Amide compound as well as preparation method and application thereof

Abstract

The invention relates to an amide compound and a preparation method and application thereof. The amide compound has the following structural general formula: # imgabs0 #; in the formula, R1 contains an alicyclic group of C5-C10; n1 is an integer from 9 to 15, and n2 is greater than or equal to 2. The amide compound can be added into a polymer as a plasticizer, so that the heat resistance of the polymer is improved, and the mechanical property of the polymer is improved.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to an amide compound and a preparation method and application thereof. Background Art

[0002] Introducing plasticizers during polymer processing or use can improve the processing properties of polymers, promote material processing and molding, and improve the gloss and texture of the material surface. However, although traditional plasticizers added to polymer materials can improve the plasticizing effect, they will reduce the heat resistance and mechanical properties of polymer materials to a certain extent. Summary of the invention

[0003] Based on this, some embodiments of the present application provide an amide compound that can be added to a polymer material as a plasticizer to improve the heat resistance of the polymer material while improving its mechanical properties.

[0004] In addition, other embodiments of the present application also provide a preparation method and application of an amide compound.

[0005] An amide compound having the following general structural formula:

[0006] ;

[0007] In the formula, R1 contains C5~C 10 Alicyclic groups;

[0008] n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

[0009] In some of these embodiments, R1 contains cyclohexyl.

[0010] In some embodiments, n1 is an integer from 11 to 15.

[0011] In some of these embodiments, n2 is 2 or 3.

[0012] In some embodiments, n2 is 2, R1 is selected from , and One or more of; or,

[0013] n2 is 3, R1 is selected from .

[0014] In some embodiments, the raw materials for preparing the amide compound include: fatty acid and alicyclic amine, and the structural formula of the fatty acid is CH3CH2(CH2) n1 COOH; the alicyclic amine contains C5~C 10The polyamine contains alicyclic groups, and the molar ratio of the carboxyl group in the fatty acid to the amine group in the alicyclic amine is (1.02~1.2):1.

[0015] In some embodiments, the raw materials for preparing the amide compound further include a catalyst and an antioxidant;

[0016] The catalyst includes one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and p-toluenesulfonic acid; the antioxidant includes one or more of hindered phenol antioxidants and phosphite antioxidants.

[0017] In some embodiments, the alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine.

[0018] In some embodiments, the antioxidant includes a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-5):1.

[0019] In some embodiments, the hindered phenol antioxidant includes one or more of 2,6-di-tert-butyl-4-methyl-phenol, N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

[0020] The phosphite antioxidant includes one or more of 2'-ethylbis(4,6-di-tert-butylphenyl)fluorophosphite and tris(2,4-di-tert-butylphenyl)phosphite.

[0021] In some embodiments, the ratio of the mass of the catalyst to the mass of the fatty acid is (0.2-1):100.

[0022] In some embodiments, the ratio of the mass of the antioxidant to the mass of the fatty acid is (1-6):100.

[0023] A method for preparing an amide compound comprises the following steps:

[0024] The fatty acid and the alicyclic amine are subjected to an amidation reaction to prepare an amide compound;

[0025] Wherein, the structural formula of the fatty acid is CH3CH2(CH2) n1 COOH; the alicyclic amine contains C5~C 10 The structural formula of the amide compound is ;

[0026] In the formula, R1 contains C5~C 10Alicyclic groups;

[0027] n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

[0028] In some embodiments, the alicyclic amine is a polyamine containing a cyclohexyl group.

[0029] In some embodiments, the alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine.

[0030] In some of the embodiments, a catalyst and an antioxidant are also added in the step of subjecting the fatty acid and the alicyclic amine to amide reaction;

[0031] Wherein, the catalyst includes one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and p-toluenesulfonic acid;

[0032] The antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-5):1.

[0033] In some embodiments, the step of subjecting the fatty acid and the alicyclic amine to amidation reaction comprises:

[0034] Under a protective atmosphere, the fatty acid, the catalyst and the antioxidant are mixed, and heated to melt the fatty acid;

[0035] Adding the alicyclic amine to the reaction system at 70° C. to 90° C.;

[0036] The reaction system was heated to 90°C~110°C and kept warm for 0.5h~2h, then continued to be heated to 190°C~220°C and kept warm for 4h~6h, and the reaction was stopped when the acid value was less than 10mgKOH / g.

[0037] Use of the above amide compound or the amide compound prepared by the above preparation method in preparing powder coatings, aqueous dispersions or polymer materials.

[0038] A polymer material comprises a polymer matrix and an auxiliary agent, wherein the auxiliary agent comprises the above-mentioned amide compound or the amide compound prepared by the above-mentioned preparation method.

[0039] In some of the embodiments, the polymer matrix includes one or more of polyamide resin, polycarbonate, polyurethane, polyvinyl chloride, polyolefin and polyacrylonitrile.

[0040] The above-mentioned amide compounds contain multiple amide polar groups and long carbon chain structures, can form covalent bonds and / or hydrogen bonds with a variety of plastic matrix materials, and have good compatibility. At the same time, the relatively soft alicyclic structure and long carbon chain structure have little effect on the mechanical properties of the plastic matrix, such as tensile strength, and can also greatly improve its fracture toughness, while also improving the heat resistance and plasticizing effect of the plastic matrix. Therefore, the above-mentioned amide compounds can be added to polymers as plasticizers to improve the heat resistance of polymers while improving their mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0042] Figure 1 A schematic diagram of a process flow of a method for preparing amide compounds according to some embodiments of the present application. DETAILED DESCRIPTION

[0043] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with the specific embodiments. The preferred embodiments of the present application are provided in the specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0045] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0046] In this application, "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0047] In the description of the present application, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0048] In this application, "one or several" refers to any one, any two or more of the listed items. Among them, "several" refers to any two or more of the listed items.

[0049] In this application, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0050] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as a limitation on the previous technical solution, nor can it be understood as a limitation on the protection scope of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0051] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0052] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0053] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0054] The terms "including" and "having" and any variations thereof in the embodiments of the present application are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units that are not listed, or may optionally include other steps or components that are inherent to these processes, methods, products, or devices.

[0055] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments.

[0056] The term "alicyclic group" refers to a non-aromatic hydrocarbon containing ring carbon atoms, which can be a monocyclic alkyl group, a spirocyclic alkyl group, or a bridged cycloalkyl group. Phrases containing this term, for example, "C5~C 10 The term "alicyclic group" refers to an alicyclic group containing 5 to 10 carbon atoms, and each occurrence thereof can be independently a C5 alicyclic group, a C6 alicyclic group, a C7 alicyclic group, a C8 alicyclic group, a C9 alicyclic group or a C 10 Alicyclic groups. Suitable examples include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. In addition, the "alicyclic group" may also contain one or more double bonds, and representative examples of alicyclic groups containing double bonds include cyclopentenyl, cyclohexenyl, cyclohexadienyl and cyclobutadienyl, etc.

[0057] The first aspect of the present application provides an amide compound having the following general structural formula:

[0058] ;

[0059] In the formula, R1 contains C5~C 10 Alicyclic groups;

[0060] n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

[0061] The above-mentioned amide compounds contain multiple amide polar groups and long carbon chain structures, can form covalent bonds and / or hydrogen bonds with a variety of plastic matrix materials, and have good compatibility. At the same time, the relatively soft alicyclic structure and long carbon chain structure have little effect on the mechanical properties of the plastic matrix, such as tensile strength, and can also greatly improve its fracture toughness, while also improving the heat resistance and plasticizing effect of the plastic matrix. Therefore, the above-mentioned amide compounds can be added to polymers as plasticizers to improve the heat resistance of polymers while improving their mechanical properties.

[0062] In the above amide compounds, R1 contains C5~C 10Compared with the fatty chain structure, the alicyclic group is applied in polymer materials to improve its heat resistance and increase the elongation at break of the material without reducing its tensile strength. Compared with the aromatic group, the introduction of the aromatic group may reduce the mechanical strength, hardness, elongation at break, etc. of the polymer material to a certain extent. In addition, the glossiness and appearance of the polymer material will also be affected to a certain extent, reducing the anti-aging performance and service life of the plastic product. In some embodiments of the present application, the amide compound has the above-mentioned general structural formula and can be added to the polymer as a plasticizer to improve the heat resistance of the polymer while improving its mechanical properties and ensuring a good appearance and glossiness.

[0063] Therefore, the above-mentioned amide compounds provided in some embodiments of the present application have a more regular structure, excellent heat resistance, high color and low acid value. They can be used as dispersants, plasticizers, release agents or lubricants for polymer materials, have good plasticizing effects, and have certain improvements on the mechanical properties of the plastic matrix.

[0064] In some embodiments, R1 contains C5~C 10 For example, R1 contains cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. In some embodiments, R1 contains cyclohexyl.

[0065] In some embodiments, R1 does not contain an aromatic group. The introduction of an aromatic group may reduce the mechanical strength, hardness, elongation at break, etc. of the polymer material to a certain extent, and the glossiness and appearance of the polymer material may also be affected to a certain extent. Therefore, in some embodiments of the present application, R1 does not contain an aromatic group.

[0066] In some embodiments, n1 is an integer from 9 to 15. For example, n1 is 9, 10, 11, 12, 13, 14, 15, or a range consisting of any two of these values. In some embodiments, n1 is an integer from 11 to 15.

[0067] In some embodiments, n2≥2. For example, n2 is 2, 3, 4, 5, or a range consisting of any two of these values. In some embodiments, n2 is 2 or 3.

[0068] In some embodiments, n2 is 2, R1 is selected from , and One or more of the .

[0069] In other embodiments, n2 is 3, R1 is selected from .

[0070] In some embodiments, the melting point of the amide compound is ≥140° C. Optionally, the melting point of the amide compound is ≥145° C. The amide compound has a high melting point and is useful for improving the heat resistance of polymer materials when used in polymer materials.

[0071] In some embodiments, the acid value of the amide compound is less than 10 mgKOH / g. Alternatively, the acid value of the amide compound is ≤ 6 mgKOH / g. The acid value of the above amide compound is low.

[0072] In some embodiments, the whiteness of the amide compound is ≤ 5. The amide compound has a high whiteness and is applied to polymer materials to improve the appearance and color of the polymer materials.

[0073] In some embodiments, the amide compound is a white powder or a white to pale yellow powder.

[0074] In some embodiments, the raw materials for preparing the amide compound include: fatty acid and alicyclic amine, and the structural formula of the fatty acid is CH3CH2(CH2) n1 COOH; alicyclic amines contain C5~C 10 In the polyamine containing alicyclic groups, the molar ratio of the carboxyl group in the fatty acid to the amine group in the alicyclic amine is (1.02-1.2): 1. For example, the molar ratio of the carboxyl group in the fatty acid to the amine group in the alicyclic amine can be, but is not limited to, 1.02: 1, 1.05: 1, 1.08: 1, 1.1: 1, 1.12: 1, 1.15: 1, 1.18: 1, 1.2: 1 or a range consisting of any two of these values.

[0075] Specifically, the fatty acid includes one or more of stearic acid, palmitic acid, lauric acid and myristic acid. In one specific example, the fatty acid is stearic acid.

[0076] Specifically, the alicyclic amine is a polyamine containing a cyclohexyl group. Optionally, the alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine.

[0077] In some embodiments, the raw materials for preparing the amide compound further include a catalyst and an antioxidant.

[0078] Specifically, the catalyst includes one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and p-toluenesulfonic acid. In some embodiments, the ratio of the mass of the catalyst to the mass of the fatty acid is (0.2-1):100. Exemplarily, the ratio of the mass of the catalyst to the mass of the fatty acid can be, but is not limited to, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1:100 or a range consisting of any two of these values.

[0079] Specifically, the antioxidant includes one or more of a hindered phenol antioxidant and a phosphite antioxidant. Optionally, the hindered phenol antioxidant includes one or more of 2,6-di-tert-butyl-4-methyl-phenol, N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol. The phosphite antioxidant includes one or more of 2′-ethylbis(4,6-di-tert-butylphenyl)fluorophosphite and tris(2,4-di-tert-butylphenyl)phosphite.

[0080] In some embodiments, the antioxidant includes a hindered phenol antioxidant and a phosphite antioxidant. Specifically, the antioxidant includes a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-5):1. For example, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant can be, but is not limited to, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or a range consisting of any two of these values. The compounding of the two types of antioxidants in the above mass ratio is beneficial to further improve the appearance and whiteness of the amide compound and the plasticizing effect, while improving the heat resistance and elongation at break of the prepared polymer material.

[0081] In some embodiments, the ratio of the mass of the antioxidant to the mass of the fatty acid is (1-6): 100. For example, the ratio of the mass of the antioxidant to the mass of the fatty acid can be, but is not limited to, 1:100, 2:100, 3:100, 4:100, 5:100, 6:100 or a range consisting of any two of these values.

[0082] In one specific example, the fatty acid is stearic acid, and the alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine.

[0083] Due to the introduction of polyamine and amide polar groups, the above-mentioned amide compounds have a more regular structure, excellent heat resistance, high color, can form covalent bonds / hydrogen bonds with a variety of plastic matrix materials, and have good compatibility. At the same time, the relatively soft alicyclic structure has little effect on the mechanical properties of the plastic matrix, the plasticizing effect is stable, and the lubrication effect is excellent, which improves the processing performance of the plastic and also broadens its application range.

[0084] The second aspect of the present application provides a method for preparing an amide compound, comprising the following steps:

[0085] The fatty acid and the alicyclic amine are subjected to an amidation reaction to prepare an amide compound;

[0086] Among them, the structural formula of fatty acids is CH3CH2(CH2) n1 COOH; alicyclic amines contain C5~C 10 The structural formula of the amide compound is ;

[0087] In the formula, R1 contains C5~C 10 Alicyclic groups;

[0088] n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

[0089] It can be understood that the specific fatty acids and alicyclic amines are as described in the first aspect above and will not be repeated here.

[0090] In some embodiments, a catalyst and an antioxidant are added during the step of subjecting the fatty acid and the alicyclic amine to amide reaction. The specific types and amounts of the catalyst and antioxidant are as described in the first aspect above and will not be repeated here.

[0091] In some embodiments, the step of subjecting the fatty acid and the alicyclic amine to an amidation reaction comprises:

[0092] Under a protective atmosphere, fatty acid, catalyst and antioxidant are mixed and heated to melt the fatty acid;

[0093] Adding the alicyclic amine to the reaction system at 70° C. to 90° C.;

[0094] The reaction system was heated to 90°C~110°C and kept warm for 0.5h~2h, then continued to be heated to 190°C~220°C and kept warm for 4h~6h, and the reaction was stopped when the acid value was less than 10mgKOH / g.

[0095] Specifically, in the step of adding the alicyclic amine to the reaction system at 70° C. to 90° C., the adding time of the alicyclic amine is 40 min to 60 min.

[0096] Specifically, each heating rate is independently 0.5°C / min to 1°C / min.

[0097] Specifically, after the step of stopping the reaction when the acid value is less than 10 mgKOH / g, the method further includes cooling the reaction system to 160° C. to 180° C. to obtain an amide compound.

[0098] In one embodiment, see Figure 1 The step of performing amidation reaction on the fatty acid and the alicyclic amine includes step S110, step S120 and step S130:

[0099] Step S110: under a protective atmosphere, a fatty acid, a catalyst and an antioxidant are mixed and heated to melt the fatty acid, wherein the ratio of the mass of the catalyst to the mass of the fatty acid is (0.2-1):100, and the ratio of the mass of the antioxidant to the mass of the fatty acid is (1-6):100.

[0100] Step S120: adding alicyclic amine to the reaction system at 70° C. to 90° C. for 40 min to 60 min, wherein the molar ratio of the amino group in the alicyclic amine to the carboxyl group in the fatty acid is 1:(1.02 to 1.2).

[0101] Step S130: Raise the temperature of the reaction system to 90°C~110°C at a rate of 0.5°C / min~1°C / min and keep it warm for 0.5h~2h, continue to raise the temperature to 190°C~220°C and keep it warm for 4h~6h, stop the reaction when the acid value is less than 10mgKOH / g, and cool to 160°C~180°C to obtain an amide compound.

[0102] Figure 1 This is a schematic diagram of a process for preparing an amide compound according to an embodiment of the present invention. It should be understood that although Figure 1 The steps in the flowchart are shown in sequence as indicated by the arrows, but these steps are not necessarily performed in the order indicated by the arrows. Unless otherwise specified in this document, there is no strict order restriction for the execution of these steps, and they can be performed in other orders. Figure 1 At least part of the steps may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily executed at the same time, but can be executed at different times. The order of execution is not necessarily sequential, but can be executed in turn or alternately with other steps or at least part of other sub-steps or stages.

[0103] In traditional technology, amide compounds are prepared by ester exchange process, for example, fatty acid esters are reacted with organic amines, but this method will leave a certain amount of fatty acid esters, which have poor antioxidant properties and are prone to oxidation and deterioration during use, resulting in a decrease in lubrication performance. In addition, fatty acid esters have a low viscosity index and their viscosity varies greatly with temperature, which is not conducive to maintaining stable viscosity and / or lubrication effect under different temperature conditions. There is also a certain risk of hydrolysis, which affects the performance of the product. In some embodiments of the present application, fatty acids and alicyclic amines are used to carry out amidation reaction to prepare amide compounds. Amide compounds are used in polymer materials, have stable plasticizing and / or lubrication effects, and do not have the risk of hydrolysis. The prepared products have better performance, such as good surface gloss.

[0104] In addition, if the alicyclic amine is an aromatic amine, the temperature of the aromatic amine reaction is higher when using the method for preparing the amide compound of some embodiments of the present application, which can easily cause the amide compound to be oxidized, and the appearance and whiteness are insufficient, thereby affecting the appearance of the polymer material. In addition, the amide compound prepared by the aromatic amine will cause a decrease in the mechanical properties of the polymer material, such as the elongation at break. Therefore, in some embodiments of the present application, an alicyclic amine and a fatty acid are used to carry out an amidation reaction to prepare an amide compound. On the one hand, the prepared amide compound has a stable plasticizing and / or lubricating effect, and has good high temperature resistance. When used in a polymer material, it is beneficial to improve its elongation at break while ensuring a high tensile strength. On the other hand, the prepared amide compound has a good appearance, and is a white powder or a white to light yellow powder, and the whiteness is less than or equal to 5.

[0105] The third aspect of the present application provides a use of an amide compound in the preparation of a powder coating, an aqueous dispersion or a polymer material.

[0106] Specifically, the amide compound can be used as one or more of a dispersant, a plasticizer, a release agent and a lubricant for powder coatings, aqueous dispersions or polymer materials.

[0107] The fourth aspect of the present application provides a polymer material, comprising a polymer matrix and an auxiliary agent, wherein the auxiliary agent comprises the amide compound of the first aspect or the amide compound prepared by the preparation method of the second aspect.

[0108] Specifically, the polymer matrix includes one or more of polyamide resin, polycarbonate, polyurethane, polyvinyl chloride, polyolefin and polyacrylonitrile.

[0109] Specifically, the auxiliary agent may be, but is not limited to, one or more of a dispersant, a plasticizer, a release agent and a lubricant.

[0110] In one example, the mass ratio of the amide compound to the polymer matrix is ​​3: 100. It can be understood that the amide compound in some embodiments of the present application has a better plasticizing effect than the traditional amide compound, and the amount added to the polymer matrix can be less, or, when the amount added is less, the effect equivalent to that of the traditional amide compound can be achieved.

[0111] The above polymer material has good heat resistance, processing performance, mechanical properties and good appearance.

[0112] In order to make the purpose and advantages of the present application clearer, the amide compounds of the present application and their effects are further described in detail in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and shall not be used to limit the present application. The following examples do not include other components except for inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature and books or the methods recommended by the manufacturer.

[0113] The sources of the main raw materials in the following examples and comparative examples are shown in Table 1.

[0114] Table 1 Sources of raw materials

[0115]

[0116] Example 1

[0117] This embodiment provides an amide compound, and the preparation steps are as follows:

[0118] According to the mass fraction, 100 parts of stearic acid, 0.2 parts of phosphorous acid, 5 parts of antioxidant 501 and 1 part of antioxidant 168 are weighed and added to the reactor. After the protective gas is passed into the reactor, the temperature is raised until the stearic acid is completely melted and stirring is started. Continue to heat up to 90 ° C, add 4,4-diaminodicyclohexylmethane to the reactor, so that the molar ratio of the amino group in 4,4-diaminodicyclohexylmethane to the carboxyl group in stearic acid is 1: 1.02. After about 40 minutes of addition, heat to 100 ° C at a rate of 1.0 ° C / min, and keep warm for 2 hours. Then heat to 200 ° C and keep warm for 5 hours for dehydration. When the acid value is less than 10mgKOH / g, the reaction is terminated, and the material is cooled to 170 ° C to obtain the amide compound of this embodiment.

[0119] This embodiment also provides a polymer material, and the preparation steps are as follows:

[0120] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Example 1 were selected by weight, mixed thoroughly and then cast to prepare a specimen for testing.

[0121] Example 2

[0122] This embodiment provides an amide compound, and the preparation steps are as follows:

[0123] According to the mass fraction, 100 parts of stearic acid, 0.6 parts of hypophosphorous acid, 0.5 parts of antioxidant 1098 and 0.5 parts of antioxidant 168 are weighed and added to the reactor. After the protective gas is passed into the reactor, the temperature is raised until the stearic acid is completely melted and stirring is started. Continue to heat up to 90 ° C, add wanamine 2300 to the reactor, so that the molar ratio of the amino group in wanamine 2300 to the carboxyl group in stearic acid is 1: 1.1, and after about 50 minutes of addition, heat up to 110 ° C at a rate of 0.8 ° C / min, keep warm for 1.5 hours, then heat up to 220 ° C, keep warm for 4 hours for dehydration. When the acid value is less than 10mgKOH / g, the reaction is terminated, and the material is cooled to 180 ° C to obtain the amide compound of the present embodiment.

[0124] This embodiment also provides a polymer material, and the preparation steps are as follows:

[0125] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Example 2 were selected by weight, mixed thoroughly and then cast to prepare a specimen for testing.

[0126] Example 3

[0127] This embodiment provides an amide compound, and the preparation steps are as follows:

[0128] According to the mass fraction, 100 parts of n-decanoic acid, 1 part of phosphorous acid, 3 parts of antioxidant 1010 and 1 part of antioxidant 168 are weighed and added to the reactor. After the protective gas is passed into the reactor, the temperature is raised to the complete melting of stearic acid and the stirring is started. Continue to heat up to 70 ° C, add isophorone diamine, and the molar ratio of the amine group in isophorone diamine to the carboxyl group in stearic acid is 1: 1.2. After about 60min of addition, the temperature is raised to 90 ° C at a rate of 0.5 ° C / min, and the temperature is kept for 0.5 hours, and then the temperature is raised to 190 ° C, and the temperature is kept for 6 hours for dehydration. When the acid value is less than 10mgKOH / g, the reaction is terminated, and the amide compound of the present embodiment is obtained by cooling to 160 ° C.

[0129] This embodiment also provides a polymer material, and the preparation steps are as follows:

[0130] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Example 3 were weighed by mass, mixed thoroughly and then cast to prepare a specimen for testing.

[0131] Example 4

[0132] This embodiment provides an amide compound, and the preparation steps are similar to those of the amide compound of Example 1, except that the alicyclic amine is different. In this embodiment, the alicyclic amine is aminomethylcyclopentylamine (structural formula: ). Other steps are the same as those in Example 1 and will not be described in detail.

[0133] This embodiment also provides a polymer material, and the preparation steps are as follows:

[0134] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Example 4 were weighed by mass, mixed thoroughly and then cast to prepare a specimen for testing.

[0135] Comparative Example 1

[0136] Comparative Example 1 provides an amide compound, and the preparation steps are as follows:

[0137] According to the mass fraction, 100 parts of stearic acid, 0.2 parts of phosphorous acid, 5 parts of antioxidant 501 and 1 part of antioxidant 168 were weighed and added to the reactor. After the protective gas was introduced into the reactor, the temperature was raised until the stearic acid was completely melted and stirring was started. The temperature was continued to rise to 90°C, and ethylenediamine was added. The molar ratio of the amine group in ethylenediamine to the carboxyl group in stearic acid was 1:1.02. After about 40 minutes of addition, the temperature was raised to 100°C at a rate of 1.0°C / min, and the temperature was kept for 2 hours, and then the temperature was raised to 200°C, and the temperature was kept for 5 hours for dehydration. The reaction was terminated when the acid value was less than 10 mgKOH / g, and the amide compound of Comparative Example 1 was obtained by cooling to 170°C.

[0138] Comparative Example 1 also provides a polymer material, and the preparation steps are as follows:

[0139] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Comparative Example 1 were weighed by mass, mixed thoroughly and then cast to prepare a specimen for testing.

[0140] Comparative Example 2

[0141] Comparative Example 2 provides a plasticizer, dioctyl phthalate.

[0142] Comparative Example 2 also provides a polymer material, and the preparation steps are as follows:

[0143] 100 parts of polyurethane WH1185EC and 3 parts of plasticizer dioctyl phthalate were weighed by mass, mixed thoroughly and then poured to prepare specimens for testing.

[0144] Comparative Example 3

[0145] Comparative Example 3 provides a polymer material, and the preparation steps are as follows:

[0146] 100 parts of polyurethane WH1185EC were weighed by mass and cast to obtain specimens for testing.

[0147] Comparative Example 4

[0148] Comparative Example 4 provides an amide compound, which is different from the amide compound of Example 1 in that cyclohexylamine is used to replace 4,4-diaminodicyclohexylmethane in Example 1. Other steps are the same as those in Example 1 and are not described in detail.

[0149] Comparative Example 4 also provides a polymer material, and the preparation steps are as follows:

[0150] 100 parts of polyurethane WH1185EC and 3 parts of the amide compound of Comparative Example 4 were selected by weight, mixed thoroughly and then cast to prepare a specimen for testing.

[0151] The amide compounds and polymer materials of the above embodiments and comparative examples were tested, and the main testing methods are as follows:

[0152] 1. Melting point determination: Determine the melting point of amide compounds according to ISO 11357-1:2023;

[0153] 2. Acid value determination: Determine the acid value of the amide compound according to ASTM D-1386-78;

[0154] 3. Whiteness test: Determine the whiteness of amide compounds according to ASTM E313-2015;

[0155] 4. Softening point and flow starting temperature: The softening point and flow starting temperature of polymer materials are tested by constant pressure capillary rheometer with a test load of 10N and a heating rate of 5℃ / min.

[0156] 5. Thermal stability determination: Determine the thermal decomposition temperature of the polymer material (at 5% weight loss) according to the thermal decomposition method;

[0157] 6. Mechanical properties determination: Determine the tensile strength and elongation at break of polymer materials in accordance with ISO 527-2:2012.

[0158] The test results of the amide compounds and polymer materials of various embodiments and comparative examples are shown in Tables 2 and 3 below.

[0159] Table 2 Test results of various embodiments

[0160]

[0161] Table 3 Test results of each comparative example

[0162]

[0163] It can be seen from the above table that the amide compound obtained in the embodiment of the present application has a low acid value and high whiteness. Compared with Comparative Example 1, it can be seen that the amide compound obtained by using alicyclic amine in the embodiment of the present application has a high melting point and a higher thermal decomposition temperature of the polyurethane. And the amide compound obtained in the embodiment has no adverse effect on the tensile strength of the polyurethane material, and greatly improves its elongation at break. Compared with Comparative Examples 2 and 3, it can be seen that the processing window (the difference between the softening point and the flow starting temperature) of the polymer material prepared in the embodiment of the present application is widened, and the plasticizing effect is obvious. Compared with Comparative Example 4, the use of alicyclic amines containing at least two amino groups in the embodiment of the present application to prepare amide compounds is beneficial to improving the thermal decomposition temperature and elongation at break of the polyurethane material, and at the same time, has a better plasticizing effect.

[0164] In addition, by optimizing the structure of the alicyclic amine, it is beneficial to further improve the whiteness and plasticizing effect of the amide compound, as well as the thermal decomposition temperature, elongation at break and other properties of the prepared polyurethane material.

[0165] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0166] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. An amide compound, characterized in that It has the following general structural formula: ； In the formula, R1 contains C5~C 10 Alicyclic groups; n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

2. The amide compound according to claim 1, characterized in that R1 contains a cyclohexyl group; and / or n1 is an integer of 11 to 15; and / or n2 is 2 or 3.

3. The amide compound according to claim 2, characterized in that n2 is 2, R1 is selected from , and One or more of; or, n2 is 3, R1 is selected from .

4. The amide compound according to any one of claims 1 to 3, characterized in that The raw materials for preparing the amide compound include: fatty acid and alicyclic amine, wherein the structural formula of the fatty acid is CH3CH2(CH2) n1 COOH; the alicyclic amine is a C5~C 10 The molar ratio of the carboxyl group in the fatty acid to the amine group in the alicyclic amine is (1.02-1.2):1; Optionally, the raw materials for preparing the amide compound further include a catalyst and an antioxidant; The catalyst includes one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and p-toluenesulfonic acid; the antioxidant includes one or more of hindered phenol antioxidants and phosphite antioxidants.

5. The amide compound according to claim 4, characterized in that One or more of the following conditions are met: (1) The alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine; (2) The antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-5):1; Optionally, the hindered phenol antioxidant includes one or more of 2,6-di-tert-butyl-4-methyl-phenol, N,N′-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; The phosphite antioxidant includes one or more of 2′-ethylbis(4,6-di-tert-butylphenyl)fluorophosphite and tris(2,4-di-tert-butylphenyl)phosphite; (3) The ratio of the mass of the catalyst to the mass of the fatty acid is (0.2-1):100; (4) The ratio of the mass of the antioxidant to the mass of the fatty acid is (1-6):

100.

6. A method for preparing an amide compound, characterized in that: The steps include: The fatty acid and the alicyclic amine are subjected to an amidation reaction to prepare an amide compound; Wherein, the structural formula of the fatty acid is CH3CH2(CH2) n1 COOH; the alicyclic amine is a C5~C 10 The structural formula of the amide compound is ; In the formula, R1 contains C5~C 10 Alicyclic groups; n1 is an integer ranging from 9 to 15, and n2 ≥ 2.

7. The method for preparing an amide compound according to claim 6, characterized in that: The alicyclic amine is a polyamine containing a cyclohexyl group; optionally, the alicyclic amine includes one or more of 4,4-diaminodicyclohexylmethane, polyaminopolycyclohexylmethane, 1,3-cyclohexyldimethylamine and isophoronediamine.

8. The method for preparing an amide compound according to claim 6 or 7, characterized in that: In the step of subjecting the fatty acid and the alicyclic amine to an amide reaction, a catalyst and an antioxidant are also added; Wherein, the catalyst includes one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and p-toluenesulfonic acid; The antioxidant comprises a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of (1-5):1; and / or, The steps of subjecting the fatty acid and the alicyclic amine to an amidation reaction include: Under a protective atmosphere, the fatty acid, the catalyst and the antioxidant are mixed, and heated to melt the fatty acid; Adding the alicyclic amine to the reaction system at 70° C. to 90° C.; The reaction system was heated to 90°C~110°C and kept warm for 0.5h~2h, then continued to be heated to 190°C~220°C and kept warm for 4h~6h, and the reaction was stopped when the acid value was less than 10mgKOH / g.

9. Use of the amide compound according to any one of claims 1 to 5 or the amide compound prepared by the preparation method according to any one of claims 6 to 8 in the preparation of powder coatings, aqueous dispersions or polymer materials.

10. A polymer material, characterized in that It comprises a polymer matrix and an auxiliary agent, wherein the auxiliary agent comprises the amide compound according to any one of claims 1 to 5 or the amide compound prepared by the preparation method according to any one of claims 6 to 8; Optionally, the polymer matrix includes one or more of polyamide resin, polycarbonate, polyurethane, polyvinyl chloride, polyolefin and polyacrylonitrile.

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