Secondary amine-terminated blocked polyamides, as well as methods for their preparation and use.

Abstract

The present invention discloses secondary amine-terminated block polyamides, as well as methods for preparing and using them, specifically block polyamides containing terminal secondary amine groups, epoxy curing compositions containing the block polyamide, epoxy formulations containing the epoxy curing composition or the block polyamide as an epoxy curing agent, curing products of the epoxy formulation, articles containing the curing products, methods for preparing the block polyamide, and the use of the block polyamide as an epoxy curing agent in coatings, adhesives, fiber-reinforced composites and mortars.

Description

Technical Field

[0001] The present invention relates to a block polyamide containing a terminal amine group, an epoxy curing composition containing the block polyamide, a method for preparing the block polyamide, and the use of the block polyamide as an epoxy curing agent in coatings, adhesives, composites, and mortars.

[0002] Background Art Epoxy is one of the most versatile classes of polymers with various applications such as coatings, adhesives, composites, etc. Most cured epoxy resins result in amorphous thermosetting resins that have excellent mechanical strength and toughness, outstanding chemical resistance, moisture resistance, and corrosion resistance, and do not release volatiles during curing and have little shrinkage.

[0003] However, some crosslinked unmodified epoxy systems exhibit brittleness, low flexibility, as well as low impact strength and fracture resistance. Generally, there are two approaches used to modify epoxy to improve these characteristics.

[0004] One approach is to use reinforcing agents in the epoxy system. Elastomers such as carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) and amine-terminated poly(butadiene-co-acrylonitrile) (ATBN) are popular as reinforcing agents for epoxy. However, these elastomers have the drawback of high cost.

[0005] Another approach involves using flexible curing agents in epoxy systems. Dimer fatty acid and polyamine-based polyamide curing agents improve flexibility or elongation by providing chain segments with greater free rotation between crosslinks. Polyoxyalkylene polyamines, such as JEFFAMINE® D230 and JEFFAMINE® D400 (Huntsman's trade name), are also common flexible curing agents used alone or modified with polyamides. However, Jeffamine can present compatibility issues when mixed with epoxy resins, and the flexibility of these curing agents still needs further improvement.

[0006] U.S. Patent No. 5,128,441 discloses a block polyamide polyamine prepared by reacting a polyoxyalkylenediamine or triamine containing terminal primary amine groups with an aliphatic or aromatic dicarboxylic acid, or its anhydride or alkyl ester, in an amount sufficient to react 1 mole of dicarboxylic acid reactant with each terminal primary amine group of the polyoxyalkylene polyamine to obtain an intermediate condensation product having terminal carboxyl groups, and by reacting 1 mole of organic diprimeramine with each terminal carboxyl group of the intermediate reaction product to obtain a primary amine-terminated polyamide block condensation product.

[0007] According to U.S. Patent No. 5,128,441, the presence of terminal primary amine groups in the block polyamidediamine and triamine condensation product is essential. While such block polyamidediamine and triamine condensation products increase rigidity or hardness, there is still room for improvement in terms of flexibility.

[0008] U.S. Patent No. 4082708 discloses a two-component epoxy adhesive composition in which part A comprises a curable liquid epoxide and part B comprises a bisaminopiperazine-containing thermoplastic polyamide curing agent. U.S. Patent No. 4082708 teaches that secondary amines may be used in the preparation of the polyamide of this invention, but terminating the polyamide with a secondary amino substituent is preferably avoided, i.e., it is preferable that the secondary amine is "embedded" in the polyamide structure.

[0009] U.S. Patent Application Publication No. 2003173707 discloses the use of a hot-melt adhesive for the manufacture of molded articles and a method for manufacture such molded articles. The hot-melt adhesive is a polyamide manufactured from [a] 80 to 100 mol% of one or more C4-C18 dicarboxylic acids, [b] 10 to 100 mol% of at least one aliphatic diamine, [c] 10 to 80 mol% of one or more alicyclic diamines, and [d] 0 to 80 mol% of polyetherdiamine. The polyamide manufactured by a one-step process is a hot-melt adhesive that is entirely different from epoxy-based curing agents.

[0010] Therefore, there is a need for polyamides used as epoxy curing agents that effectively combine cost-effectiveness and high flexibility.

[0011] Summary of the Invention The object of the present invention is to provide a novel amine-terminated block polyamide for epoxy-based curing agents that is cost-effective and highly flexible.

[0012] However, the inventors have found that the block polyamide of formula (I) according to the present invention makes it possible to solve these technical problems.

[0013] The block polyamide of the present invention is of the following formula (I): [ka] [In formula (I), Each R1 independently represents a divalent aliphatic or aromatic group having an average molecular weight of 42 to approximately 700, specifically 200 to 700, more specifically 500 to 600, and containing 3 to 42 carbon atoms, specifically 10 to 42 carbon atoms, more specifically 30 to 40 carbon atoms. R2 is [ka] This represents, In the formula, n' represents a positive number whose average value is between 2 and 80, specifically between 2 and 20, and more specifically between 2 and 10. or [ka] This represents, In the formula, -C3H6- may be linear or branched, a+c is equal to a positive number with an average value of 2 to about 10, b is a positive number with an average value of 1 to about 50, or [ka] This represents, In the formula, A represents a trivalent hydrocarbon group consisting of 3 to 6 carbon atoms, obtained by propoxylation of a propoxylable trivalent alcohol containing 3 to 6 carbon atoms. w, y, and z are positive integers, and the average value of the sum of w+y+z is between 4 and approximately 120. n represents an integer from 1 to 10. R3 is expressed independently by the formula: R4NH-R5-NR6- It represents a monovalent base having, In the formula, R4 and R5 each independently represent an aliphatic, alicyclic, or aromatic group containing 1 to 10 carbon atoms. R6 represents an aliphatic, alicyclic, or aromatic group containing a hydrogen atom or 1 to 10 carbon atoms, or R3 is expressed independently by the formula: [ka] represents a monovalent group having R7 and R8, together with the two nitrogen atoms to which R7 and R8 are attached, form a 4- to 7-membered heterocyclic ring optionally substituted with an alkyl group, or R3, each independently, has the formula:

Chemical formula

[0014] In this specification, the molecular weight is number-averaged and is tested by gel permeation chromatography (GPC).

[0015] The amine-terminated block polyamide of formula (I) is characterized by the presence of a terminal secondary amine group. Compared with a primary amine-terminated polyamide, the lower functionality of the secondary amine-terminated polyamide results in a lower crosslink density and higher flexibility when cured with an epoxy resin.

[0016] The block polyamide of the present invention is cost-effective and can achieve good strength and flexibility. Therefore, the block polyamide of the present invention can be used to replace ATBN in at least some applications.

[0017] The present invention also provides epoxy curing compositions comprising at least one of the previously defined formula (I) block polyamides, methods for preparing the block polyamides of the present invention, and the use of the block polyamides of the present invention as epoxy curing agents in coatings, adhesives, fiber-reinforced composites, and mortars.

[0018] When the aforementioned block polyamide is used in an epoxy system, the cured product exhibits fast-setting and highly flexible properties, which are attractive characteristics for many applications, such as coatings, adhesives, fiber-reinforced composites, and mortars.

[0019] Other advantages of the present invention will be apparent to those skilled in the art by reading this specification.

[0020] Detailed description of the invention However, the subject of the present invention is a secondary amine-terminated block polyamide of the following formula (I).

[0021] [ka]

[0022] According to a particular embodiment of the present invention, the block polyamide of formula (I) is such that R1 each independently comprises 3 to 42 carbon atoms, specifically 10 to 42 carbon atoms, more specifically 30 to 40 carbon atoms, and has an average molecular weight of 42 to about 700, specifically 200 to 700, and more specifically 500 to 600, representing a divalent aliphatic saturated or unsaturated hydrocarbon group.

[0023] Suitable COOH-R1-COOH compounds that can be used as starting materials for the present invention can be selected from, for example, adipic acid where R1 represents divalent butyl, dodecanediic acid where R1 represents divalent decyl, glutaric acid where R1 represents divalent propyl, azelaic acid where R1 represents divalent heptyl, sebacic acid where R1 represents divalent octyl, or dimer acids obtained by dimerization of tall oil fatty acids.

[0024] According to a particular embodiment of the present invention, the block polyamide (I) has R2, [ka] This represents, n' represents a positive number whose average value is between 2 and 80, specifically between 2 and 20, and more specifically between 2 and 10.

[0025] Representative NH2R2NH2 materials that can be used as starting materials for the present invention include JEFFAMINE® D-230 amine with an n' value of 2.6, JEFFAMINE® D-400 amine with an n' value of 5.6, and JEFFAMINE® D-2000 amine with an n' value of approximately 33.

[0026] According to another specific embodiment of the present invention, the block polyamide of formula (I) is such that R2 is [ka] This represents, In the formula, -C3H6- may be linear or branched, a+c is equal to a positive number with an average value between 2 and approximately 10, and b is a positive number with an average value between 1 and approximately 50.

[0027] Representative NH2R2NH2 compounds that can be used as starting materials for the present invention include JEFFAMINE® ED-600, where b is approximately 8.5 and a+c is approximately 2.5; JEFFAMINE® ED-900, where a+c is approximately 2.5 and b is approximately 15.5; JEFFAMINE® ED-2001, where a+c is approximately 2.5 and b is approximately 40; and Ancamine® 1922A, where a is 0, c is 1, and b is 2.

[0028] According to one embodiment of the present invention, the block polyamide has R2, [ka] This is the expression (I) that represents, In the formula, A represents a trivalent hydrocarbon group consisting of 3 to 6 carbon atoms, obtained by propoxylation of a propoxylable trivalent alcohol containing 3 to 6 carbon atoms. w, y, and z are positive integers, and the average value of the sum of w+y+z is between 4 and approximately 120.

[0029] Examples of triamine R2(NH2)3 that can be used as a starting material for the present invention include JEFFAMINE® T-403, in which A represents a trimethylolpropane core and the average sum of w+y+z is approximately 5.3; JEFFAMINE® T-3000, in which A represents a trimethylolpropane core and the average sum of w+y+z is approximately 50; and JEFFAMINE® T-5000, in which A represents a glycerol core and the average sum of w+y+z is approximately 86.

[0030] According to one embodiment of the present invention, in block polyamide (I), R6 represents a hydrogen atom.

[0031] According to a particular embodiment of the present invention, block polyamide (I) is such that R3 is independently of each other, by formula: [ka] It represents a monovalent base having, In the formula, R7 and R8, together with the two nitrogen atoms to which they are bonded, form a piperazinium ring, and the piperazinium ring is optionally substituted with an alkyl group.

[0032] According to a particular embodiment of the present invention, block polyamide (I) is such that R3 is independently of each other, by formula: [ka] It represents a monovalent base having, In the formula, R9 and R 10 R9 and R10 Together with the two nitrogen atoms to which it is bonded, it forms a piperazinium ring, and the piperazinium ring is optionally substituted with an alkyl group. R 11 This is as defined earlier.

[0033] More specifically, the diamine R3H that can be used as a starting material for the present invention represents a diamine selected from N-(2-aminoethyl)piperazine, piperazine, and 3-(cyclohexylamino)-1-propylamine. In one embodiment, R3 is derived from a diamine selected from the group consisting of N-(2-aminoethyl)piperazine, piperazine, and 3-(cyclohexylamino)-1-propylamine.

[0034] The secondary amine-terminated block polyamide of the present invention can be used as an epoxy curing agent in applications such as coatings, adhesives, fiber-reinforced composites, and mortars.

[0035] In some embodiments, the diamine R3H is N-(2-aminoethyl)piperazine. In some embodiments, the secondary amine-terminated block polyamide of the present invention is used as an epoxy curing agent in coatings.

[0036] The present invention relates to a method for preparing a secondary amine-terminated block polyamide of formula (I), (1) A carboxyl-terminated prepolymer is obtained by reacting a polyoxyalkylene polyamine NH2R2NH2 or R2(NH2)3 with a dicarboxylic acid having the formula COOH-R1-COOH, or its anhydride or C1-C4 alkyl ester. (2) Reacting a carboxyl-terminated prepolymer with diamine R3H to obtain a secondary amine-terminated block polyamide. Includes, R1, R2, and R3 are as previously defined, and we will provide further methods.

[0037] Preferably, the molar ratio of polyoxyalkylene polyamine to dicarboxylic acid or its anhydride or C1-C4 alkyl ester is 1:1.05 to 1:4, and the molar ratio of the difference between diamine R3H and the dicarboxylic acid or its anhydride or C1-C4 alkyl ester and the polyoxyalkylene polyamine is 1:1.05 to 1:4, so that 1 mole of diamine reacts with each of the terminal carboxyl groups of the prepolymer from step (1), thereby forming an amine-terminated block polyamide.

[0038] The condensation reactions in steps (1) and (2) are preferably heated to 50-280°C, preferably 150-280°C, and more preferably 180-250°C, for 2-6 hours, optionally in a vacuum. Preferably, any water produced by the reaction is removed.

[0039] The subject of the present invention is also an epoxy curing composition containing the block polyamide of formula (I) defined above. The epoxy curing composition can be used as an epoxy curing agent in applications such as coatings, adhesives, fiber-reinforced composites, and mortars.

[0040] According to a particular embodiment of the present invention, the block polyamide of formula (I) defined above accounts for 1 to 100% by weight, more specifically 10 to 90% by weight, and preferably 20 to 70% by weight, of the total weight of the epoxy curing composition.

[0041] An epoxy curing composition useful in the context of the present invention may optionally contain at least one additional polyamine conventionally used as a curing agent. This can be selected from Ancamide® 350A or Ancamine® 1618, which are commercially available from Evonik Industries AG.

[0042] The content of additional polyamide in the epoxy curing composition, if present, is generally in the range of 10 to 90% by weight, preferably 20 to 50% by weight, relative to the weight of the epoxy curing composition.

[0043] The subject of the present invention is also an epoxy formulation selected from coatings, adhesives, mortars, and fiber-reinforced composites, comprising the epoxy curing composition of the present invention as an epoxy curing agent or the block polyamide of the present invention and an epoxy resin. The epoxy resin is known in the art.

[0044] In this disclosure, the epoxy resin may preferably contain one or more glycidyl ethers selected from the group of glycidyl ethers of resorcinol, hydroquinone, 4,4'-methylenebis(2,6-dimethylphenol) (tetramethylbisphenol F), 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 (bisphenol A), bis-(4-hydroxyphenyl)-methane (bisphenol F), and any combination thereof. Epoxy resins are commercially available from various chemical manufacturers, for example, Olin Corporation's DER® 331, 351, or 731. Several epoxy compounds are also described, for example, in European Patent Application Publication No. 675185.

[0045] To provide greater functionality or characteristics and meet industrial requirements, epoxy formulations may preferably contain additives. Preferred additives can be selected from the group consisting of fillers, reinforcing agents, coupling agents, strengthening agents, defoamers, dispersants, lubricants, colorants, marking materials, dyes, pigments, IR absorbers, antistatic agents, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retardants, conductive additives, carbon black, graphite, carbon nanotubes, graphene, drying agents, release agents, leveling aids, flame retardants, separating agents, optical lighteners, rheological additives, photochromic additives, softeners, adhesion accelerators, drip inhibitors, metallic pigments, stabilizers, metallic glitter, metallic coated particles, porous inducers, plasticizers, glass fibers, nanoparticles, flow aids, and combinations thereof.

[0046] The subject of this invention is also the cured product of the epoxy compound described above. The curing method is well known in the art.

[0047] The subject of the present invention is also an article comprising the above-mentioned curing product and a substrate such as metal, plastic, ceramic, or concrete.

[0048] The subject of this invention is also the use of the previously defined block polyamide of formula (I) as an epoxy curing agent in coatings, adhesives, fiber-reinforced composites, and mortars.

[0049] In the formula, the present invention will be described in detail by the following embodiments. The scope of the present invention should not be limited to the embodiments of the examples. [Examples]

[0050] [Table 1]

[0051] [Table 2]

[0052] Example 1 (E1) JEFFAMINE® D400 (43 g, 0.1 mol) and dimer acid (116 g, 0.2 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. When the amine value fell below 1 mg KOH / g, the reaction mixture was cooled to 150 °C and N-AEP (27.13 g, 0.21 mol) was added. The reaction mixture was then maintained at 230 °C for a further 2 hours. After cooling to room temperature, an amber-colored liquid was obtained. (Amine value: 130 mg KOH / g, viscosity: 65,000 cps at 40°C)

[0053] Example 2 (E2) Ancamine® 1922A (22 g, 0.1 mol) and dimer acid (116 g, 0.2 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. When the amine value fell below 1 mg KOH / g, the reaction mixture was cooled to 150 °C and N-AEP (27.13 g, 0.21 mol) was added. The reaction mixture was then maintained at 230 °C for a further 2 hours. After cooling to room temperature, an amber liquid was obtained. (Amine value: 151 mg KOH / g, viscosity: 42,000 cps at 50°C)

[0054] Example 3 (E3) JEFFAMINE® D400 (43 g, 0.1 mol) and dimer acid (116 g, 0.2 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. When the amine value fell below 1 mg KOH / g, the reaction mixture was cooled to 150 °C and piperazine (18.06 g, 0.21 mol) was added. The reaction mixture was then maintained at 230 °C for a further 4 hours. After cooling to room temperature, an amber liquid was obtained. (Amine value: 77 mg KOH / g, viscosity: 26,000 cps at 40°C)

[0055] Comparative example 1 (CE1) In a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line, N-AEP (27.13 g, 0.21 mol), JEFFAMINE® D400 (43 g, 0.1 mol), and dimer acid (116 g, 0.2 mol) were added. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. After cooling to room temperature, an amber-colored liquid was obtained. (Amine value: approximately 128 mg KOH / g, viscosity: 50,800 cps at 40°C)

[0056] Comparative Example 2 (CE2) JEFFAMINE® D400 (43 g, 0.1 mol) and dimer acid (116 g, 0.2 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. When the amine value fell below 1 mg KOH / g, the reaction mixture was cooled to 150 °C and TETA (30.7 g, 0.21 mol) was added. The reaction mixture was then maintained at 230 °C for a further 2 hours. After cooling to room temperature, an amber liquid was obtained. (Amine value: 162 mg KOH / g, viscosity: 68,000 cps at 40°C)

[0057] Comparative Example 3 (CE3) JEFFAMINE® D400 (43 g, 0.1 mol) and dimer acid (116 g, 0.2 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated at 230 °C for 2 hours. The completion of the reaction was monitored using amine titration. When the amine value fell below 1 mg KOH / g, the reaction mixture was cooled to 150 °C and IPDA (35.76 g, 0.21 mol) was added. The reaction mixture was then maintained at 230 °C for a further 2 hours. After cooling to room temperature, an amber liquid was obtained. (Amine value: 65 mg KOH / g, viscosity: 39,000 cps at 70°C)

[0058] Comparative Example 4 (CE4) JEFFAMINE® D400 (64.5 g, 0.15 mol) and dimer acid (58 g, 0.1 mol) were added to a 250 ml four-necked flask equipped with a thermometer, addition funnel, Dean-Stark trap, stirrer, and nitrogen line. The mixture was heated to 230 °C for 2 hours. After cooling to room temperature, an amber-colored liquid was obtained. (Amine value: 40 mg KOH / g, viscosity: 66,000 cps at 25°C)

[0059] Comparative Example 5 (CE5) Huntsman's JEFFAMINE® D2000, polypropylene diamine, MW = 2000 g / mol

[0060] Table 3 below summarizes the materials and synthesis processes for Examples 1-3 and Comparative Examples 1-5. Except for the amine used in the second step, the preparation of the polyamides in Examples 1 and 3 is the same as that in Comparative Examples 2 and 3.

[0061] [Table 3]

[0062] Performance testing To test the performance of the polyamide epoxy curing agents prepared in Examples 1-3 and Comparative Examples 1-5 for adhesive applications, adhesives were prepared according to the formulations in Table 4 (using the specified parts by weight).

[0063] Furthermore, the following comparative formulations were included in the test: Formulation 1 is an adhesive formulation that does not use any modifiers, and Formulation 5 is an adhesive formulation that uses conventional ATBN as a modifier.

[0064] The performance of the adhesive was determined, and the results are summarized in Table 4 below.

[0065] The amine hydrogen equivalent (AHEW) in g / mol units is calculated by dividing the molecular weight of the amine by the number of amine hydrogen atoms per molecule.

[0066] The epoxide equivalent, or epoxide group content as expressed by EEW, is the ratio between the molecular weight of the epoxide and the number of epoxide groups.

[0067] [Table 4-1] [Table 4-2]

[0068] To test the performance of the polyamide epoxy curing agents prepared in Examples 1-2 and Comparative Examples 1-5 for coating applications, the resin portion (Part A) and curing agent portion (Part B) of the coating were prepared according to the formulations in Table 5 (using the specified parts by weight).

[0069] Furthermore, the following comparative formulations were included in the test: Formulation 11 is a coating formulation that does not use any modifiers, and Formulation 14 is a coating formulation that uses conventional ATBN as a modifier.

[0070] The performance of the coating was determined, and the results are summarized in Table 5 below.

[0071] [Table 5]

[0072] Good flexibility can be demonstrated by high elongation in adhesive formulations and high impact resistance in coating formulations. Comparative Example 4, a D400-based polyamide, and Comparative Example 5, JEFFAMINE® D2000, are two conventional flexible curing agents. However, CE4 did not exhibit high elongation and good impact resistance. The addition of CE5 improved elongation and impact resistance, but did not show improvement in overlap shear strength, one of the most important properties for adhesive applications. In addition, both CE4 and CE5 showed phase separation during the "drying time" test. This can be explained by the low compatibility between Jeffamine and the epoxy resin and the slow curing rate.

[0073] In Comparative Example 1, the same raw materials as in Example 1 were used, but the product was prepared using a different process that resulted in different terminal functional groups and molecular weights. Compared to Comparative Example 1, the formulation containing the polyamide epoxy curing agent in Example 1 showed a faster curing rate in addition to better elongation and overlapping shear strength, as shown in Table 4.

[0074] As shown in Table 4, compared to formulation 1, which contains no modifiers, the formulations of Examples 1-3, which contain polyamide epoxy curing agents, showed improved performance in both elongation at break and lap shear strength.

[0075] As shown in Table 4, formulations 2-4 (each containing the polyamide epoxy curing agents of Examples 1-3) showed better performance in tensile strength and tensile modulus compared to formulation 5, which is an adhesive formulation using conventional ATBN as a modifier. Notably, formulation 4, containing the polyamide epoxy curing agent of Example 3, showed remarkably superior overlap shear strength compared to formulation 5 and formulations 6-8, each containing the polyamide epoxy curing agents of Comparative Examples 1-3.

[0076] As shown in Table 4, comparing Examples 1 and 3 with Comparative Examples 2 and 3 clearly shows that replacing primary amine-terminated polyamides with secondary amine-terminated polyamides significantly improves both the overlap shear strength and the elongation at break.

[0077] By comparing Examples 1 and 2 with Comparative Examples 2 and 3, it is clear that the block polyamide of the present invention exhibits significantly better elongation, lap shear strength, and impact resistance than the polyamides of Comparative Examples 2 and 3, as shown in Tables 4 and 5, and demonstrates flexibility similar to that of ATBN.

[0078] As used herein, terms such as “comprise(s)” are open terms meaning “including at least” unless otherwise specified.

[0079] All references, tests, standards, literature, publications, etc., mentioned herein are incorporated herein by reference. Where numerical limits or ranges are specified, the endpoints are included. Furthermore, all values ​​and subranges within the numerical limits or ranges are included as specifically as if they were explicitly written out.

[0080] The above description is provided to enable those skilled in the art to construct and use the present invention, and is provided in the context of a particular use and its requirements. Various modifications to preferred embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and uses without departing from the spirit and scope of the invention. For this reason, the invention is not intended to be limited to the embodiments shown, but rather should be given the broadest scope consistent with the principles and features disclosed herein. In this regard, certain particular embodiments within the invention may not, when considered broadly, demonstrate all the advantages of the invention.

Claims

1. Equation (I): 【Chemistry 1】 [In the formula, each R １ This independently represents a divalent aliphatic or aromatic group having an average molecular weight of 42 to approximately 700, specifically 200 to 700, more specifically 500 to 600, and containing 3 to 42 carbon atoms, specifically 10 to 42 carbon atoms, more specifically 30 to 40 carbon atoms. R ２ teeth, 【Chemistry 2】 (In the formula, n' represents a positive number whose average value is between 2 and 80, specifically between 2 and 20, and more specifically between 2 and 10.) Does it represent, 【Transformation 3】 (In the formula, -C ３ H ６ (The negative sign may be linear or branched, a + c is equal to a positive number with an average value between 2 and approximately 10, and b is a positive number with an average value between 1 and approximately 50.) To represent, or 【Chemistry 4】 (In the formula, A represents a trivalent hydrocarbon group consisting of 3 to 6 carbon atoms, obtained by propoxylation of a propoxylable trivalent alcohol containing 3 to 6 carbon atoms; w, y, and z are positive integers; and the average value of the sum of w + y + z is between 4 and approximately 120.) This represents, n represents an integer between 1 and 10. Each R ３ The formula is: R ４ NH-R ５ -NR ６ - (wherein, R ４ and R ５ each independently represents an aliphatic, alicyclic or aromatic group containing 1 to 10 carbon atoms, and R ６ represents a hydrogen atom or an aliphatic, alicyclic or aromatic group containing 1 to 10 carbon atoms) It represents a monovalent group having, or Each R ３ The formula is: 【Transformation 5】 (In the formula, R ７ and R ８ R ７ and R ８ (Together with the two nitrogen atoms to which it is bonded, it forms a 4- to 7-membered heterocycle that is optionally substituted with an alkyl group.) It represents a monovalent group having, or Each R ３ The formula is: 【Transformation 6】 (In the formula, R ９ and R １０ R ９ and R １０ Together with the two nitrogen atoms to which it is bonded, it forms a 4- to 7-membered heterocycle which is optionally substituted with an alkyl group, R １１ (This represents a divalent aliphatic saturated or unsaturated hydrocarbon group containing 1 to 10 carbon atoms, specifically 1 to 5 carbon atoms, and more specifically 2 to 3 carbon atoms.) [Represents a monovalent base having ] A secondary amine-terminated block polyamide, A block polyamide with an average molecular weight in the range of approximately 800 to 8000.

2. R １ The polyamide according to claim 1, wherein the polyamide is selected from divalent propyl, divalent butyl, divalent heptyl, divalent octyl, or divalent decyl, or derived from a dimer acid obtained by dimerization of tall oil fatty acids.

3. R ２ but, 【Transformation 7】 (In the formula, n' = 2.6, 5.6, or 33) Represents or R ２ but, 【Transformation 8】 (In the equation, either b is approximately 8.5 and the value of a+c is approximately 2.5, or the value of a+c is approximately 2.5 and the value of b is approximately 15.5, or a+c is approximately 2.5 and the value of b is approximately 40, or a=0, c=1, b=2) Represents or R ２ but, 【Chemistry 9】 (In the formula, A represents the trimethylolpropane nucleus and the average sum of w + y + z is approximately 5.3, or A represents the trimethylolpropane nucleus and the average sum of w + y + z is approximately 50, or A represents the glycerol nucleus and the average sum of w + y + z is approximately 86.) The polyamide according to claim 1, which represents the polyamide described in claim 1.

4. R ６ A polyamide according to any one of claims 1 to 3, wherein represents a hydrogen atom.

5. R ７ and R ８ However, R ７ and R ８ The polyamide according to any one of claims 1 to 3, wherein a piperazinium ring is formed with two bonded nitrogen atoms, and the piperazinium ring is optionally substituted with an alkyl group.

6. R ９ and R １０ However, R ９ and R １０ The polyamide according to any one of claims 1 to 3, wherein a piperazinium ring is formed with two bonded nitrogen atoms, and the piperazinium ring is optionally substituted with an alkyl group.

7. R ３ The polyamide according to claim 1, wherein the polyamide is derived from a diamine selected from the group consisting of N-(2-aminoethyl)piperazine, piperazine, and 3-(cyclohexylamino)-1-propylamine.

8. A method for producing a secondary amine-terminated block polyamide according to claim 1, (1) Polyoxyalkylene polyamine NH ２ R ２ NH ２ or R ２ (NH ２ ) ３ The formula is COOH-R １ - Reacting with a COOH dicarboxylic acid, its anhydride, or its C1-C4 alkyl ester to obtain a carboxyl-terminated prepolymer, (2) The carboxyl-terminated prepolymer is diamine R ３ By reacting with H, a secondary amine-terminated block polyamide can be obtained. Includes, R １ , R ２ , R ３ A method as defined in claim 1.

9. R １ The method according to claim 8, wherein each independently represents a divalent aliphatic saturated or unsaturated hydrocarbon group containing 3 to 42 carbon atoms.

10. The method according to claim 9, wherein the dicarboxylic acid is selected from adipic acid, azelaic acid, glutaric acid, sebacic acid, and dimer acids obtained by dimerization of tall oil fatty acids.

11. R ２ but, 【Chemistry 10】 (In the formula, n' = 2.6, 5.6, or 33) Represents or R ２ but, 【Chemistry 11】 (In the equation, either b is approximately 8.5 and the value of a+c is approximately 2.5, or the value of a+c is approximately 2.5 and the value of b is approximately 15.5, or a+c is approximately 2.5 and the value of b is approximately 40, or a=0, c=1, b=2) Represents or R ２ but, 【Chemistry 12】 (In the formula, A represents the trimethylolpropane nucleus and the average sum of w + y + z is approximately 5.3, or A represents the trimethylolpropane nucleus and the average sum of w + y + z is approximately 50, or A represents the glycerol nucleus and the average sum of w + y + z is approximately 86.) The method according to claim 8, which represents the above.

12. R ６ The method according to any one of claims 8 to 11, wherein represents a hydrogen atom.

13. R ７ and R ８ However, R ７ and R ８ The method according to any one of claims 8 to 11, wherein a piperazinium ring is formed with two bonded nitrogen atoms, and the piperazinium ring is optionally substituted.

14. R ９ and R １０ However, R ９ and R １０ The method according to any one of claims 8 to 11, wherein a piperazinium ring is formed with two bonded nitrogen atoms, and the piperazinium ring is optionally substituted.

15. R ３ The method according to claim 8, wherein H represents a diamine selected from the group consisting of N-(2-aminoethyl)piperazine, piperazine, and 3-(cyclohexylamino)-1-propylamine.

16. An epoxy curing composition comprising at least a secondary amine-terminated block polyamide according to any one of claims 1 to 7.

17. An epoxy compound selected from coatings, adhesives, mortars, and fiber-reinforced composites, comprising the epoxy curing composition described in claim 16, or comprising a block polyamide and an epoxy resin as described in any one of claims 1 to 7 as an epoxy curing agent.

18. The cured product of the epoxy compound according to claim 17.

19. An article comprising the curing product described in claim 18 and a substrate such as metal, plastic, ceramic, or concrete.

20. Use of the secondary amine-terminated block polyamide according to any one of claims 1 to 7 as an epoxy curing agent in coatings, adhesives, fiber-reinforced composites, and mortars.

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