A solution of amines in polymer phenols combined with other resins.

Abstract

This disclosure provides latent curing accelerators and compositions containing such latent curing accelerators and a substance to be cured (e.g., epoxy resin). The latent curing accelerator comprises an amine and an encapsulant system having a polyphenol resin and at least one additional excipient. Methods for production and use are further provided.

Description

[Technical Field]

[0001] background Compositions containing epoxy resins and curing agents have been known for decades. Many curing agents react with epoxy resins at room temperature and must be mixed immediately before use. Other curing agents, known as latent hardeners, are stable at ambient temperature when mixed with epoxy resins and only harden when heated to high temperatures. Some compounds also act as latent hardeners, dicyandiamide (DICY), or acid anhydride accelerators, resulting in the hardening of epoxy resins at high temperatures. There is a need for latent epoxy hardeners or accelerators that exhibit long-term storage stability at ambient temperature and harden rapidly above 100°C.

[0002] U.S. Patents 3,519,576 and 3,520,905 describe the use of salts of monomeric polyvalent phenols and polyamines as latent curing agents for epoxy resins. These compositions rapidly cure the resin at ambient temperature. U.S. Patent 4,866,133 describes the use of solid solutions of polymeric polyvalent phenols and polyamines for curing epoxy resins. The polyamines used contain at least two amine groups, at least one of which is a primary amine. These curing agents are used to cure liquid epoxy resins at a concentration of at least 10% by weight relative to the epoxy resin. U.S. Patent 4,689,390 describes the preparation of latent curing agents by reacting diamines having tertiary amine groups and primary or secondary amino groups with polyepoxy compounds and phenolic resins or phenolic compounds. A solution of a tertiary polyamine in a polyphenolic resin made from bisphenol A diglycidyl ether and a polyamino secondary amine is described in U.S. Patent 9,279,032 as a latent epoxy curing agent. U.S. Patent No. 7,910,667 describes a polyphenol resin solution of a polyurea derivative of a tertiary polyamine used as a latent epoxy curing agent. U.S. Patent No. 9,546,243 describes a polyphenol resin solution of a specific class of amine used as the sole latent epoxy curing agent and DICY accelerator. Finally, U.S. Patent No. 9,000,120 reports a thermally activated DICY accelerator comprising a tertiary amine and a novolac resin.

[0003] There remains a need for lower-cost and more efficient latent epoxy curing agents. Furthermore, considering energy savings, there is a prominent need for latent epoxy curing agents and accelerators that can cure epoxy resins at lower temperatures without sacrificing the storage stability of the epoxy formulation. The above methods and curing agents have several drawbacks, including high usage levels, excessively low curing temperatures, poor storage stability, or the fact that the precursor amine is obtained through a multi-step process, such as addition with polyepoxides. In this specification, we describe a new class of latent epoxy curing agents that solve the problems inherent in current curing systems and reduce the curing temperature without impairing the latent properties of a one-component epoxy resin composition.

[0004] overview Accordingly, this specification provides epoxy curing agents and related compositions that enable lower curing temperatures without impairing the potential of the epoxy resin composition.

[0005] The inventors have found that by using a solution containing a polyphenol resin encapsulating a polyphenol resin in combination with one or more monomers or polymer compounds that may be functionalized with acidic substituents, such as OH, COOH, SO3OH, PO(OH)3, and PO(OH)2, which may be any of a specific class of amines, it is possible to obtain an epoxy curing agent with improved storage stability, a lower curing temperature, and a lower usage level (less than 10% by weight relative to the epoxy compound). Non-functional compounds or polymers do not have these functional groups and do not interact with tertiary amines.

[0006] In the first aspect, this disclosure is: It contains an amine and a mounting agent system. The aforementioned mounting agent system is Polyphenol resin and An additional excipient selected from functional components (e.g., compounds or polymers functionalized by carboxyl groups and / or hydroxyl groups) and / or non-functional components, This applies to latent curing accelerator compositions [defined herein as "Composition 1"] that include the above.

[0007] In some embodiments, composition 1 is defined as follows: 1.1 Composition 1, wherein the amine is a tertiary amine. 1.2 Amines, (a) alkyl or aryl-substituted tertiary amines (e.g., monotertiary amines), (b) Tertiary amines having more than two peralkylated nitrogen atoms, (c) Tertiary amines having more than two nitrogen permethylated atoms, (d) N,N-dimethyl polyamine having at least one primary amine and one secondary amine, (e) Crosslinked or condensed bicyclic diamines, and / or (f) Imidazoles which may be substituted with alkyl, aryl, alkylaryl, alkyl ether, alkylamino, or at least one halogen (e.g., alkylamino-substituted imidazole, 2-alkyl or aryl-substituted imidazole, e.g., 2-methylimidazole) Composition 1 or 1.1, selected from at least one of the following. 1.3 Any of the aforementioned compositions, wherein the amine comprises one or more of the following: 3,3',3''-imino-tris-(N,N-dimethylpropylamine), 1,8-diazabicyclo(5.4.0)undeca-7-ene (DBU), triethylenediamine (TEDA), 1-(3-aminopropyl)imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, [(dimethylamino)methyl]phenol, bis-[(dimethylamino)methyl]phenol, and tris-(dimethylaminomethyl)phenol (e.g., 2,4,6-tris-(dimethylaminomethyl)phenol), [(dimethylamino)methyl]phenol, and mixtures of bis- and tris-(dimethylamino)methyl substituted phenols. 1.4 Any of the above compositions, wherein the amine is an N,N-dimethyl polyamine having at least one primary amine and one secondary amine. 1.5 Any of the aforementioned compositions, wherein the amine is selected from [(dimethylamino)methyl]phenol, bis-[(dimethylamino)methyl]phenol and tris-(dimethylaminomethyl)phenol (e.g., 2,4,6-tris-(dimethylaminomethyl)phenol), and combinations thereof. 1.6 Any of the aforementioned compositions, wherein the amine comprises or consists of bis-[(dimethylamino)methyl]phenol and tris-(dimethylaminomethyl)phenol (e.g., 2,4,6-tris-(dimethylaminomethyl)phenol), and combinations thereof. 1.7 Any of the aforementioned compositions, wherein the amine comprises a mixture of bis- and tris-[(dimethylamino)methyl]phenol. 1.8 Any of the aforementioned compositions, wherein the amine is present in an amount of about 10% to about 75% by weight, about 10% to about 60% by weight, about 20% to about 60% by weight, about 30% to about 60% by weight, about 30% to about 50% by weight, or about 40% to about 50% by weight (for example, preferably about 10% to about 60%) based on the total weight of the composition. 1.9 Any of the above compositions, wherein the polyphenol resin is (a) a phenol novolac resin, or (b) a polymer or copolymer of phenol substituted with an unsaturated ethylene group. 1.10 Any of the above compositions, wherein the polyphenol resin contains or consists of a phenol novolac resin. 1.11 Polyphenol resin has the following structure: [ka] (In the formula, R1 is H, alkyl, or aryl. R2 is C 1-10 Alkyl, C 1-10 It is an alkoxy or halogen, m = 0 to 3 (n = 1 to 20) Any of the above compositions, which is a phenol novolac resin having [the specified property]. 1.12 Any of the above compositions, wherein the polyphenol resin is a phenol novolac resin selected from phenol-formaldehyde resins and p-cresol-formaldehyde resins. 1.13 Any of the above compositions, wherein the polyphenol resin is Alnovol PN320. 1.14 Any of the aforementioned compositions, wherein the polyphenol resin is present in an amount of about 10% to about 75% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 45% by weight, about 20% to about 45% by weight, or about 30% to about 45% by weight (for example, preferably about 20% to about 50%) based on the total weight of the composition. 1.15 Any of the above compositions, wherein the polyphenol resin has a molecular weight of at least 3,000D. 1.16 Any of the above compositions, wherein the polyphenol resin has a molecular weight of approximately 5,000D to approximately 30,000D. 1.17 Any of the above compositions, wherein the polyphenol resin has a molecular weight of approximately 10,000D to approximately 25,000D. 1.18 Any of the aforementioned compositions, wherein the additional excipient is a functional compound containing one or more carboxyl groups and / or hydroxyl groups, and comprises one or more of (a) monomeric carboxylic acids, sulfonic acids, phosphonic acids, phosphoric acids, or boric acids, (b) acrylic resins, (c) polyether resins, (d) polybutadiene resins, and (e) polyamide resins. 1.19 Any of the aforementioned compositions, wherein the additional excipient is present in an amount of about 10% to about 75% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 40% by weight, about 10% to about 30% by weight, or about 20% to about 30% by weight (for example, preferably about 10% to about 30%) based on the total weight of the composition. 1.20 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a functional compound present in an amount of about 10 wt% to about 75 wt%, about 10 wt% to about 60 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, or about 20 wt% to about 30 wt% (e.g., preferably about 10 wt% to about 30 wt%) based on the total weight of the composition. 1.21 Any of the aforementioned compositions, wherein the additional excipient is a monomeric carboxylic acid, sulfonic acid, phosphonic acid, phosphoric acid, or boric acid. 1.22 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a monomeric carboxylic acid. 1.23 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a monomeric sulfonic acid. 1.24 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a monomeric phosphonic acid. 1.25 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a monomeric phosphoric acid. 1.26 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of a monomeric boric acid. 1.27 Any of the aforementioned compositions, wherein the additional excipient comprises or consists of an acrylic resin. 1.28 The acrylic resin has the following formula: [Chemical formula] (wherein R1 is independently selected from H or C 1-3 alkyl, and R2 is H or C 1-8 alkyl, and the alkyl group may be substituted with -OH) Any of the aforementioned compositions having the structure according to. 1.29 The acrylic resin has the following formula: [Chemical formula] (wherein R1 is independently selected from H or CH3, R2 is H or C 1-8(It is alkyl, and the alkyl group may be substituted with -OH.) The aforementioned composition having the structure thereof. 1.30 Any of the above compositions, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer and a vinyl monomer with an unsaturated monomer containing a hydroxyl group or a carboxyl group. 1.31 Any of the above compositions, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer containing a hydroxyl group, a carboxyl group, and / or an ester group. 1.32 Any of the above compositions, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer containing a carboxyl group. 1.33 Any of the above compositions, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer containing an ester group. 1.34 Any of the above compositions, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer containing a hydroxyl group. 1.35 Any of the above compositions, wherein the acrylic resin has an acid value of approximately 50 to approximately 120 mg / KOH, approximately 60 to approximately 100 mg / KOH, or approximately 70 to approximately 90 mg / KOH (for example, approximately 70 mg / KOH). 1.36 Any of the above compositions, wherein the additional excipient comprises or consists of a polyether resin. 1.37 Any of the above compositions, wherein the additional excipient is polyalkylene glycol. 1.38 The aforementioned composition, wherein the polyalkylene glycol has a molecular weight of approximately 1,000D to approximately 100,000D. 1.39 The aforementioned composition, wherein the polyalkylene glycol has a molecular weight of approximately 1,500D to approximately 35,000D. 1.40 The aforementioned composition, wherein the polyalkylene glycol has a molecular weight of approximately 1,500D to approximately 10,000D. 1.41 Any of the above compositions, wherein the additional excipient comprises or consists of a polybutadiene resin. 1.42 The aforementioned composition, wherein the polybutadiene resin is carboxylated polybutadiene. 1.43 The above-mentioned composition, wherein the carboxylated polybutadiene has a polybutadiene skeleton microstructure consisting of a combination of vinyl 1,2 bonds, trans 1,4 bonds, and cis 1,4 bonds. 1.44 Composition 1.42 or 1.43, wherein the carboxylated polybutadiene has an average molecular weight of about 500D to about 10,000D. 1.45 A composition of any of 1.42 to 1.44, wherein the carboxylated polybutadiene has a molecular weight of approximately 1,000D to approximately 7,000D. 1.46 Any of compositions 1.42 to 1.45, wherein the carboxylated polybutadiene has a molecular structure consisting of 70-90% cis double bonds, 10-30% trans double bonds, and 0-3% vinyl double bonds. 1.47 Any of compositions 1.42 to 1.46, wherein the carboxylated polybutadiene is a maleic anhydride adduct of cis-1,4-polybutadiene (e.g., low molecular weight cis-1,4-polybutadiene), which may have succinic anhydride pendant groups randomly distributed in the polymer chain. 1.48 Any of the above compositions, wherein the additional excipient comprises or consists of a polyamide resin. 1.49 The aforementioned composition, wherein the polyamide resin is nylon (e.g., nylon-6, nylon-6-6, copolymers of nylon-6 and nylon-6-6, nylon-9, nylon-10, nylon-11, nylon-12, nylon-6-10), aromatic polyamides, elastomer polyamides, and mixtures thereof. 1.50 Composition 1.48 or 1.49, wherein the polyamide resin is an acid-functional thermoplastic polyamide. 1.51 Any of the aforementioned compositions, wherein the additional excipient is a non-functional component and is a polymer compound selected from acrylates, polybutadienes, polyamides, ketone-aldehyde condensation resins, polyimides, styrene-butadiene resins, olefin copolymers, and combinations thereof. 1.52 Any of the aforementioned compositions, wherein the additional excipients include or consist of a non-functional compound present in an amount of about 10% to about 75% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 40% by weight, about 10% to about 30% by weight, or about 20% to about 30% by weight (for example, preferably about 10% to about 30%) based on the total weight of the composition. 1.53 Any of the aforementioned compositions, wherein the weight ratio of the amine to the encapsulation system is approximately 1:0.3 to approximately 1:10, or approximately 1:0.3 to approximately 1:2, or approximately 1:0.5 to approximately 1:1.5, or approximately 1:0.8, or approximately 1:1.1, or approximately 1:1.4. 1.54 Any of the aforementioned compositions, wherein the weight ratio of polyphenols to additional excipients is about 1:4 to about 4:1, for example, about 1:3 to about 3:1, about 2:1 to about 1:2, or about 1:1. 1.55 Any of the above compositions, prepared by dissolving an amine in a encapsulating agent system comprising a polyphenol resin and additional excipients. 1.56 Any of the above compositions that form a curable epoxy system when combined with an epoxy resin. 1.57 A curable epoxy system having a starting temperature of approximately 130°C to approximately 151°C, composition 1.56. 1.58 A curable epoxy system having a starting temperature of approximately 133°C to approximately 146°C, composition 1.56 or 1.57. 1.59 A composition of any of 1.56 to 1.58, wherein the curable epoxy system has a viscosity of approximately 20,000 cP to approximately 45,000 cP. 1.60 Any of compositions 1.56 to 1.59, wherein the curable epoxy system does not gel after 4 weeks under accelerated aging conditions (i.e., 4 weeks of storage at 40°C). 1.61 A composition of any of 1.56 to 1.60 in which the curable epoxy system provides a wrap shear strength of approximately 500 psi to 1700 psi. 1.62 Any of compositions 1.56 to 1.61, wherein the additional excipient is an acrylic resin and the curable epoxy system provides a lap shear strength of approximately 800 psi to approximately 1500 psi. 1.63 A curable epoxy system having an adhesive strength of approximately 50 pli to 130 pli as determined by a T-type peel test, any of compositions 1.56 to 1.62. 1.64 Any of compositions 1.56 to 1.63, wherein the additional excipient is an acrylic resin, and the curable epoxy system has an adhesive strength of approximately 50 pli to 130 pli as determined by a T-type peel test. 1.65 Any of the aforementioned compositions, in liquid or solid powder form. 1.66 Any of the above-mentioned compositions in the form of an aqueous solution. 1.67 Any of the above compositions further comprising one or more of a wetting agent, a filler, an antifoaming agent, and a rheological modifier. 1.68 Any of the above compositions, which are latent curing agents (e.g., sole latent curing agents) for epoxy resins.

[0008] In a second aspect, this disclosure is: A latent curing accelerator composition defined by composition 1 or any of compositions 1.1 to 1.68, Epoxy resin and This applies to curable epoxy systems [defined herein as "System 1"] that include [the specified term].

[0009] In some embodiments, System 1 is defined as follows. 1.1 System 1, wherein the latent curing accelerator composition is composition 1 and any of the following. 1.2 System 1 or 1.1, wherein the epoxy is a glycidyl ether, a polyhydric phenol, or an alicyclic epoxide (including diepoxides of alicyclic esters of dicarboxylic acids). 1.3 Epoxy is given by the following formula: [ka] (In the formula, m is an integer and R is the divalent hydrocarbon group of a divalent phenol.) A polymer of any of the aforementioned systems. 1.4 Any of the aforementioned systems, further including DICY. 1.5 Any of the above systems, wherein the composition has an onset temperature of about 130°C to about 151°C. 1.6 Any of the above systems, wherein the composition has a starting temperature of about 133°C to about 146°C. 1.7 Any of the above systems, wherein the composition has a viscosity of about 20,000 cP to about 45,000 cP. 1.8 Any of the aforementioned systems in which the composition does not gel after 4 weeks under accelerated aging conditions (i.e., storage at 40°C for 4 weeks). 1.9 Any of the aforementioned systems, wherein the composition yields a wrap shear strength of approximately 500 psi to 1700 psi. 1.10 Any of the aforementioned systems, wherein the additional excipient is an acrylic resin, and the composition yields a lap shear strength of about 800 psi to about 1500 psi. 1.11 Any of the above systems, wherein the composition has an adhesive strength of approximately 50 pli to 130 pli as determined by a T-type peel test. 1.12 Any of the aforementioned systems, wherein the additional excipient is an acrylic resin, and the composition has an adhesive strength of about 50 pli to 130 pli as determined by a T-type peel test. 1.13 Any of the above systems further comprising one or more of a wetting agent, a filler, an antifoaming agent, and a rheological modifier. 1.14 Any of the aforementioned systems, wherein the composition is a latent curing agent for epoxy resins (e.g., a sole latent curing agent).

[0010] In a third aspect, this disclosure is: A method for curing a substance by using a latent curing accelerator composition comprising an amine and a encapsulating agent system, The aforementioned mounting agent system Polyphenol resin and An additional excipient selected from functional and / or non-functional components, Includes, The present invention relates to a method [defined herein as Method 1] which includes the step of combining the substance with the latent curing accelerator composition and heating the resulting mixture.

[0011] In some embodiments, Method 1 is defined as follows: 1.1 Method 1, where the substance is epoxy resin. 1.2 Method 1 or 1.1, wherein the latent curing accelerator composition is Composition 1 and subsequent compositions. 1.3 Any of the above methods, in which a mixture containing the substance and a latent curing accelerator is heated to a temperature of about 130°C to about 151°C. 1.4 Any of the methods described above, which involves heating a mixture containing the substance and a latent curing accelerator to a temperature of approximately 133°C to approximately 146°C. 1.5 Any of the above methods, wherein the latent curing accelerator composition is formed by blending an amine and a mounting agent system under a nitrogen atmosphere and heating to a temperature of 130°C to 180°C. 1.6 Any of the above methods, wherein the composition is a latent curing agent for epoxy resins (e.g., a sole latent curing agent). 1.7 Any of the methods described above, wherein the composition is used as an accelerator for curing agents for epoxy resins, such as DICY or acid anhydrides. 1.8 Any of the methods described above, in which the composition is used as a latent curing accelerator for structural adhesives and composites, electrical potting and sealing, reinforcement and / or damping, field-curing pipes, impact-resistant adhesives, filament windings, transfer molding powders, prepregs containing solid or liquid epoxy, sheet molding compounds, coatings for concrete, wood, metal and the like, resin transfer molding, and / or EV battery pack adhesives.

[0012] This disclosure further provides latent curing accelerator compositions for use in methods for curing a substance, for use in Method 1 and any of the subsequent methods.

[0013] This disclosure further provides the use of latent curing accelerator compositions in the manufacture of curable formulations comprising a substance and a latent curing accelerator composition for use in Method 1 and any of the subsequent methods.

[0014] Detailed explanation of this disclosure This disclosure provides latent curing accelerators and compositions containing such latent curing accelerators and a curing substance (e.g., epoxy resin). Methods for manufacturing and using these are further provided.

[0015] Amine The latent curing accelerator of this disclosure comprises at least one amine compound. Classes of amines used in this composition include: (a) alkyl-substituted or aryl-substituted tertiary amines (e.g., monotertiary amines), (b) Tertiary amines having more than two peralkylated nitrogen atoms, (c) Tertiary amines having more than two nitrogen permethylated atoms, (d) N,N-dimethyl polyamine having at least one primary amine and one secondary amine, (e) Crosslinked or condensed bicyclic diamines, and (f) Imidazoles which may be substituted with alkyl, aryl, alkylaryl, alkyl ether, alkylamino, or at least one halogen (e.g., alkylamino-substituted imidazole, 2-alkyl or aryl-substituted imidazole, e.g., 2-methylimidazole) These are some examples.

[0016] Non-limiting examples of amines that may be used in the disclosed compositions include 3,3',3''-iminotris(N,N-dimethylpropylamine), 1,8-diazabicyclo(5.4.0)undeca-7-ene (DBU), triethylenediamine (TEDA), 1-(3-aminopropyl)imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, [(dimethylamino)methyl]phenol, bis[(dimethylamino)methyl]phenol, and 2,4,6-tris(dimethylaminomethyl)phenol. Further examples of amines include monosubstituted phenol compounds, such as [(dimethylamino)methyl]phenol (marketed by Evonik Corporation as Ancamine 1110), and mixtures of bis- and tris-dimethylaminomethyl substituted phenols (marketed by Evonik Corporation as Ancamine K54). Other commercially available tertiary amines from Evonik Corporation, which are part of this disclosure, include pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, trimethylaminopropoxyethanol, bisdimethylaminopropylamine, dimethylaminopropylamine (DMAPA), and trisdimethylaminopropylamine.

[0017] The amine may be present in the latent curing accelerator composition in amounts of about 10% to about 75% by weight, about 10% to about 60% by weight, about 20% to about 60% by weight, about 30% to about 60% by weight, about 30% to about 50% by weight, or about 40% to about 50% by weight (for example, preferably about 10% to about 60%) based on the total weight of the composition.

[0018] Polyphenol resin The latent curing accelerator of this disclosure further comprises an encapsulating agent system comprising a phenol resin as its main component. The phenol novolac resin is prepared from mononuclear phenols and alkyl-substituted mononuclear phenols, or alkoxyphenols or halogenated phenols, and an aldehyde, such as acetaldehyde, benzaldehyde, or preferably formaldehyde. The chemical structure of such a phenol novolac resin is shown below: [ka] (In the formula, R1 is H, alkyl, or aryl. R2 is C 1-10 Alkyl, C 1-10 It is an alkoxy or halogen, m = 0 to 3, (n = 1 to 20)

[0019] Examples of preferred novolac resins include phenol-formaldehyde resins and p-cresol-formaldehyde resins. Other suitable phenolic resins are prepared from polyhydric phenols such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, and bisphenol M. The bisphenol compounds are preferably unsubstituted at both meta positions or at both meta and para positions relative to the hydroxyl group, so that reaction sites are available that can undergo condensation reactions to provide crosslinking sites between molecules of the phenolic compound. Suitable bisphenols also include bis(4-hydroxyphenyl)methane, 4,4'-hydroxydiphenyl, bis(4-hydroxyphenyl)sulfone, and 4,4'-dihydroxybenzophenone.

[0020] Polymers or copolymers of phenols substituted with unsaturated ethylene groups, such as 2-allylphenol and 4-allylphenol, or polymers and copolymers of phenol-substituted acrylates or phenol-substituted methacrylates, or polymers of vinylphenol and propenylphenol. Copolymers of such unsaturated phenols with other polymerizable alkene-substituted compounds such as styrene, α-methylstyrene, acrylic acid esters, methacrylic acid esters, and vinyl esters are also suitable for forming solid solutions with the above-mentioned amines.

[0021] The ratio of starting materials and reaction conditions are selected so that the novolac formed by the condensation reaction has a weight molecular weight of at least 3,000. The weight-average molecular weight of the novolac resin can be at least 5,000 and may be 30,000 or more. The molecular weight is limited only by the need for the novolac resin to soften or melt at a reasonable temperature so that it can be mixed with an amine to produce a latent epoxy hardener. Preferably, the novolac resin softens at a temperature of about 90 to about 200°C, particularly about 130 to 200°C. A preferred novolac resin is a phenol-formaldehyde resin having a weight-average molecular weight of 10,000 to 25,000 (e.g., Alnovol PN-320 available from Allnex GmbH).

[0022] The polyphenol resin may be present in the latent curing accelerator composition in an amount of about 1% to about 75% by weight, based on the total weight of the composition. In other embodiments, the polyphenol resin may be present in an amount of about 10% to about 75% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 45% by weight, about 20% to about 45% by weight, or about 30% to about 45% by weight (for example, preferably about 20% to about 50%), based on the total weight of the composition.

[0023] Additional excipients In various embodiments, the encapsulation systems of the present disclosure further include additional excipients, which may be functional or non-functional monomer compounds or polymer compounds. Exemplary excipients are provided below. In various embodiments, the additional excipients may be present in amounts of about 1% to about 75% by weight based on the total weight of the composition. In further embodiments, the additional excipients may be present in amounts of about 10% to about 75% by weight, about 10% to about 60% by weight, about 10% to about 50% by weight, about 10% to about 40% by weight, about 10% to about 30% by weight, or about 20% to about 30% by weight (for example, preferably about 10% to about 30%) based on the total weight of the composition. If one or more additional excipients are present, this concentration may refer to the total amount of the additional excipients or to the amount of each individual additional excipient.

[0024] functional compound Examples of functional compounds according to this disclosure include a variety of chemical substances, such as phenols, alkyl or aryl-substituted carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, and boric acids.

[0025] Representative phenolic compounds that can be used include phenols or substituted phenols (substituents include alkyl, aryl ether, or amino groups, or halogen atoms), such as p-tert-butylphenol, p-sec-butylphenol, o-tert-butylphenol, o-sec-butylphenol, p-tert-amylphenol, p-tert-octylphenol, p-nonylphenol, p-cumylphenol, p-dodecylphenol, styrylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, di-sec-butylphenol, 2,4-di-tert-amylphenol, 2,4-di-cumylphenol, o-cumyloctylphenol, α-naphthol, β-naphthol, bis-phenol A, bis-phenol F, bis-phenol TMC, and mixtures thereof, comprising at least one member selected from this group.

[0026] Representative carboxylic acids that may be used include at least one member selected from the group consisting of acetic acid, propanoic acid, hexanoic acid, 2-ethylhexanoic acid, decanoic acid, stearic acid, benzoic acid, salicylic acid, tall oil fatty acids (TOFAs), dimer acids, and mixtures thereof.

[0027] Various other acid-functional compounds may be used in the compositions of the present disclosure. Non-limiting examples of such compounds include sulfonic acids, such as p-toluenesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, phosphonic acid, phosphoric acid, and boric acid. Examples of functional polymer compounds include a variety of chemical substances, such as acrylics, polyethers, polybutadienes, polyamides, and combinations thereof.

[0028] As used herein, the terms “functional” or “functionalized” refer to a compound or polymer that contains, or is modified to contain, one or both a carboxyl group and / or a hydroxyl group.

[0029] Acrylic resin The acrylic polymers useful in this disclosure can be prepared by free radical polymerization of acrylic monomers and vinyl monomers with unsaturated monomers having hydroxyl or carboxyl groups. Useful acrylic resins include those having hydroxyl functional groups with a hydroxyl value of more than 1 to 200 and carboxyl functional groups with an acid value of more than 1 to 300. The preferred softening point of the acrylic polymer is about 50°C to 200°C.

[0030] Useful functional monomers are selected from acrylic acid, methacrylic acid, crotonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Other acrylic monomers can be selected from the group consisting of esters of α,β-ethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms. Preferred acrylic monomers are of the following formula: [Chemical formula] (wherein, R1 is independently selected from H or C 1-3 alkyl, R2 is H or C 1-8 alkyl, and the alkyl group may be substituted with -OH) and has.

[0031] Examples of acrylic monomers useful in the compositions of the present disclosure include ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, and lauryl methacrylate.

[0032] In various embodiments, the acrylic polymer can optionally contain an ethylenically monounsaturated vinyl comonomer that is different from the functional monomer and the acrylic monomer. Examples of ethylenically unsaturated vinyl comonomers that can be useful are styrene, propylene, vinyl toluene, dimethyl styrene, α-methyl styrene, and vinyl acetate. The acrylic compound can be a liquid, a solid, or the solution is an organic solvent.

[0033] Copolymers can be prepared in any known manner, preferably by free radical polymerization in bulk, solution, emulsion, or suspension. Preferably, the reaction is carried out in the presence of a free radical initiator, such as an azo compound, e.g., benzoyl peroxide, tert-butyl peroxide, decanoyl peroxide, or azobisisobutyronitrile. Such initiators may be present in an amount ranging from 0.1 to about 5% by weight of the total monomers.

[0034] In various embodiments, commercially available examples of acrylic resins used in the compositions of this disclosure include ISOCRYL C-78 (sold by Estron Chemical Inc.), ISOCRYL H-89 (sold by Estron Chemical Inc.), and JONCRYL 67 (sold by BASF).

[0035] Polyether resin A preferred polyether resin used in the compositions of this disclosure is polyalkylene glycol. Polyalkylene glycol may have a molecular weight of 1,000 to 100,000 D [Daltons], preferably 1,500 to 35,000 D, and particularly preferably 1,500 to 10,000 D. A particularly preferred polyalkylene glycol is polyethylene glycol. Furthermore, polybutylene glycol obtained from polypropylene glycol, polytetrahydrofuran, or 2-ethyloxirane or 2,3-dimethyloxirane is also suitable. Other suitable polyethers are random or block copolymers of polyalkylene glycol obtained from ethylene oxide, propylene oxide, and butylene oxide, such as polyethylene glycol-polypropylene glycol block copolymer. The block copolymer may be of type AB or ABA.

[0036] More preferred polyalkylene glycols include those alkylated at one or both terminal OH groups. Suitable alkyl groups include branched or linear C1-C12 22 Alkyl alkyl group, preferably C 1~C 18 Alkyl groups, such as methyl, ethyl, n-butyl, isobutyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, or octadecyl groups.

[0037] Preferred polyalkylene glycols include those in which one or both terminal OH groups are acid-capped. Phosphonic acid-terminated polyethers are an example of such preferred polyalkylene glycols. Another example of a preferred polyalkylene glycol is one in which polyoxyethylene chains are grafted onto a polycarboxylate-type skeleton.

[0038] The method for producing polyether copolymers according to this disclosure is generally known in the prior art. Preparation is preferably carried out by free radical polymerization in solution, in a non-aqueous organic solvent, or in a non-aqueous / aqueous mixed solvent. Suitable preparation processes are described, for example, in International Publication Nos. 2007 / 051743 and International Publication Nos. 2009 / 013202, and the disclosure relating to the preparation processes is incorporated herein by reference in whole.

[0039] Polybutadiene resin Examples of polybutadiene-based polyol resins used in the compositions of this disclosure include homopolymers, such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol; copolymers, such as poly(pentadiene butadiene) polyol, poly(butadiene styrene) polyol and poly(butadiene acrylonitrile) polyol; and hydrogenated polybutadiene-based polyol resins obtained by hydrogenating these polyol resins. These polybutadiene-based polyol resins are commercially available, for example, from Idemitsu Kosan Co., Ltd. as Poly bd R-15HT (hydroxyl value = 102.7 mg KOH / mg, Mw1200) and Poly bd R-45HT (hydroxyl value = 46.6 mg KOH / mg, Mw2800). Furthermore, due to the advantages of this disclosure, the polybutadiene-based polyol resin preferably has a hydroxyl value of 40 to 330 mg KOH / g, more preferably 40 to 110 mg KOH / g. The polybutadiene-based polyol preferably has a weight-average molecular weight (GPC) of 50 to 3,000, more preferably 800 to 1,500.

[0040] Other polybutadiene resins suitable for use in the compositions of this disclosure include carboxylated polybutadiene, which may be in the form of a liquid polymer having a polybutadiene skeletal microstructure consisting of a combination of vinyl 1,2, trans 1,4, and cis 1,4 bonds, and is transparent at room temperature. The vinyl 1,2 bonds are preferably 30% by weight or less. The cis 1,4 bonds are preferably 40% by weight or more. If the cis 1,4 bonds are less than 40% by weight, it may lead to a decrease in the adhesion of the resulting composition and is therefore undesirable.

[0041] The carboxylated polybutadiene component can be obtained by reacting a carboxyl group-introduced compound with liquid polybutadiene. The 1,3-butadiene and carboxyl group-introduced compound constituting the liquid polybutadiene are preferably used in proportions of 80-98% by mass (1,3-butadiene) and 2-20% by mass (carboxyl group-introduced compound), respectively.

[0042] The liquid polybutadiene used in the reaction preferably has a number-average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000. A broad molecular weight distribution is desirable for the liquid polybutadiene. More preferably, the liquid polybutadiene has an iodine value of 30 to 500 g of iodine per 100 g of material, as determined according to DIN 53241. Preferably, the liquid polybutadiene has a molecular structure consisting of 70 to 90% cis double bonds, 10 to 30% trans double bonds, and 0 to 3% vinyl double bonds.

[0043] Examples of carboxyl group-introduced compounds that can be used include ethylene-based unsaturated dicarboxyl compounds, such as ethylene-based unsaturated dicarboxylic acids, and their anhydrides or monoesters. Specific examples of these compounds include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleic acid, or monoethyl maleic acid. Among these, maleic anhydride is preferred due to its safety, economy, and reactivity (polybutadiene maleate is preferred).

[0044] Methods for producing polybutadiene / maleic anhydride adducts are generally known in the prior art.

[0045] The maleic acid liquid polybutadiene is determined according to DIN ISO 3682 and preferably has an acid value of 50 to 120 mg KOH / g, more preferably 70 to 90 mg KOH / g. If the acid value is less than 50 mg KOH / g, the adhesiveness of the resulting composition will decrease, but if the acid value exceeds 120 mg KOH / g, it will lead to an increase in the viscosity of the resulting composition, reducing its workability.

[0046] The maleic acid ratio of maleic acid-coated liquid polybutadiene needs to be considered along with viscosity, but is preferably 6-20%, more preferably 6-15%, and even more preferably 7-10%.

[0047] The viscosity (at 20°C) of liquid polybutadiene with maleic acid is determined according to DIN 53214 and is preferably 3 to 16 Pa·s, more preferably 5 to 13 Pa·s, and even more preferably 6 to 9 Pa·s.

[0048] Furthermore, the maleic acid-coated liquid polybutadiene contains 30% or less vinyl double bonds. Liquid polybutadiene containing cis double bonds within the above range tends to have higher flexibility and a higher maleic acid ratio (i.e., acid value) compared to liquid polybutadiene containing cis double bonds at a lower percentage than the above lower limit. As a result, the composition has high adhesiveness and sufficient polarity, and it is possible to produce a more flexible composition and easily adjust the flexibility of the composition of this disclosure. Furthermore, the resulting composition has improved decorative properties.

[0049] The viscosity of liquid polybutadiene with cis double bonds present in a proportion lower than the lower limit mentioned above increases rapidly with increasing maleic acid content, while the viscosity of liquid polybutadiene with cis double bonds within the above range shows only a slight increase. This low viscosity within the above range ensures high reactivity and improves workability. Furthermore, the resulting composition exhibits improved decorative properties.

[0050] Non-limiting examples of polybutadiene resins according to this disclosure are maleic anhydride adducts of cis-1,4-polybutadiene (e.g., low molecular weight cis-1,4-polybutadiene), which may have succinic anhydride pendant groups randomly distributed in the polymer chain. Examples of such polybutadiene resins include POLYVEST OC 800S, POLYVEST OC 1200S, and POLYVEST MA-75, each manufactured by Evonik Industries.

[0051] Polyamide resin Polyamides are typically condensation copolymers formed by the reaction of a dicarboxylic acid with a diamine, or by ring-opening of a lactam. Various polyamides can be produced by adjusting the number of carbon atoms. In the nomenclature used herein, the number of carbon atoms in the diamine is indicated first, followed by the number of carbon atoms in the diacid. Thus, polyamide-6,6 has 6 carbons from the diamine and 6 carbons from the diacid, and polyamide-6,12 has 6 carbons from the diamine and 12 carbons from the diacid. Polyamide-6 is a homopolymer formed by ring-opening polymerization (i.e., ring-opening polymerization of caprolactam). Polyamides may also be nylon-9, nylon-12, nylon-11, nylon-4,6, nylon-6,10, or any of the polyamides listed herein.

[0052] Useful polyamide resins in the compositions of this disclosure include nylon-6, nylon-6-6, copolymers of nylon-6 and nylon-6-6, nylon-9, nylon-10, nylon-11, nylon-12, nylon-6-10, aromatic polyamides, elastomer polyamides, and mixtures thereof.

[0053] The conditions and COOH / NH2 ratio for preparing polyamide resins can be selected to obtain a final product having an acid value or amine value within the intended range. A polyamide resin is classified as acid-functional if its amine value is lower than its acid value (AV). Evonik's ANCATHERM 592 is an example of an acid-functional thermoplastic polyamide.

[0054] Non-functional polymer compounds Non-functional polymer compounds useful in the compositions of this disclosure include copolymers of acrylates, polybutadienes, polyamides, ketone-aldehyde condensation resins, polyimides, styrene-butadiene resins, and other olefins, as well as combinations thereof.

[0055] Examples of non-functional resin compounds that can be used in combination with phenolic resins in this disclosure include compounds from Evonik's POLYVEST liquid polybutadiene product line, thermoplastic acrylic resins and MBS polymers from Dow's Paraloid product line, non-functional polyamides from Evonik's Vestamid product line, and styrene-based block copolymers (SBCs) from Kraton, produced from butadiene, styrene, and isoprene raw materials. Finally, ketone-aldehyde condensation resins, such as Evonik's TEGO Variplus AP, can also be used in combination with polyphenols in this disclosure.

[0056] Curable epoxy resin Solutions of amines with phenolic resins and other resins, as well as combinations thereof, are used as curing agents for epoxy resins. Epoxy resins commercially available under trade names DER 383 or DER 333 (available from Dow) and EPON 826 or EPON 828 (available from Hexion Specialty Chemicals) are suitable for use with the latent curing accelerator compositions of this disclosure.

[0057] Other epoxy resins include, but are not limited to, bifunctional epoxys, such as bisphenol-A and bisphenol-F resins. As used herein, polyfunctional epoxy resins refer to compounds containing two or more 1,2-epoxy groups per molecule. This type of epoxide compound is well known to those skilled in the art and is described by reference herein in Y. Tanaka, "Synthesis and Characteristics of Epoxides," in Epoxy Resins Chemistry and Technology (Marcel Dekker, 1988), edited by Camay.

[0058] One class of epoxy resins suitable for use in this disclosure comprises glycidyl ethers of polyhydric phenols, including glycidyl ethers of dihydric phenols. Exemplary examples, but not limited to, include 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 available as bisphenol A), bis-(4-hydroxyphenyl)-methane (commercially available as bisphenol-F, which may contain varying amounts of 2-hydroxyphenyl isomers), or any combination thereof. In addition, the following structures are used in this disclosure: [ka] (In the formula, m is an integer, and R is the divalent hydrocarbon group of a divalent phenol, for example, the divalent phenol described above.) Highly volatile phenols are also useful.

[0059] Materials according to this formula can be prepared by polymerizing a mixture of divalent phenol and epichlorohydrin, or by proceeding with a mixture of diglycidyl ether of divalent phenol and divalent phenol. In any given molecule, the value of m is an integer, but the material is always a mixture and can be characterized by an average value of m that is not necessarily an integer. Polymer materials having an average value of m from 0 to about 7 can be used in one embodiment of this disclosure. In other embodiments, the epoxy component may be a polyglycidylamine from one or more of 2,2'-methylenedianiline, m-xylenedianiline, hydantoin, and isocyanates.

[0060] The epoxy component may be a cycloaliphatic or alicyclic epoxide. Examples of suitable alicyclic epoxides include diepoxides of alicyclic esters of dicarboxylic acids, such as bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide; limonene diepoxide; bis(3,4-epoxycyclohexylmethyl) pimelate; dicyclopentadiene diepoxide; and other suitable alicyclic epoxides. Other suitable diepoxides that are alicyclic esters of dicarboxylic acids are described, for example, in International Publication No. 2009 / 089145(A1), which is incorporated herein by reference.

[0061] Other alicyclic epoxides include 3,3-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,3-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexanecarboxylate; 6-methyl-3,4-epoxycyclohexylmethylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate; and 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate. Other suitable 3,4-epoxycyclohexylmenthyl-3,4-epoxycyclohexanecarboxylates are described, for example, in U.S. Patent No. 2,890,194, which is incorporated herein by reference. In other embodiments, the epoxy component may include polyol polyglycidyl ethers from polyethylene glycol, polypropylene glycol, or polytetrahydrofuran, or combinations thereof.

[0062] In addition to the components described above, latent curing accelerators may be used in the curable epoxy composition, which may further contain additives, such as wetting agents (e.g., silicones, fatty acid alcohols, ionic and nonionic surfactants), fillers (e.g., calcium carbonate, calcium oxide, talc, coal tar, carbon black, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, silicate minerals, mica, powdered quartz, hydrated aluminum oxide, bentonite, wollastonite, kaolin, fumed silica, silica aerogel, or metal powders such as aluminum powder or iron powder), defoamers (e.g., nonionic surfactants, silicones, mineral oils), rheology modifiers (e.g., fumed silica, bentonite clay, organic clay, precipitated calcium carbonate, etc.).

[0063] In various embodiments, the latent curing accelerator compositions of the present disclosure are first prepared by introducing the components into a two-piece glass reactor equipped with a mechanical stirrer, thermocouples, and reflux condenser under an N2 atmosphere. The reactants are heated to 130-180°C for a set period of time, for example, 1 hour, and the hot solution is poured onto a Teflon block or aluminum sheet and cooled to room temperature. The resin can be added to the reactor undiluted as described above, or dissolved in a certain polar solvent, such as methanol. In the latter case, the resulting reaction mixture is refluxed for 2 hours to form a clear solution. The mixture is then cooled to room temperature and the solvent is removed by evaporation. The resulting product is further dried under vacuum.

[0064] Upon removal from the reactor, the final curing agent formulation may be liquid or solid. If solid, the material is ground into a fine powder using methods such as spray drying, ceramic bead grinding, jet grinding, or coffee grinding. The particle size of the powder may range from 1 to 100 microns. The powder is then kneaded into the epoxy resin and mixed using a speed mixer, Cowles blade mixer, or planetary mixer. If the final curing agent is liquid, it is kneaded directly into the resin using a similar mixing method. Optional additives, such as wetting agents, fillers, defoamers, and rheology modifiers, may be added as needed.

[0065] This composition, acting as a curing agent, can be used to cure epoxy resins, either as a standalone component or as an accelerator in combination with DICY. In addition, it can be used as an accelerator for anhydride-cured epoxies, polymercaptan-cured epoxies, and other amine-cured epoxies.

[0066] Epoxy formulations containing this composition as a curing agent, either alone or as an accelerator, can be used in a variety of applications where epoxy systems are preferred. Applications of particular interest include, but are not limited to, structural adhesives and composites, electrical potting and sealing, compositions for reinforcement and / or damping, field-curing pipes, impact-resistant adhesives, filament windings, transfer molding powders, prepregs containing solid or liquid epoxy, sheet molding compounds, coatings for concrete, wood, metal, etc., resin transfer molding, and EV battery pack adhesives. [Examples]

[0067] Example 1: Preparation of amine solutions in polymer phenols combined with other resins The amine is added to a two-piece glass reaction flask under an N2 atmosphere and heated to 130-180°C. The non-phenolic resin is then slowly added with stirring, followed by the phenolic resin (Alnovol PN-320). Once the additions are complete, the mixture is held at 130-180°C for another hour. The molten solution is poured onto a Teflon block or aluminum sheet and cooled to room temperature. The solid product is pulverized and then finely ground to the appropriate size using ceramic beads in a speed mixer. The following amine solutions were prepared using this method. (a) Formulation 1: A solution of 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine K54) in a polyphenol resin and β-naphthol blend (PN320 / β-naphthol). Blends of amine and polyphenol resin / β-naphthol in weight ratios of 100 / 140, 100 / 110, and 100 / 80 were prepared as follows. The weight ratio of polyphenol resin to β-naphthol used in this example is 75 / 25. The formulation was prepared as described above using 110 g of 2,4,6-tris(dimethylaminomethyl)phenol, 38.5 g of β-naphthol, and 115.5 g of polyphenol resin. The second blend was prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 34.37 g of β-naphthol, and 103.12 g of polyphenol resin. The third blend was similarly prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 25 g of β-naphthol, and 75 g of polyphenol resin. The preparation of formulation 1 is summarized below. [Table 1] (b) Formulation 2: Solution of 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine K54) in a polyphenol resin and polyacrylic resin blend (PN320 / Isocryl C-78). Blends of amine and polyphenol resin / polyacrylic resin in weight ratios of 100 / 140, 100 / 110, and 100 / 80 were prepared as described above using 110 g of 2,4,6-tris(dimethylaminomethyl)phenol, 77 g of acrylic resin, and 77 g of polyphenol resin. A second blend was prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 68.75 g of acrylic resin, and 68.75 g of polyphenol resin. A third blend was prepared similarly using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 50 g of acrylic resin, and 50 g of polyphenol resin. The preparation of Equation 3 is summarized below. [Table 2] (c) Formulation 3: Solution of 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine K54) in a polyphenol resin and polyacrylic resin blend (PN 320 / Joncryl 67). Blends of amine and polyphenol resin / polyacrylic resin in weight ratios of 100 / 140, 100 / 110, and 100 / 80 were prepared as described above using 110 g of 2,4,6-tris(dimethylaminomethyl)phenol, 77 g of acrylic resin, and 77 g of polyphenol resin. A second blend was prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 68.75 g of acrylic resin, and 68.75 g of polyphenol resin. A third blend was prepared similarly using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 50 g of acrylic resin, and 50 g of polyphenol resin. The preparation of formulation 4 is summarized below. [Table 3] (d) Formulation 4: Solution of 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine K54) in a polyphenol resin and polyacrylic resin blend (PN 320 / Epomatt G-152). Blends of amine and polyphenol resin / polyacrylic resin in weight ratios of 100 / 140, 100 / 110, and 100 / 80 were prepared as described above using 110 g of 2,4,6-tris(dimethylaminomethyl)phenol, 77 g of acrylic resin (Epomatt G-152), and 77 g of polyphenol resin. A second resin was prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 68.75 g of acrylic resin, and 68.75 g of polyphenol resin. A similar mixture was prepared using 125 g of 2,4,6-tris(dimethylaminomethyl)phenol, 50 g of acrylic resin, and 50 g of polyphenol resin. The preparation of formulation 5 is shown below. [Table 4]

[0068] Example 2: Differential scanning calorimetry (DSC) of amine solutions in polymer phenols combined with other resins. DSC as a DICY accelerator A sample of the amine solution from Example 1 was mixed with dicyandiamide (DICY), fumed silica, and bisphenol A diglycidyl ether (mass ratio 2:6:2:100). The mixture was analyzed by DSC (TA instruments QA20, software V24.10 Build 122) to determine the curing onset temperature, reaction heat (ΔH), and glass transition temperature (Tg). DSC was performed using the software included with the DSC, following standard procedures. The sample was heated from -25°C to 300°C at a heating rate of 10°C per minute. 2,4,6-tris(dimethylaminomethyl)phenol (Ancamine K54) and a 1:1.1 combination of 2,4,6-tris(dimethylaminomethyl)phenol and polyphenol resin (Alnovol PN-320) were used as controls. The results are summarized in the table below. [Table 5]

[0069] Example 3: Latency of amine solutions in polymer phenols combined with other resins A sample of the amine solution from Example 1 was mixed with dicyandiamide (DICY), fumed silica, and bisphenol A diglycidyl ether (mass ratio 2:6:2:100). The latent properties of the resulting epoxy formulation were monitored using a 0.5 mL sample at 25°C with a Brookfield Cone and Plate viscometer (model HADV II+CP) equipped with a #52 spindle, as measured by the viscosity change during aging at 40°C. Storage stability was determined by visual observation, and the gelation time was determined. The results are shown in the table below. [Table 6]

[0070] Example 4: Adhesion characteristics The adhesive properties of a simple epoxy adhesive formulation containing the curing agent of Example 1 were measured by lap shear strength and T-peel technique. Lap shear strength measurements were performed at least five times in an Instron Model 1125 apparatus according to ASTM method D1876. The test material was applied to a 1-inch x 0.4-inch x 0.32-inch cold-rolled steel panel (ACT COLD ROLL Steel 01X04X032 B952 P60 DIW: unpolished). The material was applied to the 1 / 2-inch end of a coupon along with 10 mil glass beads (1% based on the weight of the formulation). Another coupon was placed on top, overlapping the 1 / 2-inch strip of the other coupon. The panel containing the test material was cured at a temperature of 130°C to 160°C for 15 to 30 minutes, and then cooled to room temperature before measurement.

[0071] T-type delamination was performed at least five times in an Instron Model 1125 apparatus according to the ASTM method D1876 for lap shear strength. The test material was applied to a 1-inch x 4-inch x 0.32-inch cold-rolled steel panel (ACT COLD ROLL Steel 01X04X032 B952 P60 DIW: unpolished) that had been pre-bent at a right angle 7 / 8 inch from the edge, leaving a 3 1 / 8-inch x 1-inch surface. The material was applied together with 10 mil glass beads (1% based on the weight of the mixture). The test material was cured at a temperature of 130°C to 160°C for 15 to 30 minutes, and then cooled to room temperature before measurement. The results of the lap shear strength and T-type delamination measurements are shown in the table below. [Table 7]

[0072] While this disclosure has been described with reference to specific aspects or embodiments, those skilled in the art will understand that various modifications may be made and elements may be replaced with equivalents without departing from the scope of this disclosure. Furthermore, many modifications may be made to adapt the teachings of this disclosure to specific circumstances or materials without departing from the essential scope of this disclosure. Thus, this disclosure is not limited to the specific aspects or embodiments disclosed as the best mode intended for carrying out this disclosure, and is intended to include all embodiments that fall within the scope of the appended claims, including the use of aspects or embodiments of this disclosure individually or in combination with each other.

Claims

1. It contains an amine and a mounting agent system. The aforementioned mounting agent system is Polyphenol resin and An additional excipient selected from functional and / or non-functional components, A latent curing accelerator composition containing the following.

2. The aforementioned amine, (a) alkyl or aryl-substituted tertiary amines (e.g., monotertiary amines), (b) Tertiary amines having more than two peralkylated nitrogen atoms, (c) Tertiary amines having more than two permethylated nitrogen atoms, (d) N,N-dimethyl polyamine having at least one primary amine and at least one secondary amine, (e) Crosslinked or condensed bicyclic diamines, and / or (f) Imidazoles which may be substituted with alkyl, aryl, alkylaryl, alkyl ether, alkylamino, or at least one halogen (e.g., alkylamino-substituted imidazole, 2-alkyl or aryl-substituted imidazole, e.g., 2-methylimidazole) The composition according to claim 1, selected from at least one of the following.

3. The composition according to claim 1 or 2, wherein the amine comprises one or more of the following: 3,3',3''-imino-tris-(N,N-dimethylpropylamine), 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), triethylenediamine (TEDA), 1-(3-aminopropyl)imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, [(dimethylamino)methyl]phenol, bis-[(dimethylamino)methyl]phenol, and tris-(dimethylaminomethyl)phenol (e.g., 2,4,6-tris-(dimethylaminomethyl)phenol), [(dimethylamino)methyl]phenol, and mixtures of bis- and tris-(dimethylamino)methyl substituted phenols.

4. The composition according to any one of claims 1 to 3, wherein the amine is selected from [(dimethylamino)methyl]phenol, bis-[(dimethylamino)methyl]phenol and tris-(dimethylaminomethyl)phenol (e.g., 2,4,6-tris-(dimethylaminomethyl)phenol), and combinations thereof.

5. The composition according to any one of claims 1 to 4, wherein the polyphenol resin is a phenol novolac resin (for example, a novolac resin selected from phenol-formaldehyde resin and p-cresol-formaldehyde resin).

6. The composition according to any one of claims 1 to 5, wherein the polyphenol resin has a molecular weight of about 5,000 D to about 30,000 D.

7. The composition according to any one of claims 1 to 6, wherein the additional excipient is a functional polymer compound, for example, a polymer compound containing one or more carboxyl groups and / or hydroxyl groups.

8. The composition according to any one of claims 1 to 7, wherein the additional excipient is selected from one or more of polyamide resins, polybutadiene resins, polyether resins, and acrylic resins.

9. The composition according to any one of claims 1 to 8, wherein the additional excipient is an acrylic resin.

10. The aforementioned acrylic resin is given by the following formula: 【Chemistry 1】 (In the formula, R １ is H or C １－３ Selected independently of alkyl, R ２ is H or C １－８ (It is an alkyl group, and the alkyl group may be substituted with -OH.) The composition according to claim 8 or 9, having the structure of the following.

11. The composition according to any one of claims 8 to 10, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer and a vinyl monomer with an unsaturated monomer containing a hydroxyl group or a carboxyl group.

12. The composition according to any one of claims 8 to 11, wherein the acrylic resin is formed by free radical polymerization of an acrylic monomer containing a hydroxyl group, a carboxyl group, and / or an ester group.

13. The composition according to any one of claims 1 to 12, wherein the weight ratio of the amine to the mounting agent system is about 1:0.3 to about 1:10, or about 1:0.3 to about 1:2, or about 1:0.5 to about 1:1.5, or about 1:0.8, or about 1:1.1, or about 1:1.

4.

14. The composition according to any one of claims 1 to 13, wherein the weight ratio of the polyphenol to the additional excipient is about 1:4 to about 4:1, for example, about 1:3 to about 3:1, about 2:1 to about 1:2, or about 1:

1.

15. The composition according to any one of claims 1 to 14, wherein a curable epoxy system is formed in combination with an epoxy resin, and the curable epoxy system does not gel after 4 weeks under accelerated aging conditions (for example, storage at 40°C for 4 weeks).

16. The composition according to any one of claims 1 to 15, wherein the epoxy resin is combined to form a curable epoxy system, the curable epoxy system yielding a lap shear strength of at least 500 psi, for example, about 500 psi to 1700 psi.

17. A method for curing a substance by using a latent curing accelerator composition comprising an amine and a encapsulating agent system, The aforementioned mounting agent system Polyphenol resin and An additional excipient selected from functional and / or non-functional components, Includes, A method comprising the steps of combining the substance with the latent curing accelerator composition and heating the resulting mixture.

18. The method according to claim 17, wherein the substance is an epoxy resin.

19. The method according to claim 17 or 18, wherein the composition is a latent curing agent for epoxy resins (e.g., a sole latent curing agent), or the composition is used as an accelerator for a curing agent for epoxy resins, such as DICY or an acid anhydride.

20. The method according to any one of claims 17 to 19, wherein the composition is used as a latent curing accelerator for structural adhesives and composites, compositions for electrical potting and sealing, reinforcement and / or damping, field-curing pipes, impact-resistant adhesives, filament windings, transfer molding powders, prepregs containing solid or liquid epoxy, sheet molding compounds, coatings for concrete, wood, metal and the like, resin transfer molding, and / or EV battery pack adhesives.

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