Phenalamine epoxy curing agent from methylene-bridged poly(cyclohexyl-aromatic)amine and epoxy resin composition containing the same

Abstract

To provide a phenalkamine curing agent composition having enhanced low temperature surface appearance, improved chemical resistance, and improved coating performance, a new structural class of phenalkamine as a curing agent used for the curing agent composition, a method of making the phenalkamine, and a method of making the composition.SOLUTION: The phenalkamine curing agent compositions of the present invention can be prepared by reacting cardanol with an aldehyde compound and a mixture of methylene bridged poly(cycloaliphatic-aromatic)amines. These curing-agent compositions may be used to cure, harden, and / or crosslink an epoxy resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a new type of phenalkamine, a phenalkamine curing agent composition, a method for producing such a phenalkamine, and a method for producing such a composition. The phenalkamine curing agent composition of the present invention can be produced by reacting cardanol with a mixture of an aldehyde compound and a methylene-bridged poly(cycloaliphatic-aromatic)amine. These curing agent compositions can be used to cure and / or crosslink epoxy resins.

Background Art

[0002] The Mannich reaction is based on the reaction of an aldehyde, such as formaldehyde, a phenolic compound, and an amine. Various forms of phenolic compounds, amines, and aldehydes are utilized in this reaction. These Mannich base products are particularly suitable for curing epoxy resins.

[0003] Phenalkamine curing agents are a type of Mannich base obtained by reacting cardanol, i.e., the phenolic extract of cashew nut shell liquid, an aldehyde compound, such as formaldehyde, and an amine. Generally, the Mannich base is produced from the reaction of 1 molar equivalent of cardanol with 1 - 2 molar equivalents of aliphatic polyethylene polyamine and 1 - 2 molar equivalents of formaldehyde at 80 - 100 °C. Aromatic polyamines are also suitable for this reaction.

[0004] Commercially available phenalkamines, NC 541 and NC 540 available from Cardolite Inc. and Sunmide CX105 available from Evonik Corp., use ethylenediamine and diethylenetriamine as their amine sources. The Sunmide 1151 phenalkamine available from Evonik Corp. utilizes m-xylenediamine as its amine raw material.

[0005] Phenalkamines are good epoxy resin curing agents for room temperature or low temperature curing applications. Moreover, they offer good chemical resistance, excellent water resistance, good compatibility with epoxy resins, low toxicity and good flexibility. As a result, they are used in marine, industrial maintenance and civil engineering applications.

[0006] British Patent No. 1529740 (GB 1,529,740) describes phenalkamines as a mixture of cardanol with poly(aminoalkylene) substituted phenols (the following structure) produced from polyethylene polyamine and formaldehyde. Generally, easy control of the molecular weight distribution of these products is not possible, and thus they are usually viscous liquids. [Chemical formula] R is a hydrocarbyl substituent having 15 carbon atoms, X = 1 - 5, n = 1 - 3, and R' = H.

[0007] U.S. Patent No. 6262148 (US 6,262,148 B1) describes compositions of phenalkamines having aromatic or alicyclic rings. These compositions were produced from cardanol with aldehydes and alicyclic or aromatic polyamines. International Publication No. 2009 / 080209 (WO 2009 / 080209 A1) describes the production of epoxy curing agents containing phenalkamines blended with polyamine salts. These curing agents were used to increase the curing rate of epoxy resins. [Prior Art Documents] [Patent Documents]

[0008] [Patent Document 1] British Patent No. 1529740 [Patent Document 2] U.S. Patent No. 6262148 [Patent Document 3] International Publication No. 2009 / 080209

Summary of the Invention

Problems to be Solved by the Invention

[0009] The problem of the present invention is to provide a new type of structure of phenalkamine, a phenalkamine curing agent composition, a method for producing such a phenalkamine, and a method for producing such a composition.

Means for Solving the Problems

[0010] The present invention relates to phenalkamines obtained using a mixture of methylene-bridged poly(cycloaliphatic-aromatic) amines (sometimes referred to as "MPCA") as an amine source. Accordingly, the present disclosure discloses a new type of structure of phenalkamines, curing agent compositions, a method for producing such phenalkamines, and a method for producing such compositions. These curing agent compositions can be used to cure and / or crosslink epoxy resins. Moreover, these phenalkamine curing agents of the present invention can provide dry curing of epoxy coatings within <8 h at ambient temperature (23 °C) or within <16 h at 5 °C, and provide improved coating performance as demonstrated by an enhanced low-temperature surface appearance and an improvement in chemical resistance. This combination of properties anticipates further utilization of MPCA-based phenalkamines as curing agents for cryogenic tank linings where improved chemical resistance is required for the transport and storage of chemicals in the oil and gas fields.

[0011] The MPCA-based phenalkamine of the present invention has the advantage of providing a faster amine-epoxy reaction rate compared to the state-of-the-art phenalkamines. This unique property offers the advantages of a lower tendency to carbamate and a shorter time to dry the coating compared to conventional phenalkamine products derived from alkylene amines such as ethylenediamine. Moreover, coating compositions based on the MPCA phenalkamine hardener of the present invention exhibit extremely good chemical resistance to a range of chemical reagents including alcohols (ethanol, methanol), xylenes, ketones (methyl isobutyl ketone), caustic soda, and sulfuric acid, and in this regard are superior to coatings produced from phenalkamines derived from ethylenediamine.

[0012] In the production of the MPCA mixture, a condensation product of aniline or toluidine and formaldehyde, containing a substantial amount of oligomers, is subjected to a catalytic hydrogenation process. The more volatile hydrogenation and partial hydrogenation products are separated by distillation, and the heavier component (MPCA) or bottoms of the original mixture are thereby obtained. MPCA is represented by the following chemical structure:

Chemical formula

Chemical formula

[0013] The present invention relates to a phenolicamine mixture obtained by reacting cardanol (structure according to formula III below) with MPCA (structure according to formula II above) and an aldehyde to obtain a composition represented by the structure according to formula IV below. While formula IV represents the composition of the aldehyde and cardanol with one amino group of MPCA, the other amino groups of MPCA can react in a similar manner to produce a mixture of amine-substituted products.

Chemical formula

Chemical formula

[0014] The present disclosure also provides a curing agent composition comprising the phenolicamine mixture of formula (IV).

[0015] A preferred curing agent composition of the present disclosure has an amine hydrogen equivalent (AHEW) of about 50 to about 500 based on 100% solids. In another aspect, the present disclosure provides an amine-epoxy composition and a cured product produced therefrom. For example, an amine-epoxy composition according to the present disclosure contains a novel phenolicamine composition containing at least one cardanol group and having at least two active amine hydrogen atoms, and an epoxy composition containing at least one polyfunctional epoxy resin, and comprises a curing agent composition.

[0016] The present disclosure also provides the use of a hardener composition comprising a phenalkamine mixture of formula (IV) as a hardener for epoxy resins. Manufactured articles produced from the amine-epoxy compositions disclosed herein include, but are not limited to, adhesives, coatings, primers, sealants, curable compounds, construction products, flooring products, and composite products. Further, such coatings, primers, sealants, or curable compounds may be applied to metallic or cementitious substrates. The mix of hardener and epoxy resin often does not require a "cure time" to obtain a contact product with high gloss and clarity. The cure time or pot life is defined as the time from when the epoxy resin is mixed with the amine until the product is applied to the intended substrate. The time can also be defined as the time required for the mix to become clear.

[0017] Detailed Description of the Invention The novel phenalkamine mixture of the present invention can be produced by reacting cardanol with an aldehyde compound and MPCA to produce a composition represented by the following structure of formula (IV):

Chemical formula

Chemical formula

[0018] In a preferred embodiment, the phenalamine mixture is represented by a structure according to the following formula (V): [Chemical formula] where n = 0, 2, 4, or 6; R is independently selected from H and CH3; [Chemical formula] are independently selected from cyclohexyl and phenyl; A is independently selected from CH2 and NH; B is independently selected from H, OH, and NH2; R′ = H, C1-C 10 alkyl, Ph, a C5-C6 cycloaliphatic group, or a C5-C 10 aromatic group; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2. Preferably, R′ = H or C1 alkyl.

[0019] In another preferred embodiment, the phenalamine mixture is represented by a structure according to the following formula (VI): [Chemical formula] where n = 0, 2, 4, or 6; [Chemical formula] are independently selected from cyclohexyl and phenyl; A is independently selected from CH2 and NH; B is independently selected from H, OH, and NH2; R′ = H, C1-C 10 alkyl, Ph, a C5-C6 cycloaliphatic group, or a C5-C 10 aromatic group; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2. Preferably, R′ = H or C1 alkyl.

[0020] Preferably, the phenalamine mixture comprises at least one phenalamine selected from the following group: [Chemistry] Here, n = 0, 2, 4, or 6; and R′ = H, C1-C 10 alkyl, Ph, C5-C6 cycloaliphatic group, or C5-C 10 aromatic group. In a preferred embodiment, the phenalamine mixture contains each of the six phenalamines listed in the above group. Preferably, in the curing agent composition containing a phenalamine mixture containing six phenalamines from the phenalamines of formulas (VII), (VIII), (IX), (X), (XI), and (XII), the phenalamine is present in the mixture as follows: 3-9% by mass of the phenalamine of formula (VII), 3-11% by mass of the phenalamine of formula (VIII), 30-45% by mass of the phenalamine of formula (IX), 10-17% by mass of the phenalamine of formula (X), 5-10% by mass of the phenalamine of formula (XI), and 15-30% by mass of the phenalamine of formula (XII). Preferably, R′ = H or C1 alkyl.

[0021] The present disclosure also provides a curing agent composition containing a phenalamine mixture of any of formulas (IV), (V), or (VI). In a preferred embodiment, the curing agent composition contains a phenalamine mixture containing at least one phenalamine of formulas (VII), (VIII), (IX), (X), (XI), or (XII). In another preferred embodiment, the curing agent composition contains a phenalamine mixture containing six phenalamines from the phenalamines of formulas (VII), (VIII), (IX), (X), (XI), and (XII).

[0022] In a preferred embodiment, the curing agent composition may further include a further amine having at least two amine functional groups. The phenalamine curing agent of the present invention may be used to cure an epoxy resin in combination with a further amine curing agent (as a co-curing agent).

[0023] Preferred examples of further amines having at least two amine functional groups are diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexamethylenediamine (HMDA), 1,3 - pentanediamine (DYTEK (商標) EP), 2 - methyl - 1,5 - pentanediamine (DYTEK (商標)A), triaminononane, N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N′-1,2-ethanediylbis-1,3-propanediamine (N4-amine), or dipropylenetriamine; arylaliphatic amines such as m-xylylenediamine (mXDA), or p-xylylenediamine; cycloaliphatic amines such as 1,3-bis(aminomethyl)cyclohexylamine (1,3-BAC), isophoronediamine (IPDA), 4,4′-methylenebiscyclohexaneamine, 1,2-diaminocyclohexylamine (DCHA), aminopropylcyclohexylamine (APCHA), methylene-bridged poly(cycloaliphatic-aromatic) amines such as MPCA, aromatic amines such as m-phenylenediamine, diaminodiphenylmethane (DDM), or diaminodiphenylsulfone (DDS); heterocyclic amines such as N-aminoethylpiperazine (NAEP), or 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro(5,5)undecane;Polyalkoxyamines [wherein the alkoxy group may be oxyethylene, oxypropylene, oxy-1,2-butylene, oxy-1,4-butylene or a copolymer thereof], for example 4,7-dioxadecane-1,10-diamine, 1-propanamine, 3,3′-(oxybis(2,1-ethanediyl-oxy))bis(diaminopropylated diethylene glycol) (ANCAMINE 1922A), poly(oxy(methyl-1,2-ethanediyl)), α-(2-aminomethylethyl)-ω-(2-aminomethylethoxy) (JEFFAMINE D 230, D-400), triethylene glycol diamine and oligomers (JEFFAMINE XTJ-504, JEFFAMINE XTJ-512), poly(oxy(methyl-1,2-ethanediyl)), α,α′-(oxydi-2,1-ethanediyl)bis(ω-(aminomethylethoxy)) (JEFFAMINE XTJ-511), bis(3-aminopropyl)polytetrahydrofuran 350, bis(3-aminopropyl)polytetrahydrofuran 750, poly(oxy(methyl-1,2-ethanediyl)), α-hydro-ω-(2-aminomethylethoxy) ether and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1) (JEFFAMINE T-403), and diaminopropyldiaminopropyldipropylene glycol are included.;

[0024] Other additional amines having at least two amine functional groups include amidoamines and polyamide curing agents. Polyamide curing agents are composed of the reaction product of dimerized fatty acids (dimer acids) and polyethylene amines, and usually a certain amount of monomeric fatty acids that help control the molecular weight and viscosity. "Dimerized" or "dimer" or "polymerized" fatty acids refer to polymerized acids obtained from unsaturated fatty acids. Ordinary monofunctional unsaturated C-6 to C-20 fatty acids, which are also used in the production of polyamides, include tall oil fatty acids (TOFA), soybean fatty acids, and the like.

[0025] Other additional amines having at least two amine functional groups include phenalkamines and Mannich bases of phenolic compounds with amines and formaldehyde. The present disclosure also provides amine-epoxy compositions and cured products produced therefrom. The latter are (a) A curing agent composition comprising a Mannich base (phenalkamine) derived from MPCA of cardanol shown below:

Chemical formula

Chemical formula

[0026] The present disclosure also provides the use of a curing agent composition comprising a phenalkamine mixture of any of formulas (IV), (V), or (VI) as a curing agent for an epoxy resin. The present disclosure also provides the use of a curing agent composition comprising a phenalkamine mixture comprising at least one phenalkamine of formulas (VII), (VIII), (IX), (X), (XI), or (XII) as a curing agent for an epoxy resin. In a preferred embodiment, the curing agent composition comprises a phenalkamine mixture comprising at least six phenalkamines from the phenalkamines of formulas (VII), (VIII), (IX), (X), (XI), and (XII).

[0027] The amine-epoxy composition of the present disclosure includes a curing agent composition and an epoxy composition containing at least one polyfunctional epoxy resin. As used herein, a polyfunctional epoxy resin describes a compound containing two or more 1,2-epoxy groups per molecule. The epoxy resin is preferably selected from the group consisting of aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, glycidyl ester resins, thioglycidyl ether resins, N-glycidyl ether resins, and combinations thereof.

[0028] Preferred aromatic epoxy resins suitable for use in the present disclosure include glycidyl ethers of polyhydric phenols, including glycidyl ethers of dihydric phenols. More preferred are glycidyl ethers such as resorcinol, hydroquinone, bis-(4-hydroxy-3,5-difluorophenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 2,2-bis-(4-hydroxy-3-methylphenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis-(4-hydroxyphenyl)-propane (commercially known as bisphenol A), bis-(4-hydroxyphenyl)-methane (commercially known as bisphenol F and may contain various amounts of 2-hydroxyphenyl isomers), or any combination thereof. Additionally, advanced method dihydric phenols of the following structures are also useful in the present disclosure:

Chemical formula

[0029] In one aspect of the present disclosure, the at least one polyfunctional epoxy resin is preferably diglycidyl ether of bisphenol A (DGEBA), an advanced form of DGEBA or a higher molecular weight variant, diglycidyl ether of bisphenol F, diglycidyl ether of a novolak resin, or any combination thereof. The higher molecular weight variant or derivative of DGEBA is produced by the advanced method, where excess DGEBA reacts with bisphenol A to yield a product having epoxy as the end group. The epoxy equivalent weight (EEW) of such products ranges from about 450 to about 3000 or more. Since these products are solids at room temperature, they are often referred to as solid epoxy resins.

[0030] In a preferred embodiment, the at least one polyfunctional epoxy resin is a diglycidyl ether of bisphenol F or bisphenol A represented by the following structure:

Chemical formula

[0031] Examples of alicyclic epoxy compounds include, but are not limited to, polyglycidyl ethers of polyols having at least one alicyclic ring, or compounds containing cyclohexene oxide or cyclopentene oxide obtained by epoxidizing compounds containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent. Some specific examples are hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate; 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate; bis(3,4-epoxycyclohexylmethyl) adipate; methylene-bis(3,4-epoxycyclohexane); 2,2-bis(3,4-epoxycyclohexyl) propane; dicyclopentadiene diepoxide; ethylene-bis(3,4-epoxycyclohexane carboxylate); dioctyl epoxyhexahydrophthalate; and di-2-ethylhexyl epoxyhexahydrophthalate, but are not limited thereto.

[0032] Examples of aliphatic epoxy compounds include, but are not limited to, polyglycidyl ethers of aliphatic polyols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, and copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers. Some specific examples include glycidyl ethers of polyols, such as 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; triglycidyl ether of glycerin; triglycidyl ether of trimethylolpropane; tetraglycidyl ether of sorbitol; hexaglycidyl ether of dipentaerythritol; diglycidyl ether of polyethylene glycol; and diglycidyl ether of polypropylene glycol; and polyglycidyl ethers of polyether polyols obtained by adding one type, or two or more types, of alkylene oxide to aliphatic polyols such as ethylene glycol, propylene glycol, trimethylolpropane, and glycerin, but are not limited thereto.

[0033] Glycidyl ester resins are obtained by reacting a polycarboxylic acid compound having at least two carboxylic acid groups in the molecule with epichlorohydrin. Examples of such polycarboxylic acids include aliphatic, cycloaliphatic, and aromatic polycarboxylic acids. Examples of aliphatic polycarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid, or dimerized or trimerized linoleic acid. Cycloaliphatic polycarboxylic acids include tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid, and aromatic polycarboxylic acids include phthalic acid, isophthalic acid or terephthalic acid.

[0034] The thiodiglycidyl ether resin is derived from a dithiol, for example, ethan-1,2-dithiol or bis(4-mercaptomethylphenyl) ether.

[0035] The N-glycidyl resin is obtained by dehydrochlorination of the reaction product of epichlorohydrin and an amine containing at least two amine hydrogen atoms. Such amines are, for example, aniline, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine or bis(4-methylaminophenyl)methane. However, the N-glycidyl resin also includes triglycidyl isocyanurate, cycloalkylene ureas, for example, the N,N'-diglycidyl derivatives of ethylene urea or 1,3-propylene urea, and the diglycidyl derivatives of hydantoins, for example, 5,5-dimethylhydantoin.

[0036] For one or more of these embodiments, the resin component further includes a reactive diluent. A reactive diluent is a compound that participates in a chemical reaction with the curing agent component during the curing process and becomes incorporated into the cured composition, and is preferably a monofunctional epoxide. The reactive diluent may be used to change the viscosity and / or curing characteristics of the curable composition for various applications. For some applications, the reactive diluent can impart a lower viscosity to the curable composition, affecting flow characteristics, extending pot life, and / or improving adhesion characteristics. For example, the viscosity may be reduced to allow an increase in the level of pigment in the formulation or composition while still allowing for easy application, or to allow the use of higher molecular weight epoxy resins. Thus, it is within the scope of the present disclosure for an epoxy component containing at least one polyfunctional epoxy resin to further contain a monofunctional epoxide. Examples of monoepoxides include, but are not limited to, styrene oxide, cyclohexene oxide, and glycidyl ethers of phenol, cresols, tert-butylphenol, other alkylphenols, butanol, 2-ethylhexanol, C4 - C14 alcohols, or combinations thereof. The polyfunctional epoxy resin may be present in solution or emulsion, in which case the diluent is water, an organic solvent, or a mixture thereof. The amount of the polyfunctional epoxy resin may range from about 50% to 100% by weight, about 50% to about 90% by weight, about 60% to about 90% by weight, about 70% to about 90% by weight, and in some cases from about 80% to about 90% by weight of the epoxy component. For one or more of these embodiments, the reactive diluent is less than 60% by weight of the total mass of the resin component.

[0037] Particularly suitable polyfunctional epoxy compounds are the diglycidyl ethers of bisphenol A and bisphenol F, the advanced diglycidyl ethers of bisphenol A and bisphenol F, and epoxy novolac resins. The epoxy resin may be the sole resin or a mixture of mutually compatible epoxy resins.

[0038] The amine-epoxy composition of the present disclosure preferably has a stoichiometric ratio of epoxy groups in the epoxy composition to amine hydrogens in the curing agent composition in the range of 1.5:1 to 0.7:1. For example, such an amine-epoxy composition may preferably have a stoichiometric ratio of 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 0.9:1, 0.8:1, or 0.7:1. In another aspect, the stoichiometric ratio is in the range of 1.3:1 to 0.7:1, or 1.2:1 to 0.8:1, or 1.1:1 to 0.9:1.

[0039] The combined cardanol MPCA-derived Mannich base (phenalamine) and amine co-curing agent-epoxy composition of the present disclosure preferably has a stoichiometric ratio of epoxy groups in the epoxy composition to amine hydrogens in the curing agent composition in the range of 1.5:1 to 0.7:1. For example, such an amine-epoxy composition may have a stoichiometric ratio of 1.5:1, 1.4:1, 1.3:1, 1.2:1, 1.1:1, 1:1, 0.9:1, 0.8:1, or 0.7:1. In another aspect, the stoichiometric ratio is in the range of 1.3:1 to 0.7:1, or 1.2:1 to 0.8:1, or 1.1:1 to 0.9:1.

[0040] Preferably, the mass ratio of the Mannich base (phenalamine) derived from MPCA of cardanol and the amine co-curing agent is from about 1:1 to about 1:0.05. In another embodiment, preferably, the mass ratio of the Mannich base (phenalamine) derived from MPCA of cardanol and the amine co-curing agent is from about 1:0.75 to about 1:0.25.

[0041] The present disclosure also relates to a method for producing a phenalamine mixture represented by any of formula (IV), (V), or (VI), (i) cardanol represented by the formula [Chemical formula] [wherein n = 0, 2, 4, or 6]; (ii) the formula [Chemical formula] [wherein, R is independently selected from H and CH3; [Chemical formula] are independently selected from cyclohexyl and phenyl; A is independently selected from CH2 and NH; B is independently selected from H, OH, and NH2; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2] MPCA represented by; and (iii) reacting an aldehyde.

[0042] In a preferred embodiment of the present method, the molar ratio of cardanol to MPCA is in the range of 1:1 to 1:3. In another embodiment, preferably, the molar ratio of cardanol to MPCA is in the range of 1:1 to 1:2. Preferably, the molar ratio of MPCA to aldehyde is in the range of 1:1 to 1:3. In another embodiment, preferably, the molar ratio of MPCA to aldehyde is in the range of 1:1 to 1:1.2.

[0043] In a preferred embodiment of the present method, the reaction can be carried out in a one-step process by mixing the cardanol with the amine and treating this mixture with formaldehyde at the desired reaction temperature. Alternatively, in another preferred embodiment of the present method, the cardanol may preferably be mixed with the aldehyde and treated with the MPCA at the reaction temperature. The reaction may be carried out at 40°C to 150°C. In another preferred embodiment, the reaction may be carried out at 80°C to 120°C. The product is preferably obtained by distillation of water after the reaction is complete.

[0044] In a preferred embodiment of the present method, the aldehyde compound used is represented by the structural formula RCOH, where R = H, C1 - C 10 alkyl, Ph, C5 - C6 cycloaliphatic group, C5 - C 10It is an aromatic group or a mixture thereof. Preferred aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, benzaldehyde, cyclopentanecarboxaldehyde, and cyclohexanecarboxaldehyde. The most preferred aldehydes are formaldehyde and acetaldehyde. Formaldehyde can be used as an aqueous solution or paraformaldehyde in its polymeric form.

[0045] The molar ratio of cardanol to MPCA and the aldehyde determines the degree of reaction of the amino substituents in MPCA. A mixture of amino substituents is predicted. The ratio of more highly substituted (>1) amine substituents on cardanol increases when the molar ratio of the amino group to cardanol is >1.0, assuming an equimolar ratio of the amino group to the aldehyde.

[0046] The present disclosure also relates to a method for manufacturing a curing agent composition, which includes the step of combining a phenalamine of any of formula (IV), (V), or (VI) and a further amine having at least two amine functional groups.

[0047] The compositions of the present disclosure may be used to manufacture a variety of cured manufactured articles. Depending on the requirements during the manufacture of the article or the requirements for the end-use application of the article, various additives may be used in the formulation and composition to manufacture to specific properties. These additives include, but are not limited to, solvents (including water), accelerators, plasticizers, fillers, fibers such as glass fibers or carbon fibers, pigments, pigment dispersants, rheology modifiers, thixotropic agents, flow or leveling aids, surfactants, defoamers, biocides, or any combination thereof. Other mixtures or materials known in the art may be included in the composition or formulation and are understood to be within the scope of the present disclosure.

[0048] The present disclosure also relates to the use of the compositions of the present invention for manufacturing cured manufactured articles. For example, the article may comprise an amine-epoxy composition comprising a curing agent composition and an epoxy composition. The curing agent composition may comprise a Mannich base (phenalkamine) derived from MPCA of cardanol. The epoxy composition may comprise at least one polyfunctional epoxy resin. Optionally, various additives may be present in the composition or formulation used to manufacture the article to be post-processed, depending on the desired properties. These additives may include, but are not limited to, solvents (including water), accelerators, plasticizers, fillers, fibers such as glass or carbon fibers, pigments, pigment dispersants, rheology modifiers, thixotropic agents, flow or leveling aids, surfactants, defoamers, biocides, or any combination thereof. The selection and amount of these additives are at the discretion of the formulator. Representative accelerators that may be used but are not essential include: boron trifluoride amine complexes, substituted phenols such as 2,4,6-tri(dimethylaminomethyl)phenol, tertiary amines such as benzyldimethylamine and imidazoles.

[0049] Preferred articles according to the present disclosure include, but are not limited to, coatings, adhesives, primers, sealants, curable compounds, construction products, flooring products, composite products, laminates, potting compounds, grouts, fillers, cementitious grouts, or self-leveling flooring. Coatings based on these amine-epoxy compositions may contain diluents, such as water or organic solvents, as required for particular applications. The coatings may contain various types and levels of pigments for use in paint and primer applications. The amine-epoxy coating composition includes a layer having a thickness in the range of 40 to 400 μm (micrometers), preferably 80 to 300 μm, more preferably 100 to 250 μm, for use in protective coatings applied to metal substrates. Moreover, for use in flooring products or construction products, the coating composition includes a layer having a thickness in the range of 50 to 10,000 μm, depending on the type of product and the desired final properties. Coating products that provide limited mechanical resistance and chemical resistance include a layer having a thickness in the range of 50 to 500 μm, preferably 100 to 300 μm, whereas coating products that provide high mechanical resistance and chemical resistance, such as self-leveling floors, include a layer having a thickness in the range of 1000 to 10,000 μm, preferably 1500 to 5000 μm.

[0050] Additional components or additives may be used in conjunction with the compositions of the present disclosure to manufacture articles. Further, such coatings, primers, sealants, curable compounds or grouts may be applied to metal or cementitious substrates.

[0051] The relative amount selected for the epoxy composition relative to the relative amount of the hardener composition can vary, for example, depending on the end-use article, its desired properties, and the secondary processing methods and conditions used to manufacture the end-use article. For example, in coating applications, using a certain amine-epoxy composition and incorporating more epoxy resin relative to the amount of the hardener composition can result in a coating with an increased drying time, but with an improved appearance as measured by increased hardness and gloss.

[0052] A variety of substrates are suitable for the application of the coatings of the present invention with appropriate surface preparation, as is well known to those skilled in the art. Such substrates include, but are not limited to, concrete and various types of metals and alloys, such as steel and aluminum. The coatings of the present disclosure are suitable for coating or covering large metal objects or cementitious substrates, including ships, bridges, industrial plants and equipment, and floors.

[0053] The coatings of the present invention may be applied by a fairly large number of techniques, including spray, brush, roller, paint mitt, etc. For applying the very high solids or 100% solids coatings of the present invention, a multi-component spray application apparatus may be used, in which the amine and epoxy components are mixed by being led together in a line leading to the spray gun, within the spray gun itself, or by mixing the two components together as they leave the spray gun. Using this technique can alleviate limitations regarding the pot life of the formulation, which typically decreases while both the amine reactivity and the solids content increase. A multi-component apparatus that is heated may be used to lower the viscosity of the components, thereby improving the ease of application.

[0054] Construction and flooring applications include compositions comprising the amine-epoxy compositions of the present disclosure in combination with concrete or other materials commonly used in the construction industry. Uses of the compositions of the present disclosure include, but are not limited to, their use as primers, deep penetration primers, coatings, curable compounds, and / or sealants for new and old concrete, as referenced in ASTM C309-97, which is incorporated herein by reference. As a primer or sealant, the amine-epoxy compositions of the present disclosure can be applied to a surface to improve adhesion prior to the application of a coating. Since this relates to the application of concrete and cementitious materials, a coating is an agent used for application on a surface to produce a protective or decorative layer or coat. Crack injection and crack filling products may be manufactured from the compositions disclosed herein. The amine-epoxy compositions of the present disclosure can be mixed with cementitious materials, such as concrete mixes, to form polymer cement or modified cement, tile grout, and the like. Non-limiting examples of composite products or articles comprising the amine-epoxy compositions disclosed herein include tennis rackets, skis, bike frames, airplane wings, fiberglass reinforced composites, and other molded articles.

[0055] In a particular use of the hardener compositions of the present disclosure, coatings can be applied at low temperatures with a fast curing rate and good coating appearance to a variety of substrates, such as concrete and metal surfaces. This is particularly important for topcoat applications where a good aesthetic is desired and provides a solution to a long-standing challenge in the industry of overcoming low temperature fast curing with a good coating appearance. With a fast low temperature curing rate, the downtime of a service or apparatus can be reduced, or for outdoor applications, the working season can be extended in cold climates.

[0056] Epoxy fast curing agents enable amine-cured epoxy coatings to cure to a high degree of cure within a short period of time. The curing rate of the coating is monitored by the Thin Film Set Time (TFST), which measures the period during which the coating dries. The TFST is classified into four stages: Phase 1, touch dry; Phase 2, tack dry; Phase 3, dry to touch; and Phase 4, fully cured dry. The dry time of Phase 3 indicates how quickly the coating cures and dries. For ambient temperature fast curing coatings, the dry time of Phase 3 is less than 6 hours, or preferably less than 4 hours, or less than 4 hours. Low temperature curing typically refers to a curing temperature below ambient temperature, 10°C or 5°C, or in some cases 0°C. For low temperature fast curing, the dry time of Phase 3 at 5°C is less than 16 hours, at which point significant productivity benefits are provided at values where the dry time of Phase 3 is less than 10 hours and preferably less than 8 hours.

[0057] How well the coating cures is measured by its degree of cure. The degree of cure is often determined by using DSC (Differential Scanning Calorimetry) techniques well known to those skilled in the art. A fully cured coating has a degree of cure at ambient temperature (25°C) of at least 85%, or at least 90%, or at least 95% after 7 days. A fully cured coating has a degree of cure at 5°C of at least 80%, or at least 85%, or at least 90% after 7 days.

[0058] Many of these low temperature epoxy fast curing agents can cure epoxy resins quickly. However, due to the poor compatibility of the epoxy resin and curing agent, especially at low temperatures of 10°C or 5°C, there is phase separation between the resin and the curing agent and migration of the curing agent to the coating surface, resulting in a poor coating appearance manifested as a sticky and cloudy coating. Good compatibility between the epoxy resin and the curing agent results in a clear and glossy coating with good carbamation resistance and good coating appearance. The curing agent composition of the present disclosure provides a combination of fast curing rate, good compatibility, and high degree of cure.

Examples

[0059] These examples are provided to demonstrate some aspects of the present invention and are not intended to limit the scope set forth in the claims appended hereto.

[0060] Example 1: Synthesis of phenalamine of MPCA having a molar ratio of cardanol:MPCA:formaldehyde (1:1:1) Cardanol (298 g, 1.0 mol) and MPCA (350 g, 1.0 mol) were charged into a three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe. The mixture was heated to 80 °C. A 37% solution of formaldehyde (81 g, 37 mass%, 30 g, 1.0 mol) was added to maintain a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled off at 120 °C, and the product was obtained as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (34.7 g) and benzyl alcohol (173 g). The resulting product had a viscosity of 5710 mPa·s at 23 °C and a theoretical AHEW of 150 g / eq.

[0061] Example 2: Synthesis of phenalamine of MPCA having a molar ratio of cardanol:MPCA:formaldehyde (1:1.5:1.0) Cardanol (298 g, 1.0 mol) and MPCA (525 g, 1.50 mol) were charged into a three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe. The mixture was heated to 80 °C. A 37% solution of formaldehyde (81 g, 37 mass%, 30 g, 1.0 mol) was added to maintain a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled off at 120 °C, and the product was obtained as a light brown liquid. This product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (43.95 g) and benzyl alcohol (219.74 g). The resulting product had a viscosity of 6290 mPa·s at 23 °C and a theoretical AHEW of 154 g / eq.

[0062] Example 3: Synthesis of phenalamine of MPCA having a molar ratio of cardanol:MPCA:formaldehyde (1:1.5:1.25) A three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe was charged with cardanol (298 g, 1.0 mol) and MPCA (525 g, 1.50 mol). The mixture was heated to 80 °C. A 37% solution of formaldehyde (101.35 g, 37 mass%, 37.5 g, 1.25 mol) was added to maintain a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled at 120 °C, and the product was obtained as a light brown liquid. The product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (44.10 g) and benzyl alcohol (220.5 g). The resulting product had a viscosity of 10970 mPa·s at 23 °C and a theoretical AHEW of 182 g / eq.

[0063] Example 4: Synthesis of phenalamine of MPCA having a molar ratio of cardanol:MPCA:aminopropylcyclohexylamine:formaldehyde (1:0:0.8:0.2:1.0) A three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe was charged with cardanol (298 g, 1.0 mol), MPCA (280 g, 0.8 mol), and aminopropylcyclohexylamine (31.25 g, 0.2 mol). The mixture was heated to 80 °C. A 37% solution of formaldehyde (81 g, 37 mass%, 30 g, 1.0 mol) was added to maintain a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled at 120 °C, and the product was obtained as a light brown liquid. The product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (32.7 g) and benzyl alcohol (163.6 g). The resulting product had a viscosity of 2440 mPa·s at 23 °C and a theoretical AHEW of 233 g / eq.

[0064] Example 5: Synthesis of phenolic amine of MPCA having a molar ratio of cardanol:MPCA:aminopropylcyclohexylamine:formaldehyde (1:0:1.2:0.3:1.0) A three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe was charged with cardanol (298 g, 1.0 mol), MPCA (420 g, 1.2 mol), and aminopropylcyclohexylamine (46.88 g, 0.3 mol). The mixture was heated to 80 °C. A 37% solution of formaldehyde (81 g, 37 mass%, 30 g, 1.0 mol) was added while maintaining a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled off at 120 °C, and the product was obtained as a light brown liquid. The product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (40.9 g) and benzyl alcohol (204.5 g). The resulting product had a viscosity of 2250 mPa·s at 23 °C and a theoretical AHEW of 230 g / eq.

[0065] Example 6: Synthesis of phenolic amine of MPCA having a molar ratio of cardanol:MPCA:triaminononane:formaldehyde (1:0:0.65:0.65:1.3) A three-necked 1 L round-bottom flask equipped with an N2 inlet, a dropping funnel, and a temperature probe was charged with cardanol (298 g, 1.0 mol), MPCA (227.5 g, 0.65 mol), and triaminononane (112.65 g, 0.65 mol). The mixture was heated to 80 °C. A 37% solution of formaldehyde (105.4 g, 37 mass%, 39 g, 1.3 mol) was added while maintaining a reaction temperature of 80 - 90 °C. After the addition, the mixture was held at 90 - 95 °C for 1 h. Water was distilled off at 120 °C, and the product was obtained as a light brown liquid. The product was cooled to ambient temperature and treated with 2,4,6-tri(dimethylaminomethyl)phenol (34.41 g) and benzyl alcohol (172.03 g). The resulting product had a viscosity of 2100 mPa·s at 23 °C and a theoretical AHEW of 136 g / eq.

[0066] Performance Test Unless otherwise specified, the curing agent mixtures were prepared by mixing the ingredients given in the above examples with the epoxy component of a standard bisphenol A-based epoxy resin (Epon 828, DER 331 type) with an EEW of 190. The formulations used are defined in Table 1. They were then mixed using a stoichiometric level of 1:1 (amine:epoxy equivalent).

[0067] Table 1. Clearcoat Formulation Screening - MPCA Phenalkamine [Table 1] · For formulation [E], the EDA-based phenalkamine is the commercial product Sunmide® CX105 (from Evonik). Anchor K54 was added to the formulation to achieve the same accelerator level present in all MPCA-based formulations (formulations [A] - [D]). · Formulation [F] is an example of a blend with the co-amine fast curing agent Ancamine® 2801 (from Evonik) as in Example 1.

[0068] The formulations as defined in Table 1 were subjected to a series of application tests to determine their performance attributes. The adapted test protocol is defined in Table 2. Table 2: Test Methods [Table 2]

[0069] The gelation time characterizes the time for the composition to transition from a liquid to a gel. The gelation time of the amine-epoxy composition was measured using a TECHNE gelation timer model FGT 6 in accordance with ASTM D2471. The drying time or thin-film set time (TFST) was determined using a Beck-Koller recorder in accordance with ASTM D5895. The amine-epoxy coating was produced on a standard glass panel with an undried film thickness of 150 μm WFT (wet film thickness) using a Bird applicator, resulting in a dry film thickness of ±100 μm. The coating was cured in a Lunaire (TPS) environmental chamber at 23 °C and 5 °C and 60% relative humidity (RH). Data for all evaluated systems are reported in Table 3. Table 3. Performance Characteristics of MPCA Phenalkamine Hardeners

Table 3

[0070] Coating compositions based on the hardeners of the present invention exhibit several improved properties when cured at 23 °C and 5 °C compared to those obtained with standard commercially available EDA-based phenalkamines. These include faster thin-film drying times, hardness development, and improved low-temperature surface appearance, most notably when the coating is cured under adverse low-temperature conditions. The results are considered significant performance benefits for these types of coatings, as faster property development and improved low-temperature curing performance can provide productivity benefits in the coating markets for marine and protective coatings. Formulation [F] is an example where the performance characteristics can also be enhanced by adding a second hardener to the new MPCA phenalkamine to form a mixture. In this example, the Ancamine 2801 hardener at 5% reduces the initial hardener viscosity by ±40% as shown in Example 1 and, moreover, provides an improvement in the low-temperature cure development without adversely affecting other properties such as the water spot resistance.

[0071] At 23 °C, all coatings showed good gloss development and contained no oily amines and no surface defects. At lower application temperatures, the MPCA-based coatings maintained extremely high gloss and a surface free of oily substances, while the reference phenalkamine used in formulation [E] showed a clearcoat with a decrease in gloss and slight cloudiness, which became more pronounced when this system was applied and cured at 5 °C. The gloss and surface retention for the MPCA-phenalkamine-based formulations developed in Examples 1, 2, and 6 are excellent compared to the EDA-based controls, indicating improved compatibility for this hardener technology based on the MPCA amines. The results obtained clearly show that the coatings containing the hardener of the present invention have both rapid curing and a good coating appearance, indicating good compatibility between the hardener and the epoxy resin.

[0072] Many amine-based systems suffer from poor initial water spot resistance and are prone to carbamation. The latter occurs when free amines present on the surface of the coating react with atmospheric moisture and carbon dioxide, and the result is the formation of insoluble white salts on the coating surface. To evaluate this, a clear coating was applied using a Bird applicator to a clean Lenata chart at an undried film thickness of approximately 75 μm (undried film thickness). The Lenata chart was cleaned with ethanol before use. The coating was cured at 23 °C and 5 °C and 60% relative humidity (RH) for 1 day and 7 days. A lint-free cotton patch was placed on the test panel, ensuring that it was at least 12 mm from the edge of the panel. The cotton patch was wetted with 2 - 3 ml of deionized water and covered with a suitable lid (e.g., a watch glass). The panel was gently left for the specified time (the standard time is 24 h). After that time, the patch was removed and the coating was dried with a cloth or tissue. The panel was immediately tested and rated for carbamation. In the tests used by Evonik, a rating of 5 represents no carbamation and an excellent surface, while 0 represents excessive whitening or severe carbamation. For the water spot test, water droplets are applied to the coating in the absence of the lint-free cloth. The rating for water spot resistance is the same as for carbamation. The data summarized in Table 3 show that coatings cured with the hardener of the present invention provide improved carbamation and water spot resistance compared to the reference phenolic amine, especially when applied at a low temperature of 5 °C.

[0073] Chemical Resistance Study Several formulations based on the amine hardener were also evaluated for their basic chemical resistance properties. In this test, cured pucks (±55 mm diameter, ±10 mm thickness) with an approximate mass of 20.00 g were produced. Immersion studies according to ASTM D543 were carried out using a standard liquid bisphenol A-based (DGEBA, EEW = 190) epoxy resin cured at 23 °C for 7 days with the hardener from Example 1. Two samples were tested for each reagent. Table 4 shows the average percentage mass change after immersion in various chemicals for 7 days and 28 days at 23 °C.

[0074] Table 4: Chemical Resistance of MPCA - Phenalkamine - Continuous Immersion [Table 4] These studies show that coating compositions based on the MPCA phenalkamine hardener of the present invention exhibit very good chemical resistance over a range of chemical reagents. Most notably when compared to a standard EDA - based phenalkamine, is the excellent resistance to xylene mixtures and methyl isobutyl ketone (MIBK). In this study, pucks based on formulation [A] showed a very low level of weight gain during immersion, whereas the EDA control showed some swelling and weight gain after 28 days immersion in MIBK and xylene of 18.9% and 44.4% respectively.

[0075] Aspects of the present invention are as follows: 1. A phenalkamine mixture, of formula (IV) [Chemical formula] [wherein n = 0, 2, 4, or 6; R is independently selected from H and CH3; [Chemical formula] are independently selected from cyclohexyl and phenyl; A is independently selected from CH2 and NH; B is independently selected from H, OH, and NH2; R′ = H, C1-C 10 alkyl, Ph, a C5-C6 cycloaliphatic group, or a C5-C 10 aromatic group; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2], the phenolic amine mixture comprising at least one phenolic amine represented by the structure. 2. The at least one phenolic amine is of formula (V)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Claims

1. A phenalkamine mixture represented by formula (IV) 【Chemical 1】 [wherein, n = 0, 2, 4, or 6; R is, independently of one another, H and CH ３ selected from; 【Chemical 2】 is independently selected from cyclohexyl and phenyl; A is independently selected from CH ２ and NH; B is independently selected from H, OH, and NH ２ ; R′ = H, C １ -C １０ alkyl, Ph, C ５ -C ６ cycloaliphatic group, or C ５ -C １０ aromatic group; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2], and includes at least one phenalamine represented by the structure of The phenalkamine mixture comprises the following six phenalkamines: [Chemical Formula 3] [wherein n = 0, 2, 4, or 6; and R' = H, C1-C10 alkyl, Ph, C5-C6 cycloaliphatic group, or C5-C10 aromatic group], said phenalkamine mixture.

2. A curing agent composition comprising the phenalkamine mixture according to Claim 1.

3. The curing agent composition according to Claim 2, further comprising a further amine having at least two amine functional groups.

4. Use of the phenalkamine mixture according to Claim 1 or the curing agent composition according to Claim 2 or 3 as a curing agent for an epoxy resin.

5. A method for producing the phenalkamine mixture according to Claim 1, comprising: (i) a cardanol represented by the formula 【Chemical Formula 4】 [wherein n = 0, 2, 4, or 6]; (ii) reacting with the formula [Chemical Formula 5] [wherein, n = 0, 2, 4, or 6; R is, independently of one another, selected from H and CH ３ ; and 【Chemical Formula 6】 are independently selected from cyclohexyl and phenyl; A is independently selected from CH ２ and NH; B is independently selected from H, OH, and NH ２ ; y = 0 to 1; z = 0 to 1; and the sum of y and z is 0 to 2] represented by a methylene-bridged poly(cycloaliphatic-aromatic)amine; and (iii) an aldehyde The method comprising the step of reacting.

6. The method according to Claim 5, wherein the molar ratio of cardanol to methylene-bridged poly(cycloaliphatic-aromatic) amine is in the range of 1:1 to 1:3, and the molar ratio of methylene-bridged poly(cycloaliphatic-aromatic) amine to aldehyde is in the range of 1:1 to 1:

3.

7. The method according to Claim 5, wherein the cardanol and at least one methylene-bridged poly(cycloaliphatic-aromatic) amine are mixed at a temperature of 40 to 150 °C, and then treated with an aldehyde at a temperature of 40 to 150 °C.

8. The method according to Claim 5, wherein the cardanol and the aldehyde are mixed at a temperature of 40 to 150 °C, and then treated with at least one methylene-bridged poly(cycloaliphatic-aromatic) amine at a temperature of 40 to 150 °C.

9. The method according to Claim 5, wherein the aldehyde is selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, heptanal, octanal, nonanal, decanal, benzaldehyde, cyclopentanecarboxaldehyde, and cyclohexanecarboxaldehyde.

10. A method for producing the curing agent composition according to Claim 3, comprising combining the phenalkamine mixture of formula (IV) and a further amine having at least two amine functional groups.

11. Use for producing a cured manufactured article of the phenalkamine mixture according to claim 1 or the hardener composition according to claim 2 or 3, together with at least one epoxy resin.

12. The use according to claim 11, wherein the article is a coating, an adhesive, a construction product, a flooring product, or a composite product.

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