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% CIS-1,3-bis(aminomethyl)cyclohexane calculated on the total weight of 1,3-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include at least 1 wt.% the Rance-1,3-bis(aminomethyl)cyclohexane, calculated on the total weight of 1,3-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% TRANS-1,3-bis(aminomethyl)cyclohexane calculated on the total weight of 1,3-bis(aminomethyl)cyclohexane.

In some embodiments of the invention the mixture of amine curing agents may include isomeric mixture of 1,4-bis(aminomethyl)cyclohexane. In some embodiments of the invention the mixture of amine curing agents may include at least some amount of CIS-1,4-bis(aminomethyl)cyclohexane and at least some amount of TRANS-1,4-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include at least 1 wt.% CIS-1,4-bis(aminomethyl)cyclohexane, based on the total weight of 1,4-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% CIS-1,3-bis(aminomethyl)cyclohexane calculated on the total weight of 1,4-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include at least 1 wt.% TRANS-1,4-bis(aminomethyl)cyclohexane, p is the score on the total weight of 1,4-bis(aminomethyl)cyclohexane. In various other embodiments of the invention the mixture of amine curing agents may include up to 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90 and up to 99 wt.% TRANS-1,4-bis(aminomethyl)cyclohexane calculated on the total weight of 1,4-bis(aminomethyl)cyclohexane.

In some embodiments of the invention the mixture of amine curing agents may include from 1 to 97 wt.% CIS-1,3-bis(aminomethyl)cyclohexane with the calculation on the total weight of the isomeric mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane. In other embodiments of the invention the mixture of amine curing agents may include from 1 to 97 wt.% TRANS 1,3-bis(aminomethyl)cyclohexane in relation to the total weight of the isomeric mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane.

In some embodiments of the invention the mixture of amine curing agents may include from 1 to 97 wt.% CIS 1,4-bis(aminomethyl)cyclohexane with the calculation on the total weight of the isomeric mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane. In some embodiments of the invention the mixture of amine curing agents may include from 1 to 97 wt.% TRANS-1,4-bis(aminomethyl)cyclohexane in relation to the total weight of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane.

Obtaining mixtures of amine curing agents, revelation is passed in this document, can lead to the formation of impurities, such as bicyclic amines, bicyclic diamines and bicyclic imine. In some embodiments of the invention, the various isomers of bis(aminomethyl)cyclohexane can be cleaned and removed with the use of such a separation process, as distillation.

In some embodiments of the invention the mixture of amine curing agents may include various impurities which may be formed in the process of getting a curing agent. For example, amine curing agents disclosed herein can include bicyclic amines, such as 3-azabicyclo[3.3.1]nonan, bicyclic imine, such as 3-azabicyclo[3.3.1]non-2-ene, and bicyclic diamines, such as 3-azabicyclo[3.3.1]nonan-2-amine. In some embodiments of the invention a mixture of amine curing agents disclosed herein, may include 50 to 100 wt.% a mixture of CIS - and TRANS-isomers of 1,3 - and 1,4-bis(aminomethyl)cyclohexane and at least one of the following three bicyclic compounds: (i) from greater than 0 to about 30 wt.% bicyclic amine, (ii) from greater than 0 to about 25 wt.% bicyclic diamine and (iii) from greater than 0 to about 15 wt.% bicyclic imine. Unexpectedly found that the velocities of the different reactions of epoxy resins with this mixture of things the public does not depend on the presence of bicyclic impurities.

In some embodiments, the implementation can be used derivatives of the above amines with the formation of the composition of the hardener. In other embodiments of the invention may be used the above-described mixture of amines with obtaining compositions formalising hardener. Composition formalising hardener can be formed by the interaction of the above mixture of amines with epoxy resins, epichlorohydrin, ethylene oxide, etc.

Other curing agents

The above mixture of amines optionally can be mixed with other conventional curing agents. A number of other put in a mixture of traditional curing agent will depend on the requirements of the end product, and the efficiency that you want to achieve. If the end use does not require a product that has a high end physical properties, and/or not important reduced processing times, in a mixture with curing agent composition according to the invention can be introduced increased number of low-cost conventional curing agents. The amount of curing agent in the curing agent composition water-based may lie in the range from about 1 to 50 wt.% in calculating the masses of all curing agents, but the pre is respectfully from 50 wt.% to 100 wt.%.

Traditional curing agents are usually polyamine at least 2 nitrogen atoms in the molecule and at least two reactive hydrogen atoms of amine groups on the molecule. The nitrogen atoms are connected divalent hydratability groups. Other gidrolabilna groups, such as aliphatic, cycloaliphatic or aromatic group can also be attached with a simple link to some of the nitrogen atoms. Data polyamine contain at least 2 carbon atoms in the molecule. Preferably polyamine contain from about 2 to about 6 nitrogen atoms of amine groups per molecule, from about 2 to about 8 amino hydrogen atoms per molecule and from 2 to about 50 carbon atoms.

Examples of polyamines that can be used as a conventional curing agents for epoxy resins include aliphatic polyamine, such as Ethylenediamine, ethylendiamin, Triethylenetetramine, Tetraethylenepentamine, pentamethylenebis, dipropylenetriamine, tributylamine, hexamethylenediamine were, directlyrelated, 1,2-propandiamine, 1,3-propandiamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, 2,5-dimethyl-2,5-hexanediamine and the like; cycloaliphatic polyamine, such as ISOPHORONEDIAMINE, 4,4'-diaminophenyl hekselman, metandienon, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, or amines formed "dimer acids" (diarizonae fatty acids), which are formed by condensation of dimeric acids with ammonia, and then the de-hydration and hydrogenation; adducts of amines with epoxy resins, such as adduct of ISOPHORONEDIAMINE with simple diglycidyl ether diatomic phenol, or the corresponding adducts with Ethylenediamine or m-xylylenediamine; analiticheskie polyamine, such as 1,3-bis(aminomethyl)benzene; aromatic polyamine, such as 4,4'-methylenedianiline, 1,3-phenylenediamine and 3,5-diethyl-2,4-toluidine; amidoamine, such as condensates of fatty acids with Diethylenetriamine, Triethylenetetramine etc.; and polyamides, such as condensates of dimeric acids with Diethylenetriamine, Triethylenetetramine etc. Some commercial examples of polyamines include the hardener EPI-CURE® 3140 (adduct of dimeric acid and aliphatic polyamine), hardener EPI-CURE® 3270 (modified aliphatic polyamine), hardener EPI-CURE® 3274 (modified aliphatic polyamine), hardener EPI-CURE® 3295 (adduct of aliphatic amine), compound EPI-CURE® 3282 (adduct of aliphatic amine), compound EPI-CURE® 3055 (amidopolyamine), hardener EPI-CURE® 3046 (amidopolyamine) and hardener EPI-CURE® 3072 (modified amidoamine) and hardener EPI-CRE® 3483 (aromatic polyamine), available from Shell Chemical Company. Can also be used mixtures of polyamines.

Other curing agents which may be used in combination with a mixture of amine curing agents described above, may include phosphines, amines, Quaternary ammonium salts and phosphonium, such as tetraethylammonium, Tetramethylammonium, tetraethylammonium, tetraethylammonium, Tetra(n-butyl)ammoniacal, Tetra(n-butyl)ammoniumbromide, Tetra(n-butyl)ammoniated, Tetra(n-butyl)ammoniacal, Tetra (n-octyl)ammoniacal, Tetra(n-octyl)ammoniumbromide, Tetra(n-octyl)ammoniated, Tetra(n-octyl)ammoniacal, methyltris(n-octyl)ammoniacal, bis(tetraphenylphosphonium)ammoniacal, complex atilde-p-tolylphosphino/acetic acid complex ethyltriphenylphosphonium/acetic acid, or combinations thereof, and the like, as described in U.S. patent No. 5208317, 5109099 and 4981926.

Other aliphatic amine curing agents that may be used in combination with a mixture of amine curing agents described above, may include amines, such as C_5-15aliphatic and cycloaliphatic diamines, and polyamine, such as 2-methyl-1,5-pentanediamine, 1,2-diaminocyclohexane, Triethylenetetramine, Diethylenetriamine, 1,4 - or 1,3-diaminocyclohexane, ISOPHORONEDIAMINE, 1,3-bis(aminomethyl)benzene, and Mernie mixture of bis(4-aminocyclohexane)methane, oligo(propylene oxide)diamine, and adducts of the above amines with epoxy resins, epichlorohydrin, Acrylonitrile, ethylene oxide, etc.

In other variants of the invention, the curing agents on the basis of arylamidine, which can be used in combination with a mixture of amine curing agents described above, may include those which contain at least two primary amine groups, one primary amine group, used for reaction with the carboxyl group, phenolic compounds and other primary amine group available for reaction with monoglycidyl connection. Examples of the polyamines used in the disclosed herein embodiments for carrying out the invention may include metropolitaine, ethyltoluene, butyltoluene, Propylenediamine, pentylaniline, hexylaniline, heptylaniline etc. are also included higher homologues data amines and related aminoalkylsilane of piperazines. Specific examples of these polyamines include Ethylenediamine, Triethylenetetramine, Tris(2-amino-ethyl)amine, 1,2 - and 1,3-Propylenediamine, trimethylenediamine, 1,2 - and 1,4-butanediamine, hexamethylenediamine were, decamethylenediamine, octamethylene, Diethylenetriamine, Triethylenetetramine, di(heptamethine)triamine, dipropylenetriamine, Tetraethylenepentamine is, trimethylenediamine, pentamethylenebis, di(trimethylene)triamine, n - and m-xylylenediamine, methylenedianiline, 2,4-toluidine, 2,6-toluidine, polymethylenepolyphenylene and mixtures thereof. Can also be used higher homologs obtained by condensation of two or more of the above mentioned alkylamino. More preferred are those polyamine that contain at least one secondary amino group, in addition to at least two primary amino groups, and numerous divalent hydrocarbon radical containing 2-4 carbon atoms.

Other curing agents known to specialists in this field can also be used in combination with the above-described mixture of amines.

In some embodiments of the invention other curing agents used in combination with a mixture of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, or derivatives thereof, may be present in amount less than 50 wt.% in the composition of hardener, based on the total weight of 1,3 - and 1,4-bis(aminomethyl)cyclohexane and other curing agents or derivatives used in the composition of the hardener.

Accelerator

The accelerator does not need to be introduced to speed up the curing system epoxy resin - curing agent. Can be used different is e-compatible with amine accelerators, because they are soluble in the amine curing agents. One particular accelerator that can be used in the variants of implementation of the present invention is benzyl alcohol.

Examples of accelerators include metal salts, such as, for example, sulfonates, phosphonates, sulfates, tetrafluoroborates, carboxylates, and nitrates of the metals of groups IA, IIA and series transition metals of the Periodic table (CAS version), preferably salts of Mg, Ca, Zn and Sn and their complexes, inorganic acids such as, for example, HBF₄H₂SO₄H₂NSO₃H and H₃PO₄; carboxylic acids, preferably replacement carboxylic acids, such as, for example, salicylic, lactic, glycolic and resorcinol; phenolic compounds, such as, for example, phenol, t-butylphenol, Nonylphenol and bisphenol a; hydroxyl compounds such as benzyl alcohol; imidazoles; cyanamide compounds such as dicyandiamide and cyanamide; sulfonamides, such as, for example, p-toluensulfonate, methanesulfonate, N-methylbenzenesulfonamide and sulphonamide; and imides, such as, for example, phthalimide, succinimide, deemed perylenetetracarboxylic acid and saccharin.

In some embodiments of the invention may be used with the accelerator, when the rate of curing at the desired temperature t is aetsa below optimal. For example, for adhesive applications and civil construction where it is desirable to use at low temperature in the composition can be advantageously included accelerator. As another example, the accelerator may be entered when cured composition employed contains amino group, or when the concentration of amino groups is low.

In other embodiments of the invention accelerators may include, for example, alkylbenzenesulfonate calcium, calcium nitrate, alkanesulfonyl magnesium, tetracarbonyl acid, salicylic acid, carbolic acid, dichloracetic acid, triperoxonane acid and mercaptohexanol acid. In other embodiments of the invention accelerators may include triphenylphosphine, tributylphosphine, three(p-were)phosphine, three(nonylphenyl)phosphine, triphenylphosphine-triphenylboron, three(nonylphenyl)phosphine, triphenylphosphine-triphenylboron, tetraphenylporphin-tetraphenylborate or similar compounds phosphate type; triethylamine, benzylideneamino, alpha methylbenzhydrylamine, 1,8-diazabicyclo{5.4.0}undec-7-ene, or similar connection tertiary amine; 2-Mei, the 2-phenylimidazole, 2-phenyl-4-Mei or similar connection imidazole type.

Accelerators can be used in some embodiments, the implementation of whom subramania in the amount of from about 0.1 wt.% to about 20 wt.% based on the weight of epoxy resin. In other embodiments of the invention accelerators can be used in amounts of from about 0.1 wt.% to about 5 wt.%, based on the weight of epoxy resin.

Solvents

Suitable solvents that can be used in the present invention include, for example, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, simple glycol ethers, amides, sulfoxidov, sulfones, and combinations thereof, and the like, Particularly suitable solvents include, for example, methanol, ethanol, isopropanol, hexane, heptane, octane, Nanan, decane, toluene, xylene, simple methyl ether of ethylene glycol, easy-ethyl ether of ethylene glycol, a simple n-butyl ether of ethylene glycol, simple phenyl ether of ethylene glycol, simple methyl ether of propylene glycol, a simple phenyl ether of propylene glycol, simple methyl ester tripropyleneglycol simple methyl ether of diethylene glycol, easy-ethyl ether of diethylene glycol, a simple n-butyl ether of diethylene glycol, a simple phenyl ether of diethylene glycol, simple methyl ester butyleneglycol, N,N-dimethylacetamide, dimethylsulfoxide, sulfolan, combinations thereof, etc.

In some embodiments of the invention, the solvent may be used in amounts of from approximately 5 to approximately 95 percent by weight in the region of the account on the combined weight of solvent, epoxide and mixtures of amine curing agents. In another embodiment of the invention, the solvent may be used in amounts from about 20 to about 60 wt.% and from about 30 to about 40 wt.% in other embodiments of the invention, where the percentage by weight calculated on the combined weight of the solvent, epoxy and mixtures of amine curing agents.

Epoxides

The epoxy resin used in embodiments of the invention disclosed in the present description, can vary and include traditional and commercially available epoxy resins which can be used individually or in combinations of two or more of them, including, for example, Novolac resin modified with isocyanate epoxy resin and carboxylate adducts, among other things. When choosing an epoxy resin compositions disclosed in this document, it is necessary to consider not only the properties of the final product, but also the viscosity and other properties that may affect the processing composition based on resin.

Component-based epoxy resin may be any type of epoxy resin used in the compositions for forming, including any material containing one or more reaction oxirane groups identified in this d is the document "epoxy group or epoxy functionality. The epoxy resin used in embodiments of the invention disclosed herein include mono-functional epoxy resin, multi - or poly-functional epoxy resin, and combinations thereof. Monomeric and polymeric epoxy resins may be aliphatic, cycloaliphatic, aromatic or heterocyclic epoxy resins. Polymeric epoxides include linear polymers containing terminal epoxy groups (for example, a simple diglycidyl ether polyoxyethyleneglycol), polymeric skeletal oxirane links (for example, polybutadienes) and polymers having side epoxy group (such as, for example, glycidylmethacrylate polymer or copolymer). The epoxides can be a pure compound, but they usually represent a mixture or compound containing one, two or more epoxy groups per molecule. In some embodiments the invention, the epoxy resin may also include reactive-Oh groups, which can interact at elevated temperatures with anhydrides, organic acids, amino, phenolic resins or epoxy groups (when catalyzed) with the formation of additional cross-linking.

In General, the epoxy resin can be glycidaldehyde resins, C is kalifatidis resins, epoxydecane oils and so forth. Piridilsoderzhashchimi resins often are a product of the interaction of simple pilgramage ether, such as epichlorohydrin, and befooling compounds, such as bisphenol a; C₄-C₂₈allylglycidyl ethers; C₂-C₂₈alkyl - and alanylhistidine esters; C₁-C₂₈alkyl-, mono - and polyphenoloxidase ethers; simple polyglycidyl ethers of polyvalent phenols, such as pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane (or bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenyl, 4,4'-dihydroxydiphenylmethane (or bisphenol a), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylamine, 4,4'-dihydroxydiphenylsulfone and Tris(4-hydroxyphenyl)methane; simple polyglycidyl esters of products of chlorination and synthesized above diphenols; simple esters polyglycerol novolacs; simple polyglycidyl esters of diphenols obtained by the esterification of ethers of diphenols obtained by the esterification of salts of aromatic hydrocarbonic acids dihalogenoalkane or dihalogenoalkane simple ether; simple polyglycidyl ethers of polyphenols obtained by condensing phenols and long-chain halogenated paraffins, the content is asih, at least two of the halogen atom. Other examples of epoxy resins used in embodiments of the invention disclosed herein include a simple diglycidyl ether of bis-4,4'-(1-methylethylidene)phenol and simple diglycidyl ether (chloromethyl)oxiranemethanol A.

In some embodiments the invention, the epoxy resin may include connection type simple pilgramage ether; type complex pilgramage ether; heterocyclic type and halogenated epoxy resins and the like, non-limiting examples of suitable epoxy resins may include cresol Novolac epoxy resin, phenolic Novolac epoxy resin, biphenylene epoxy resin, hydrogenerating resin, stilbenoids resin, and their mixtures and combinations.

Suitable polyepoxide connection may include diglycidyl simple ether of resorcinol (1,3-bis-(2,3-epoxypropoxy)benzene), simple diglycidyl ether of bisphenol a (2,2-bis(p-(2,3-epoxypropoxy)phenyl)propane), triglycidyl p-aminophenol(4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline), simple diglycidyl ether bromobisphenol A (2,2-bis(4-(2,3-epoxypropoxy)-3-bromophenyl)propane), simple diglycidyl ether of bisphenol F (2,2-bis(p-(2,3-epoxypropoxy)phenyl)methane), simple triglycerol ether meta and/or para-aminophenol (3-(2,3-epoxy is repossi)-N,N-bis(2,3-epoxypropyl)aniline) and tetraphenylmethane (N,N,N,N-Tetra(2,3-epoxypropyl) 4,4'-diaminodiphenylmethane) and a mixture of two or more polyepoxide compounds. A more comprehensive list of usable epoxy resins can be found in Lee, H. And Neville, K., Handbook of Epoxy Resins, McGraw-Hill Book Company, reprint 1982.

Other suitable for use resin include polyepoxide compounds based on aromatic amines and epichlorohydrin, such as N,N'-diglycidylether; N,N'-dimethyl-N,N'-diglycidyl-4,4'-diaminodiphenylmethane; N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; simple glycidyloxy ether N-diglycidyl-4-aminophenol and N,N,N',N'-tetraglycidyl-1,3-propylene bis-4-aminobenzoate. Epoxy resins can also include glycidyloxy derivatives of one or more aromatic diamines, aromatic monoperiodic amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids.

Suitable for use with epoxy resins include, for example, a simple polyglycidyl ether of polyhydric polyols, such as ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol and 2,2-bis(4-hydroxycyclohexyl)propane; simple polyglycidyl esters of aliphatic and aromatic polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-natalijagolosova acid and diarizonae linoleic acid; simple polyglycidyl ethers of polyphenols, is aka as, for example, bisphenol a, bis-phenol F, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)isobutane, and 1,5-dihydroxynaphthalene; modified epoxy resins with acrylate or urethane fragments; glycidamide epoxy resin and Novolac resin.

Epoxy compounds may be cycloaliphatic or the alicyclic epoxides. Examples of cycloaliphatic epoxides include diepoxide cycloaliphatic esters of dicarboxylic acids, such as bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexyl)adipate, bis(3,4-epoxycyclohexylmethyl)pimelate; vinylcyclohexane; limonepiemonte; Dicyclopentadiene etc. Other suitable cycloaliphatic epoxides of esters of dicarboxylic acids are described, for example, in U.S. patent No. 2750395.

Other cycloaliphatic epoxides include carboxylates 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, such as carboxylate 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane; carboxylate 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexane; carboxylate 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane; carboxylate 3,4-epoxy-2-methylcyclohexyl-3,4-epoxy-2-methylcyclohexane; carboxylate 3,4-epoxy-3-methylcyclohexyl-3,4-epoxy-3-is ethylcyclohexane; carboxylate 3,4-epoxy-5-methylcyclohexyl-3,4-epoxy-5-methylcyclohexane etc. Other suitable carboxylates 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane described, for example, in U.S. patent No. 2890194.

Additional epoxydodecane materials that are particularly suitable for use include materials on the basis of simple Monomeric diglycidyl esters. Examples are simple di - or polyglycidyl ethers of polyhydric phenols obtained by the reaction of a polyhydric phenol with an excess of chlorohydrin, such as epichlorohydrin. Data polyhydric phenols include resorcinol, bis(4-hydroxyphenyl)methane (known as bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (known as bisphenol a), 2,2-bis(4'-hydroxy-3',5'-dibromophenyl)propane, 1,1,2,2-tetrakis(4'-hydroxyphenyl)ethane or condensates of phenols with formaldehyde which are obtained in an acidic environment, such as phenolic Novolac and crenoline novolak. Examples of epoxy resins of this type are described in U.S. patent No. 3018262. Other examples include simple di - or polyglycidyl esters of polyhydric alcohols, such as 1,4-butanediol, or polyalkylene glycols, such as propylene glycol, and a simple di - or polyglycidyl ethers of cycloaliphatic polyols, such as 2,2-bis(4-hydroxycyclohexyl)propane. Other examples are mono-functional resins, such as to tillytilly simple ether or butespecially simple ether.

Another class of epoxy compounds is a complex polyglycidyl esters and complex poly(beta-methylglycerol) esters of polyvalent carboxylic acids, such as phthalic acid, terephthalic acid, tetrahydrophtalic acid or hexahydrophthalic acid. An additional class of epoxy compounds are N-glycidyloxy derivatives of amines, amides and heterocyclic nitrogen bases, such as N,N-diglycidylether, N,N-diglycidylether, N,N,N',N'-tetraglycidyl(4-AMINOPHENYL)methane, tripyridyltriazine, N,N'-digitalisation, N,N'-diglycidyl-5,5-dimethylhydantoin and N,N'-diglycidyl-5-isopropylidene.

Still other epoxydodecane materials are copolymers of esters of acrylic acid and glycidol, such as glycidylmethacrylate and glycidylmethacrylate, with one or more copolymerizable vinyl compounds. Examples of these copolymers are 1:1 styrene-glycidylmethacrylate, 1:methyl 1-Methacrylonitrile and 62.5:24:13.5 methyl methacrylate-acrylate-glycidylmethacrylate.

Epoxy compounds that are easily available include octadecanoid; glycidylmethacrylate; D.E.R. 331 (bisphenol a liquid epoxy resin) and D.E.R. 332 (simple diglycidyl ether of bisphenol a, available from The Dow Chemical Company, Midland, Michigan; dioxide vinylcyclohexane; carboxyl the t 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane; carboxylate 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexene; adipate bis(3,4-epoxy-6-methylcyclohexylamine); simple bis(2,3-amoxicillinbuy ether; aliphatic epoxide-modified polypropylenglycol; depotentiated; epoxydecane polybutadiene; silicone resin containing epoxy functionality; retarding the ignition epoxy resin (such as epoxy resin type, brominated bisphenol a, available under the trademark D.E.R. 580 from The Dow Chemical Company, Midland, Michigan); simple diglycidyl ether of 1,4-butanediol and phenol-formaldehyde Novolac resin (as those available under the trademarks D.E.N. 431 and D.E.N. 438 available from The Dow Chemical Company, Midland, Michigan); and simple diglycidyl ether of resorcinol. Although not specifically mentioned, but can also be used for other epoxy resin under the trade names D.E.R. and D.E.N., available from The Dow Chemical Company.

Epoxy resins can also include modified isocyanates epoxy resin. Polyepoxide polymers or copolymers with isocyanate or polyisocyanate functionality may include the copolymers of epoxypolyester. These materials can be obtained by using polyepoxides prepolymer containing one or more oxirane rings, with the formation of 1,2-epoxy functionality, and is containing a series of open oxirane ring, which can be used as the hydroxyl group for dihydroxystearic compounds for reaction with the diisocyanate or polyisocyanates. Isocyanate fragment opens oxirane ring, and the reaction proceeds the reaction of an isocyanate with a primary or secondary hydroxyl group. Polyepoxide resin has sufficient epoxy functionality to provide epoxypolyester copolymer, preserving effective oxirane rings. Linear polymers can be obtained by reaction of diepoxides and diisocyanates. In some embodiments the invention, the di - or polyisocyanates can be aromatic or aliphatic.

Other suitable epoxy resins are disclosed, for example, in U.S. patents№№7163973, 6632893, 6242083, 7037958, 6572971, 6153719 and 5405688 and in publications of patent applications U.S. No. 20060293172 and 20050171237, each of which is introduced herein by reference.

Catalysts

Catalysts may include imidazole compounds, including compounds containing one imidazole ring in the molecule, such as imidazole, 2-Mei, 2-ethyl-4-Mei, the 2-undecylenate, 2-getdelimiter, 2-phenylimidazole, 2-phenyl-4-Mei, 1-benzyl-2-Mei, the 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 1-cyanoethyl-2-marked Idasa, 1-cyanoethyl-2-ethyl-4-Mei, 1-cyanoethyl-2-undecylenate, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazole-(1)']ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4-methylimidazole-(1)']ethyl-s-triazine, 2,4-diamino-6-[2'-undecylenate-(1)']ethyl-s-triazine, adduct 2-methylimidazole-isocyanuric acid adduct of 2-phenylimidazole-isocyanuric acid, 1-amino-ethyl-2-Mei, the 2-phenyl-4,5-dihydroxyethylene, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole and the like; and compounds containing 2 or more imidazole rings in the molecule, which is obtained by dehydration of the above-mentioned hydroxyethylstarch imidazole compounds such as 2-phenyl-4,5-dihydroxypyrimidine, 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4-benzyl-5-hydroxymethylimidazole; and their condensation reaction off formaldehyde, for example, 4,4'-methylene-bis-(2-ethyl-5-Mei), etc.

Supplements

The curing agent composition of the present invention may include other additives, such as fillers, elastomers, stabilizers, filling additives, plasticizers, accelerators, pigments, reinforcing fillers, rheology modifiers and flame retardants, depending on the area of use. If necessary, the composition of this izaberete the Oia can be combined with a thermoplastic resin, thermoplastic elastomer, an organic synthetic rubber, agent voltage reduction silicone type or similar, Carnauba wax, higher fatty acids, synthetic waxes or similar waxes; carbon black or similar coloring agents; halogen acceptors, etc. cured compositions disclosed herein can be used in coatings and some sectors of civil construction, such as floor coverings, liquid mortars and adhesives.

In the field of coatings based component curable epoxy resin, or a mixture of amine curing agents may also contain pigments of the traditional type, such as iron oxides, lead oxides, strontium chromate, carbon black, titanium dioxide, talc, barium sulfate, phthalocyanine blue and green, cadmium red, chrome green, lead silicate, silicon dioxide, silicates, etc. these pigments can be added to the component polyamino curing agent or component epoxy resin before mixing them together. However, pigment, iron blue, calcium carbonate and pigments that are considered reactionary due to their basic nature, may be incompatible in cured compositions when used in large numbers. Usually they are only a component of origaudio agent. Defoamers, dyes, agents that increase the slip, thixotropic additives, etc. are conventional auxiliary additives to most surfaces and can be used in compositions based on epoxy resins of the present invention. The used amount of the additive may be in the range from 20 to 100 parts by weight based on the weight of epoxy resin and a mixture of amine curing agents.

When using floor coverings component curable epoxy resin or a mixture of amine curing agents may also contain fillers such as sand, other silicon-containing materials, iron and other metals. A small number tixotropic agents, coloring agents, inert plasticizers and leveling agents also, if desired, can be introduced into the cured composition. Data cured floor compositions can be applied by smoothing, spray or kstewangel floor substrate.

Reinforcing fillers can be added to any component, epoxide or mixture of amine curing agents include natural and synthetic fibers in the form of a fabric, a nonwoven fabric, monofilament yarns, etc. Other materials for reinforcement include glass, ceramics, nylon, rayon, cotton, aramid, graphite, and combinations thereof. Suitably the e fillers include inorganic oxides, inorganic carbonate, ceramic microspheres, plastic microspheres, glass microspheres, clay, sand, gravel, and combinations thereof. Fillers can be used in quantities appropriate components from 0 to 100 parts by weight calculated on the combined amount of the epoxide and mixtures of amine curing agents.

The polymer binder may include a wide variety of other additives, such as, for example, hardeners, dyes, pigments and rheology modifiers, flame-retardant agents, dessicant and all types of additives used in the present invention in a known order. Examples of flame retardants include monoammonium phosphate, diammonium phosphate, and aluminum trihydrate. Data supplements can be in the form of liquids or particles, because the binding remains solid, has a desirable particle size and does not impact negatively on the binder.

Cured composition

In some embodiments of the invention overredoese composition or curable composition can be prepared by mixing one or more epoxy resins with a mixture of amine curing agents as described above. In other embodiments the invention, the cured composition or curable composition can be prepared by mixing one or not is how many epoxy resins with forprimary hardener, obtained by the reaction of epoxy resin with a mixture of amine curing agents as described above. In other embodiments the invention, the cured composition can be obtained by mixing one or more epoxy resins with a mixture of amine curing agents and forprimary hardener obtained by the reaction of epoxy resin with a mixture of amine curing agents.

The number of epoxy resins, used in curing the composition may depend on the desired molecular weight and functionality of the epoxide. In some embodiments the invention, the epoxy resin may be used in amount from about 30 wt.% to about 85 wt.% calculated on the total mass of the cured composition (epoxy resin, a mixture of amine curing agents and formalising hardener obtained from a mixture of amine curing agents). In other embodiments the invention, the epoxy resin can be used in curing the composition in an amount from about 40 wt.% up to 75 wt.%; and from about 45 wt.% to about 70 wt.% in another embodiment of the invention, calculated on the total weight of the curing composition.

In some embodiments the invention, the epoxy resin may be overiden the above-described mixture of 1,3 - and 1,4-bi is(aminomethyl)cyclohexanol. In other embodiments the invention, the epoxy resin may be overiden the above-described mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexanol in combination with one or more other epoxy curing agents such as phenols, amines, carboxylic acids, phenol-formaldehyde resin and anhydrides, as well as on the hydroxyl groups of epoxy resin.

In some embodiments of the invention may be implemented interaction epoxy resin with forprimary hardener, such as, for example, forprimary curing agent obtained by the reaction of the epoxide with a mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexane. In other embodiments the invention, the epoxy resin may be overiden forprimary hardener obtained by the reaction of the epoxide with the above-described mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexanol in combination with one or more other epoxy curing agents such as phenols, amines, carboxylic acids, phenol-formaldehyde resin and anhydrides. For example, forprimary curing agent may be a polymer with amine terminal groups or polymer blend comprising a polymer with amine terminal groups and one or more polymers with carboxyl end groups, phenol-formaldehyde polymer, polymer with phenol, the limit is mi groups, multifunctional amine, carboxylic acid or phenol.

Curing and final application

The above components (including a mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexanol and epoxy resin, and other optional components, such as the above other curing agents, additives and accelerators) can be mixed and/or solidified at a temperature between -25°C and 200°C. In other embodiments of the invention the temperature at which can be carried out the curing reaction may depend on the specific compounds and used curing compositions. In other embodiments of the invention the curing temperature may be in the range from approximately 15°to approximately 200°C, from about 30°to about 180°C. in other embodiments of the invention; from about 40°to about 160°C. in other embodiments of the invention; from about 50°to about 150°C. in other embodiments of the invention. In other embodiments the invention, the curable composition can be overiden at a temperature in the range of from about -40°C. to about 100°C.

Curable composition can be overiden in the previous temperature curing for a period of time sufficient to utverzhdeni the epoxy resin. In some embodiments of the invention, the curing time may be less than 72 hours. In various other embodiments of the invention, the curing time may be less than 48 hours, less than 24 hours less than 16 hours, less than 12 hours less than 10 hours, less than 8 hours, less than 6 hours less than 4 hours and less than 2 hours. In other embodiments of the invention, the curing time may be less than 60 minutes, less than 45 minutes or less than 30 minutes.

The mixture of amines may be contained in the composition in an amount effective for curing epoxy resins, usually in the amount of average size in the range of from about 0.6 to about 2 equivalents per epoxy resin.

In some embodiments of the invention the mixture of amine curing agents are used in amounts of from 0 wt.% to about 1 wt.%. In other embodiments of the invention the mixture of amine curing agents may be used in amounts of from about 0.01 wt.% up to about 0.5 wt.%; from about 0.1 wt.% up to about 0.2 wt.% in other embodiments of the invention, based on the combined weight of resin and a mixture of amine curing agents.

Cured compositions described above, which may be used as coatings and can be applied to the substrate by brush, spraying or rolling. In addition to the use as coatings, cured compositions according to the invention can be used in such applications as flooring, casting, sealing cracks or defects, molding, adhesives, sealants, spinning fibers, encapsulation, construction and electrical laminates, composites, etc.

Cured compositions can be used in various fields of industrial application or other applications of epoxides, such as coatings, laminates and composites. Industrial coatings are protective surface coating (coating of paint)applied to the substrates, which otverzhdajutsja or are vulcanized with the formation of continuous films for decorative purposes, and also for protection of the substrate. The protective coating typically comprises an organic polymeric binder, pigments, and various coloring additives, where the polymeric binder acts as a fluid medium for pigments and gives rheological properties of liquid paint to cover. After curing or vulcanization of the polymer binder hardens, acts as a binder for pigments and provides a desirable adhesion of the film of paint to the substrate. The pigments may be organic or inorganic and can functionally affect the transparency and color,in addition to the durability and hardness.

Can be obtained powder coatings, which include cured compositions described herein, and suitable pigments, catalysts and additives. Data powdered dyes and coatings of them can have a surprisingly good combination of properties. Depending on the choice and quantity of epoxide, a mixture of amine curing agent and optional components, powder dyes derived from them, can have good flow properties, good chemical resistance, high gloss and high resistance to scratching, good physical and mechanical properties, good durability and good lasting color.

In other embodiments the invention, the cured compositions described herein can be part of dispersions in aqueous or oil-based. For example, the composition of the coating is water-based, containing cured compositions disclosed herein can be used in compositions for coating containers and spiral.

Cured compositions can be used in construction and may contain epoxy resin based on or containing simple diglycidyl esters diatomic phenols, curing agent containing a mixture of amine curing agents as described above, and the diluent based on the adduct is an aliphatic alcohol - accelerated. Cured compositions used to apply the coatings can contain simple diglycidyl esters diatomic phenols and/or products of the interaction of simple diglycidyl esters of diatomic alcohols with bisphenolate, curing agent containing a mixture of amine curing agents as described above, and the diluent based on the adduct of an aliphatic alcohol - accelerated. Epoxy resin can be mixed with a mixture of amine curing agents containing the diluent, or mixed with forprimary hardener formed by the mixture of amine curing agents, the adduct of aliphatic alcohol - accelerated and optional accelerator, simultaneously or in any order at a temperature below the temperature of curing, such as, for example, below approximately 100°C. the Ratio of epoxy resin to a mixture of amine curing agents may lie in the range from about 10:90 to about 90:10 in some embodiments of the invention and from about 20:80 to about 80:20 percent by weight of another in other embodiments of the invention.

In other embodiments the invention, the cured composition can be used in the coating of ships, protective coatings, civil engineering, adhesives and as odnokon entogo composite. For example, the composites formed using the cured compositions disclosed herein can be used in the blades of windmills and other applications.

In some embodiments of the invention, epoxy resins are used for these different applications may include simple diglycidyl ether of bisphenol a, simple diglycidyl ether of bisphenol F or epoxy phenol Novolac resin.

EXAMPLES

Example 1

In order to assess the reaction of the curing of epoxy resins a cycloaliphatic diamines are using the method of differential scanning calorimetry (DSC). Epoxy resin based on bisphenol a (EPON® 828, available from Shell) is mixed with the diamine (or with a mixture of amine curing agents include CIS and TRANS isomers of 1,3 - and 1,4-bis(aminomethyl)cyclohexane, referred to herein as UNOXOL® diamine (example 1)or with isophorondiamine (ACCESSORIES>) (comparative example 1)in an equivalent ratio 1:1, and are studying the curing reaction at a temperature from 20°C to 120°C at a heating rate of 1°C/min in the DSC. The temperature at which the heat for the reaction mixture depending on the temperature reaches its maximum, is considered by the curing temperature. The curing reaction UNOXOL® Diamine with EPON® 828 has the t peak at 65,14°C, because both amine groups have the same reactivity, whereas the curing reaction of isophorondiamine (ACCESSORIES>) EPON® 828 has two peaks at 69,75°C and 93,69°C, corresponding to the difference reactionary abilities of two different amine groups in ACCESSORIES>. The results show that with respect to epoxy resins UNOXOL® diamine has a much higher reactivity than ACCESSORIES>. Therefore, UNOXOL® diamine can be used for curing epoxy resins at lower temperatures than ACCESSORIES>.

The operational properties of epoxy coatings, hardened or UNOXOL® diamine, or isophorondiamine shown in table 1. Shear connection steel to steel lap joint with epoxy resin (EPON® 828), utverzhdenii UNOXOL® diamine at 65°C for one hour is significantly higher than for the corresponding system, utverzhdenii ACCESSORIES>. Hydrolytic resistance of the coating with an epoxy-based primer mixture of three epoxy resins was determined depending on diamines curing agent by immersing the samples in water for one week after curing coatings at room temperature for two days. Coating, caulk ACCESSORIES > showed bubbling while coating, caulk UNOXOL® diamine, can lead to the development of coatings that exceed the properties of the coating, from eridania ACCESSORIES>.

Example 2

The composition containing formilitary hardener of UNOXOL® diamine (example 2), was compared with the industrial standard hardener ANCAMINER® 1618 (available from Air Products) (comparative example 2). In the composition containing forprimary hardener UNOXOL® diamine was added 20% benzyl alcohol. In both compositions used epoxy resin D.E.R. 331. The formulations were applied to steel cold rolled (thickness in a wet state is approximately 10 mm). Weight percents of the components of the compositions are presented in table 2. Table 3 shows the Physical properties of these compounds, obtained using industry standard test method listed in the table.

As you view the th from table 3, the composition containing forprimary hardener of CIS - and TRANS-isomers of 1,3 - and 1,4-bis(aminomethyl)cyclohexane (part 2), develops the best indentation hardness and the pendulum hardness of the first (day 1) and retains the best hardness throughout (day 7). The time of drying of a thin film is much better for the composition containing forprimary hardener of CIS - and TRANS-isomers of 1,3 - and 1,4-bis(aminomethyl)cyclohexane compared with industrial hardener ANCAMINER® 1618.

Example 3

The composition containing forprimary hardener UNOXOL® diamine (example 3) was compared with a similar forprimary hardener ACCESSORIES > (comparative sample 3). In both compounds as epoxy resin used D.E.R. 331 and both included the accelerator benzyl alcohol. Formulation compositions shown in table 4. The formulations were applied to the panel from bonderite (wet thickness of 10 mm). Physico-mechanical properties of these compositions are shown in tables 5 and 6.

As can be seen from tables 4-6, compositions containing forprimary hardener of CIS - and TRANS - 1,3 - and 1,4-bis(aminomethyl)cyclohexane (part 2), develop better indentation hardness and pendulum hardness, from day 1, and retaining the best hardness after 7 days. Part 2 also has a better Shine than 7 days. The time of drying of a thin film is much better for the composition containing forprimary hardener of CIS - and TRANS - isomers of 1,3 - and 1,4-bis(aminomethyl)cyclohexane compared to ACCESSORIES > forprimary hardener.

Example 4.The reactivity and viscosity of destruction

Reactivity and viscosity at the destruction of UNOXOL® diamine (example 4) and ACCESSORIES > (comparative sample 4) was compared to the composition containing D.E.R. 331. Formulations of the compositions shown below in table 7.

Study of the reactivity of (kinetics) was performed using differential scanning calorimeter (the SC). Reactivity was measured as % conversion at room temperature. Comparison of the results of the study of the reactivity shown in figure 1. When cured at room temperature, the composition containing UNOXOL® diamine, reaches 80% conversion in less than 24 hours, whereas the structure on the basis ACCESSORIES > reaches a maximum conversion of 65%. Due to this high reactivity of compounds containing UNOXOL® diamine achieve better physical-mechanical properties at room temperature in less than 24 hours.

Measured viscosity at the destruction of samples, the measurement results are shown in figure 2. The study of the viscosity when the destruction was carried out on a transparent casting size 1/8 inch according to ASTM D5045. As you can see, the viscosity at the destruction for compositions containing UNOXOL® diamine, more than for samples containing ACCESSORIES>.

Example 5

In this example, the measured reactivity UNOXOL® diamine and mixtures UNOXOL® diamine with impurities bicyclic amine (VA), bicyclic diamine (BDA) and bicyclic imine (BI). The structure of the diamine (DC1, DC2, and so on) are presented in table 8.

Compositions on the basis of the diamine was mixed with D.E.R. 331 according to the formulations listed in table 9 and compared on the reactivity of D.E.R. 331 accessories > with the industry standard. Reactivity of mixtures based on D.E.R. 331 was measured using a differential scanning calorimeter (DSC) by monitoring the enthalpy during the curing reaction. Reactivity was measured as the percent conversion at room temperature. The results of the reactions were compared in table 10.

As the results in table 10, there is no significant difference in the reaction rate UNOXOL® diamine and mixtures UNOXOL® diamine with impurities bicyclic amine, bicyclic diamine and bicyclic imine with epoxy resin. Impurities may be up to 25 percent by weight without a significant drop in reactivity. In addition, the reaction rate of each diamines of the composition is significantly higher than the industry standard ACCESSORIES>.

As the results in table 10, the purification of a mixture of diamines may not be required, to lead to a suitable reaction rate. In some embodiments of the invention diamines composition may include 50 to 100 percent by weight of UNOXOL® diamine, 0-30% by weight of bicyclic amine, 0-25 percent by weight of bicyclic biamino and 0-15 percent by m of the magnetic resonance bicyclic imine.

Measured indicators of physico-mechanical properties of the resulting resins to determine the effect of bicyclic impurities formed on the resin. Measured values of the properties presented in table 11. The glass transition temperature was measured using DMTA.

Samples 7 and 8 have a slightly lower glass transition temperature is about comparison with samples 5 and 6. Tensile strength at break and modulus tensile comparable for all samples, and the percentage strain at break slightly lower for sample 8. In General, achieved good material properties, regardless of bicyclic impurities.

Measured viscosity at the destruction of samples 5-9 and comparative sample 5, the results shown in figure 3. The study of the viscosity when the destruction was carried out on a transparent casting size 1/8 inch according to ASTM D5045. As you can see, the viscosity at the destruction for compositions containing UNOXOL® diamine, including bicyclic impurities greater than that of comparative sample 5 containing ACCESSORIES>.

Mainly embodiments of the invention disclosed herein can provide improved hydrolytic resistance, excellent adhesive properties, shorter curing times and lower temperature curing, good color/turbidity and good chemical resistance. In addition, embodiments of the invention disclosed herein can provide improved viscosity at destruction in comparison with standard compounds.

Isomeric mixture of 1,3 - and 1,4-bis(aminomethyl)cyclohexane can be used for curing epoxy resins at lower temperatures and to give coatings with excellent properties in comparison with others is the other aliphatic diamines and relevant forprimary hardeners, as ISOPHORONEDIAMINE or its derivatives.

Although the invention is described with a limited number of embodiments, the experts in this field, possessing knowledge of the advantages of the present invention, will see what can be implemented in other embodiments of the invention without deviating from the scope of claims of the invention, as discussed herein. Accordingly, the scope of the claims of the invention should be limited only by the attached claims.

1. The composition of the hardener of epoxy resins containing
(a) 1,3-bis(aminomethyl)cyclohexane and
(b) 1,4-bis(aminomethyl)cyclohexane.

2. The hardener composition according to claim 1, containing CIS - and TRANS-isomers of at least one component (a) and component (b).

3. The hardener composition according to claim 1 or 2, containing CIS - and TRANS-isomers of both components (a) and (b).

4. The hardener composition according to claim 1 or 2, containing at least 5 wt.% component (b) calculated on the total weight of the component (a) and component (b).

5. The hardener composition according to claim 1 or 2, containing approximately 50 wt.% component (b) calculated on the total weight of the component (a) and component (b).

6. The hardener composition according to claim 2, containing
from 1 to 97 wt.% CIS-1,3-bis(aminomethyl)cyclohexane;
from 1 to 97 wt.% TRANS 1,3-bis(aminomethyl)cyclohexane;
from 1 to 97 wt.% CIS 1,4-bis(aminomethyl)C is clohexane and from 1 to 97 wt.% TRANS-1,4-bis(aminomethyl)cyclohexane;
where the above percentages calculated on the total weight of CIS-1,3-bis(aminomethyl)cyclohexane, TRANS-1,3-bis(aminomethyl)cyclohexane, CIS-1,4-bis(aminomethyl)cyclohexane and TRANS-1,4-bis(aminomethyl)cyclohexane.

7. The hardener composition according to claim 1, where the curing agent comprises 50-100 wt.% a mixture of (a) and (b), from 0 to 30 wt.% bicyclic amine, from 0 to 25 wt.% bicyclic diamine and from 0 to about 15 wt.% bicyclic imine.

8. The hardener composition according to claim 1 or 2, containing 50 to 100 wt.% a mixture of (a) and (b) and at least one of the following three bicyclic compounds: (i) from greater than 0 to about 30 wt.% bicyclic amine, (ii) from greater than 0 to about 25 wt.% bicyclic diamine and (iii) from greater than 0 to about 15 wt.% bicyclic imine.

9. Composition formalising hardener for epoxy resins containing the product of the interaction of the epoxide and hardener compositions according to any one of claims 1 to 8.

10. Curing a composition containing a hardener composition according to any one of claims 1 to 8, and epoxy resin.

11. Curing the composition containing the composition formalising hardener according to claim 9 and epoxy resin.

12. Method of bonding two substrates comprising the epoxy resin and the hardener composition according to any one of claims 1 to 8 on one or both of the substrates and bringing the substrates into contact.

13. the procedure indicated in paragraph 12, additionally comprising curing the epoxy resin at a temperature and for a time sufficient to cure the epoxy resin.

14. The method according to item 13, where the curing temperature is a value between approximately -20°C-100°C.

15. The method according to item 13, where the curing time is less than 24 hours

16. Method of coating a substrate comprising applying the composition for coating on a substrate, where the composition for coating includes epoxy resin and the hardener composition according to any one of claims 1 to 8.

17. Method of coating a substrate comprising applying the composition for coating on a substrate, where the composition for coating includes epoxy resin and the composition formalising hardener according to claim 9.

18. Aqueous epoxy resin or dispersion of epoxy resin containing a hardener composition according to any one of claims 1 to 8, and epoxy resin.

19. A method of obtaining a composition formalising hardener, including the interaction of components (a) and (b) with the epoxide, where the components (a) and (b) defined in claim 1.