Polyamides obtained from renewable sources and methods for making same

Abstract

Methods of making polyamides from renewable materials, such as natural oils, are generally disclosed herein. In some embodiments, the polyamide is nylon-10. In some such embodiments, nylon-10 is made by polymerizing 10-aminodecanoic acid, or an ester thereof. In some further such embodiments, the 10-aminodecanoic acid monomer (or ester thereof) is derived from a natural oil via metathesis of an unsaturated fatty acid moiety of the natural oil.

Description

[0001] This application is a divisional application of the Chinese invention patent application with application number 201780064846.3 and invention name “Polyamide obtained from renewable sources and its manufacturing method”.

[0002] Cross-reference to related applications

[0003] This application claims the benefit of priority to U.S. Provisional Application No. 62 / 412,709, filed on October 25, 2016, which is hereby incorporated by reference as if fully set forth herein. Technical Field

[0004] Disclosed herein are generally methods for producing polyamides from renewable materials, such as natural oils. In some embodiments, the polyamide is nylon-10. In some such embodiments, nylon-10 is produced by polymerizing 10-aminodecanoic acid, or an ester thereof. In some further such embodiments, the 10-aminodecanoic acid monomer (or an ester thereof) is derived from a natural oil by metathesis of the unsaturated fatty acid moiety of the natural oil, such as by reacting the unsaturated fatty acid moiety with a short-chain alpha-olefin. Background Art

[0005] Polyamide homopolymers, such as nylon 12, possess certain desirable properties and have found widespread use in a variety of industries. These longer-chain polyamides often exhibit properties that lie between those of short-chain polyamides, such as nylon 6,6 or nylon 6, and those of polyolefins. However, the availability of these long-chain polyamides is limited by the manufacturing costs of the monomers from which they are made.

[0006] For example, nylon 12 is typically produced at high temperatures by the ring-opening polymerization of laurolactam or by the homopolymerization of ω-aminolauric acid. In both cases, the starting materials are dependent on the availability of starting materials, which can be expensive and unpredictable in supply. For example, in 2012, a global shortage of nylon 12 occurred due to an accident at a single German plant that produced the precursors for the starting materials.

[0007] Furthermore, the most common process for making nylon 12, the ring-opening polymerization of laurolactam, uses cyclododecatriene to produce the laurolactam monomer. Cyclododecatriene is derived from the trimerization of butadiene, which is typically obtained as a byproduct of petroleum cracking (e.g., by steam cracking). Consequently, as end users increasingly seek to increase the "green" content of their products, the use of such petroleum-derived materials is becoming increasingly undesirable in the marketplace.

[0008] Therefore, there is a continuing need to develop materials that can serve as suitable replacements for long-chain polyamides and thereby overcome one or more of the above-mentioned disadvantages of nylon 12. Summary of the Invention

[0009] The present disclosure overcomes one or more of the above-mentioned disadvantages by providing a process for making the long-chain polyamide Nylon 10 via a process in which the majority of the carbon in the resulting polyamide is derived from renewable sources.

[0010] In a first aspect, the present disclosure provides a method for making a polyamide from a natural oil, the method comprising: providing 9-decenoic acid, wherein providing the 9-decenoic acid comprises deriving the 9-decenoic acid from a natural oil composition; reacting the 9-decenoic acid with a brominating agent to form 10-bromodecaneic acid; reacting the 10-bromodecaneic acid with an aminating agent to form 10-aminodecanoic acid; and polymerizing the 10-aminodecanoic acid to form a nylon-10 polymer.

[0011] In a second aspect, the present disclosure provides a method for producing polyamide from natural oil, the method comprising: providing 9-decenoic acid C 1-8 Alkyl esters, wherein 9-decenoic acid C 1-8 Alkyl esters include 9-decenoic acid C obtained from natural oil compositions 1-8 Alkyl ester; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 Alkyl ester; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 Alkyl ester; the 10-aminodecanoic acid C 1-8 The alkyl ester is converted to 10-aminodecanoic acid; and the 10-aminodecanoic acid is polymerized to form a nylon-10 polymer.

[0012] In a third aspect, the present disclosure provides a method for producing polyamide from natural oil, the method comprising: providing 9-decenoic acid C 1-8 Alkyl esters, wherein 9-decenoic acid C 1-8 Alkyl esters include 9-decenoic acid C obtained from natural oil compositions 1-8 Alkyl ester; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 Alkyl ester; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 Alkyl ester; and 10-aminodecanoic acid C 1-8 The alkyl esters are polymerized to form nylon-10 polymer.

[0013] Other aspects and embodiments are provided in the detailed description and claims. DETAILED DESCRIPTION

[0014] The following description describes various aspects and embodiments of the invention disclosed herein. No specific embodiment is intended to limit the scope of the invention. Instead, the embodiments provide non-limiting examples of various compositions (ingredients) and methods within the scope of the claimed invention. The description should be interpreted from the perspective of one of ordinary skill in the art. Therefore, it is not necessary to include information known to one of ordinary skill in the art.

[0015] definition

[0016] The following terms and phrases have the meanings shown below, unless otherwise specified in this article. The present disclosure may adopt other terms and phrases that are not clearly defined herein. Such other terms and phrases should have the meanings that they will have in the context of the present disclosure for those of ordinary skill in the art. In some cases, a term or phrase can be defined in the singular or plural. In such cases, it is understood that any term in the singular can include its plural counterpart and conversely also holds true, unless clearly indicated otherwise.

[0017] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to "a substituent" encompasses a single substituent as well as two or more substituents, and so forth.

[0018] As used herein, "for example," "such as," "for example," or "including" are intended to introduce examples that further illustrate a higher-level subject matter. Unless otherwise expressly stated, such examples are provided merely as an aid for understanding the embodiments shown in this disclosure and are in no way intended to be limiting. These phrases also do not indicate any kind of priority over the disclosed embodiments.

[0019] As used herein, "polymer" refers to a substance having a chemical structure comprising multiple repetitions of structural units formed from substances of relatively low relative molecular mass relative to the molecular mass of the polymer. The term "polymer" encompasses soluble and / or fusible molecules having chains of repeating units, and also encompasses insoluble and infusible networks. As used herein, the term "polymer" may encompass oligomeric materials having only a few (e.g., 3-100) structural units.

[0020] As used herein, " natural oil " refers to the oil derived from plant or animal origin. The term also includes modified (modified, transformed, modified) plant or animal origin (for example, genetically modified (genetically modified) plant or animal origin), unless otherwise indicated. The example of natural oil includes, but is not limited to, vegetable oil, algae oil, fish oil, animal fat, tall oil, the derivative of these oils, the combination of any one of these oils etc. The representative non-limiting example of vegetable oil includes rapeseed oil (canola oil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, iris oil, camelina oil and castor oil. The representative non-limiting example of animal fat includes lard, tallow, poultry fat, yellow grease and fish oil. Tall oil is a by-product of wood pulp manufacturing. In some embodiments, the natural oil or natural oil feedstock comprises one or more unsaturated glycerides (e.g., unsaturated triglycerides). In some such embodiments, the natural oil comprises at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least 95% by weight, or at least 97% by weight, or at least 99% by weight of one or more unsaturated triglycerides based on the total weight of the natural oil.

[0021] Term " unsaturated natural fatty acid " refers to the unsaturated fatty acid obtained by (above definition) natural oil.Similarly, term " unsaturated natural fatty acid ester " refers to the ester of such unsaturated fatty acid, such as glyceride (for example, monoacylglyceride, diacylglyceride and triacylglyceride), alkyl ester etc.

[0022] As used herein, "metathesis" refers to olefin metathesis. As used herein, "metathesis catalyst" encompasses any catalyst or catalyst system that catalyzes an olefin metathesis reaction.

[0023] As used herein, "metathesis" refers to reacting raw materials in the presence of a metathesis catalyst to form a "metathesis product" comprising a new olefinic compound, i.e., a "metathesis" compound. Metathesis is not limited to any particular type of olefin metathesis, and can refer to cross-metathesis (i.e., co-metathesis), self-metathesis, ring-opening metathesis, ring-opening metathesis polymerization ("ROMP"), ring-closing metathesis ("RCM"), and acyclic diene metathesis ("ADMET"). In some embodiments, metathesis refers to reacting two triglycerides present in natural raw materials in the presence of a metathesis catalyst (self-metathesis), wherein each triglyceride has an unsaturated carbon-carbon double bond, thereby forming a new mixture of olefins and an ester that can include a triglyceride dimer. Such a triglyceride dimer can have more than one olefinic bond, thereby also forming higher oligomers. Additionally, in some other embodiments, metathesis can refer to reacting a triglyceride with at least one unsaturated carbon-carbon double bond in an olefin, such as ethylene, and a natural raw material, thereby forming new olefin molecules and new ester molecules (cross-metathesis).

[0024] As used herein, "olefin" or "multiple olefins" refers to a compound with at least one unsaturated carbon-carbon double bond. In certain embodiments, the term "(multiple) olefins" refers to a group of unsaturated carbon-carbon double bond compounds with different carbon lengths. Unless otherwise indicated, the term "olefin" or "multiple olefins" encompasses "polyunsaturated olefins" or "poly-olefins" with more than one carbon-carbon double bond. As used herein, the term "monounsaturated olefin" or "mono-olefin" refers to a compound with only one carbon-carbon double bond. Compounds with terminal carbon-carbon double bonds may be referred to as "terminal olefins" or "α-olefins", while olefins with non-terminal carbon-carbon double bonds may be referred to as "internal olefins". In some embodiments, the α-olefin is a terminal chain olefin, which is a chain olefin (as defined below) with a terminal carbon-carbon double bond. Additional carbon-carbon double bonds may be present.

[0025] The number of carbon atoms in any group or compound can be expressed by the following terms: z ”, which refers to a group of compounds with z carbon atoms; and “C x-y ", which refers to a group or compound containing xy (including endpoints) carbon atoms. For example, "C 1-6 "Alkyl" means an alkyl chain having 1 to 6 carbon atoms and includes, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. As a further example, "C 4-10“Alkenes” refers to alkene molecules having 4 to 10 carbon atoms and include, for example, but are not limited to, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene, 1-nonene, 4-nonene, and 1-decene.

[0026] As used herein, the term "short-chain alpha olefins" refers to short-chain alpha olefins having at least one terminal carbon-carbon double bond. 2-14 Range, or C 2-12 Range, or C 2-10 Range, or C 2-8 Any one or combination of unsaturated linear, branched, or cyclic hydrocarbons within the scope of the present invention. Such olefins also include dienes or trienes. Examples of short-chain alpha olefins include, but are not limited to: ethylene, propylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1,4-pentadiene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, and 4-methyl-1-pentene.

[0027] As used herein, "alkyl" refers to a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, which may be optionally substituted as further described herein, with various degrees of substitution being tolerated. Examples of "alkyl" as used herein include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in an alkyl group is represented by the following phrases: C x-y "alkyl" refers to an alkyl group as defined herein containing xy (inclusive) carbon atoms. Thus, "C 1-6 "Alkyl" means an alkyl chain having 1-6 carbon atoms and includes, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In some cases, an "alkyl" group may be divalent, in which case the group may alternatively be referred to as an "alkylene" group.

[0028] As used herein, "mixing" or "mixed" or "mixture" refers broadly to any combination of two or more components. The two or more components need not be of the same physical state; thus, a solid can be "mixed" with a liquid, for example, to form a slurry, a suspension, or a solution. Further, these terms do not require any degree of uniformity or homogeneity of the components. Such a "mixture" can be homogeneous or heterogeneous, or can be uniform or non-uniform. Further, the terms do not require the use of any specific equipment for mixing, such as an industrial mixer.

[0029] As used herein, "optionally" means that the subsequently described event may or may not occur. In some embodiments, the optional event does not occur. In some other embodiments, the optional event occurs one or more times.

[0030] As used herein, "comprising" refers to an open set, meaning that the set may include additional members in addition to those explicitly recited. For example, the phrase "comprising A" means that A must be present, but other members may also be present. The terms "comprising," "having," and "consisting of," and their grammatical variations, have the same meaning. In contrast, "consisting of" refers to a closed set. For example, the phrase "consisting of A" means that A and only A is present.

[0031] As used herein, "or" should be given its broadest reasonable interpretation and should not be limited to either / or structures. Thus, the phrase "comprising A or B" means that A may be present and B may not be present, or B may be present and A may not be present, or both A and B may be present. Further, if A, for example, defines a class that may have multiple members, such as A1 and A2, then one or more members of the class may be present at the same time.

[0032] In some cases herein, organic compounds are described using a "line structure" method in which chemical bonds are represented by lines, in which carbon atoms are not explicitly labeled, and in which hydrogen atoms covalently bonded to carbon (or C-H bonds) are not shown at all. For example, according to this convention, the formula In some cases herein, a squiggly bond is used to indicate that a compound can have any of two or more isomers. For example, the structure It can refer to (E)-2-butene or (Z)-2-butene. The same is true when drawing an olefin structure where it is unclear which isomer is being referred to. For example, CH3-CH=CH-CH3 can refer to (E)-2-butene or (Z)-2-butene.

[0033] As used herein, the various functional groups shown will be understood to have a point of attachment at the functional group with a dash or hyphen (-) or an asterisk (*). In other words, in the case of -CH2CH2CH3, it will be understood that the point of attachment is the leftmost CH2 group. If a group is recited without an asterisk or hyphen, the point of attachment is represented by the usual and ordinary meaning of the recited group.

[0034] As used herein, polyatomic divalent species should be read from left to right. For example, if the specification or claims recite ADE and D is defined as -OC(O)-, the resulting group if D is replaced is A-OC(O)-E rather than AC(O)OE.

[0035] Other terms are defined in other parts of this specification although not included in this section. Omega-amino acids Method for producing polyamide by aqueous condensation

[0036] In at least one aspect, the present disclosure provides a method of making a polyamide from a natural oil, the method comprising: providing 9-decenoic acid; reacting the 9-decenoic acid with a brominating agent to form 10-bromodecanoic acid; reacting the 10-bromodecanoic acid with an aminating agent to form 10-aminodecanoic acid; and polymerizing the 10-aminodecanoic acid to form a nylon-10 polymer.

[0037] In some embodiments, providing 9-decenoic acid comprises obtaining 9-decenoic acid from a natural oil composition, such as a natural oil (as defined above), or any composition comprising a natural oil. Obtaining 9-decenoic acid from a natural oil can be accomplished by any suitable means. For example, in some embodiments, obtaining 9-decenoic acid from a natural oil comprises: providing a natural oil composition comprising an unsaturated natural fatty acid ester; reacting the unsaturated natural fatty acid ester with a short-chain α-olefin in the presence of a metathesis catalyst to form a 9-decenoic acid ester and 1-decene; and converting the 9-decenoic acid ester into 9-decenoic acid.

[0038] The esters described in the foregoing embodiments may be any suitable esters, for example, esters made from any suitable alcohol. In some embodiments, the unsaturated natural fatty acid esters are unsaturated natural fatty acid C 1-8 Alkyl esters, and wherein the 9-decenoic acid ester is 9-decenoic acid C 1-8 In some further embodiments, the unsaturated natural fatty acid ester is an unsaturated natural fatty acid methyl ester, and wherein the 9-decenoic acid ester is 9-decenoic acid methyl ester. In some other embodiments, the unsaturated natural fatty acid ester is an unsaturated natural fatty acid glyceride, and wherein the 9-decenoic acid ester is 9-decenoic acid glyceride. In such an embodiment, any suitable glyceride can be used, comprising monoacylglycerol, diacylglycerol and triacylglycerol. In some further embodiments, the ester is a triacylglycerol, such as those found conventionally in natural oils.

[0039] Any suitable unsaturated natural fatty acid can be used in the method disclosed herein. In some embodiments, the unsaturated natural fatty acid is an unsaturated fatty acid having a carbon-carbon double bond between the 9th and 10th carbon atom counting from the ester group (comprising the carbon in the carbonyl of the ester). In some embodiments, the unsaturated natural fatty acid is selected from myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid. In some further embodiments, the unsaturated natural fatty acid is selected from oleic acid, linoleic acid, and alpha-linolenic acid.

[0040] The conversion of the 9-decenoic acid ester to 9-decenoic acid can be performed by any suitable means. In some embodiments, the conversion of the 9-decenoic acid ester to 9-decenoic acid comprises (e.g., using standard hydrolysis conditions) hydrolyzing the 9-decenoic acid ester to form 9-decenoic acid. In some other embodiments, the conversion of the 9-decenoic acid ester to 9-decenoic acid comprises: saponifying the 9-decenoic acid ester to form a 9-decenoic acid anion; and acidifying the 9-decenoic acid anion to form 9-decenoic acid. In some other embodiments, when the 9-decenoic acid is an ester other than an alkyl ester (e.g., a glyceride), the conversion to the acid does not occur directly, but first involves transesterification to an alkyl ester, which is then converted to the acid. For example, in some embodiments, the conversion of the 9-decenoic acid ester to 9-decenoic acid comprises: reacting 9-decenoic acid glyceride with C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 Ester; and the 9-decenoic acid C 1-8 In such a process, any suitable C 1-8 Monohydric alkanol (i.e., R-OH, where R is C 1-8 alkyl). Non-limiting examples include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol. In some embodiments, the C 1-8 The monohydric alkanol is methanol.

[0041] In any of the aforementioned embodiments, the unsaturated natural fatty acid ester is reacted with a short-chain alpha-olefin in the presence of a metathesis catalyst and can be carried out by any suitable means. The principle of metathesis is discussed in more detail in the subsequent subsections and can be applied here. Any suitable short-chain alpha-olefin can be used. For example, in some embodiments, the short-chain alpha-olefin is selected from: ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. In some further such embodiments, the short-chain alpha-olefin is selected from: ethylene, propylene, and 1-butene. In some further such embodiments, the short-chain alpha-olefin is selected from: ethylene or 1-butene.

[0042] The bromination can be carried out by any suitable means. In some embodiments, the brominating agent is hydrobromic acid. Depending on the scale involved, known hydrobromination methods can be appropriately modified to achieve the desired results.

[0043] The amination can be carried out by any suitable means. In some embodiments, the aminating agent is ammonia. Depending on the relevant scale, known methods for reacting alkyl bromides with ammonia can be appropriately modified to achieve the desired results.

[0044] Method for producing polyamides by aqueous condensation of ω-amino esters

[0045] In another aspect, the present disclosure provides a method for producing polyamide from natural oil, the method comprising: providing 9-decenoic acid C 1-8 Alkyl ester; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 Alkyl ester; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 Alkyl ester; the 10-aminodecanoic acid C 1-8 The alkyl ester is converted to 10-aminodecanoic acid; and the 10-aminodecanoic acid is polymerized to form a nylon-10 polymer.

[0046] In some embodiments, 9-decenoic acid C is provided 1-8 Alkyl esters include 9-decenoic acid C 2-decenoic acid obtained from a natural oil composition such as a natural oil (as defined above) or any composition comprising a natural oil. 1-8 Alkyl esters. 9-decenoic acid C is obtained from natural oils 1-8 The alkyl esters can be prepared by any suitable means. For example, in some embodiments, 9-decenoic acid C is obtained from natural oils. 1-8 Alkyl esters include: providing unsaturated natural fatty acids C 1-8 natural oil composition of alkyl esters; and making the unsaturated natural fatty acid C 1-8 Alkyl esters react with short-chain α-olefins in the presence of a metathesis catalyst to form 9-decenoic acid C 1-8 Alkyl ester and 1-decene. 1-8 The alkyl ester may be any suitable such ester. In some embodiments, the unsaturated natural fatty acid C 1-8 The alkyl ester is an unsaturated natural fatty acid methyl ester; the 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester; the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate; and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

[0047] Obtaining 9-decenoic acid C from natural oil 1-8 The alkyl esters may be prepared by any suitable means. In some embodiments, 9-decenoic acid C is obtained from natural oils. 1-8 The alkyl ester comprises: providing a natural oil composition comprising an unsaturated natural fatty acid glyceride; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and reacting the 9-decenoic acid glyceride with C1-8 monohydric alkanol to form 9-decenoic acid C 1-8 ester.

[0048] In some other embodiments, obtaining 9-decenoic acid methyl ester from a natural oil comprises: providing a natural oil composition comprising unsaturated natural fatty acid glycerols; reacting the unsaturated natural fatty acid glycerols with a short chain a-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glycerol ester and 1-decene; and reacting the 9-decenoic acid glycerol ester with C 1-8 monohydric alkanol to form 9-decenoic acid C 1-8 alkyl ester.

[0049] In some further such embodiments, the C 1-8 monohydric alkanol. In some embodiments, the C 1-8 monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, neopentanol, hexanol, heptanol, octanol, and 2-ethylhexanol. In some further such embodiments, the C 1-8 monohydric alkanol is methanol.

[0050] In the methods disclosed herein, any suitable unsaturated natural fatty acid can be used. In some embodiments, the unsaturated natural fatty acid is an unsaturated fatty acid having a carbon-carbon double bond between the 9thand 10thcarbon atoms, counting from the ester group (including the carbon in the carbonyl of the ester). In some embodiments, the unsaturated natural fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, linolelaidic acid, and a-linolenic acid. In some further embodiments, the unsaturated natural fatty acid is selected from the group consisting of oleic acid, linoleic acid, and a-linolenic acid.

[0051] In any of the foregoing embodiments, reacting the unsaturated natural fatty acid ester with a short chain a-olefin in the presence of a metathesis catalyst can be carried out by any suitable means. The principles of metathesis are discussed in more detail in the subsections that follow, and can be applied here. Any suitable short chain a-olefin can be used. For example, in some embodiments, the short chain a-olefin is selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. In some further such embodiments, the short chain a-olefin is selected from the group consisting of ethylene, propylene, and 1-butene. In some further such embodiments, the short chain a-olefin is selected from the group consisting of ethylene or 1-butene.

[0052] converting the 10-aminodecanoic acid C 1-8 alkyl ester to 10-aminodecanoic acid can be carried out by any suitable means. In some embodiments, converting the 10-aminodecanoic acid C 1-8The conversion of the alkyl ester into 10-aminodecanoic acid comprises converting the 10-aminodecanoic acid C 1-8 The alkyl ester is hydrolyzed to form 10-aminodecanoic acid. In some other embodiments, the 10-aminodecanoic acid C 1-8 The conversion of the alkyl ester into 10-aminodecanoic acid comprises: 1-8 saponification of the alkyl ester to form a 10-aminodecanoate anion; and acidification of the 10-aminodecanoate anion to form 10-aminodecanoic acid. 1-8 The alkyl ester is 9-decenoic acid methyl ester, the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate, and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

[0053] The bromination can be carried out by any suitable means. In some embodiments, the brominating agent is hydrobromic acid. Depending on the scale involved, known hydrobromination methods can be appropriately modified to achieve the desired results.

[0054] The amination can be carried out by any suitable means. In some embodiments, the aminating agent is ammonia. Depending on the relevant scale, known methods for reacting alkyl bromides with ammonia can be appropriately modified to achieve the desired results.

[0055] Method for producing polyamide from ω-amino ester by alcohol condensation

[0056] In another aspect, the present disclosure provides a method for producing polyamide from natural oil, the method comprising: providing 9-decenoic acid C 1-8 Alkyl ester; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 Alkyl ester; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 Alkyl ester; and 10-aminodecanoic acid C 1-8 The alkyl esters are polymerized to form nylon-10 polymer.

[0057] In some embodiments, 9-decenoic acid C is provided 1-8 Alkyl esters include 9-decenoic acid C 2-decenoic acid obtained from a natural oil composition such as a natural oil (as defined above) or any composition comprising a natural oil. 1-8 Alkyl esters. 9-decenoic acid C is obtained from natural oils 1-8 The alkyl esters can be prepared by any suitable means. For example, in some embodiments, 9-decenoic acid C is obtained from natural oils. 1-8 Alkyl esters include: providing unsaturated natural fatty acids C 1-8natural oil composition of alkyl esters; and making the unsaturated natural fatty acid C 1-8 Alkyl esters react with short-chain α-olefins in the presence of a metathesis catalyst to form 9-decenoic acid C 1-8 Alkyl ester and 1-decene. 1-8 The alkyl ester may be any suitable such ester. In some embodiments, the unsaturated natural fatty acid C 1-8 The alkyl ester is an unsaturated natural fatty acid methyl ester; the 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester; the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate; and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

[0058] Obtaining 9-decenoic acid C from natural oil 1-8 The alkyl esters may be prepared by any suitable means. In some embodiments, 9-decenoic acid C is obtained from natural oils. 1-8 The alkyl ester comprises: providing a natural oil composition comprising an unsaturated natural fatty acid glyceride; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and reacting the 9-decenoic acid glyceride with C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 ester.

[0059] In some other embodiments, obtaining 9-decenoic acid methyl ester from natural oil comprises: providing a natural oil composition comprising unsaturated natural fatty acid glycerides; reacting the unsaturated natural fatty acid glycerides with short chain α-olefins in the presence of a metathesis catalyst to form 9-decenoic acid glycerides and 1-decene; and reacting the 9-decenoic acid glycerides with C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 Alkyl esters.

[0060] In the immediately preceding embodiment, any suitable C 1-8 In some embodiments, the C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol. 1-8 The monohydric alkanol is methanol.

[0061] Any suitable unsaturated natural fatty acid can be used in the method disclosed herein. In some embodiments, the unsaturated natural fatty acid is an unsaturated fatty acid having a carbon-carbon double bond between the 9th and 10th carbon atom counting from the ester group (comprising the carbon in the carbonyl of the ester). In some embodiments, the unsaturated natural fatty acid is selected from myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid. In some further embodiments, the unsaturated natural fatty acid is selected from oleic acid, linoleic acid, and alpha-linolenic acid.

[0062] In any of the aforementioned embodiments, the unsaturated natural fatty acid ester is reacted with a short-chain alpha-olefin in the presence of a metathesis catalyst and can be carried out by any suitable means. The principle of metathesis is discussed in more detail in the subsequent subsections and can be applied here. Any suitable short-chain alpha-olefin can be used. For example, in some embodiments, the short-chain alpha-olefin is selected from: ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. In some further such embodiments, the short-chain alpha-olefin is selected from: ethylene, propylene, and 1-butene. In some further such embodiments, the short-chain alpha-olefin is selected from: ethylene or 1-butene.

[0063] The bromination can be carried out by any suitable means. In some embodiments, the brominating agent is hydrobromic acid. Depending on the scale involved, known hydrobromination methods can be appropriately modified to achieve the desired results.

[0064] The amination can be carried out by any suitable means. In some embodiments, the aminating agent is ammonia. Depending on the relevant scale, known methods for reacting alkyl bromides with ammonia can be appropriately modified to achieve the desired results.

[0065] polymerization

[0066] The polycondensation, whether by elimination of water or C 1-8 The reaction of the alkanol may be carried out by any suitable means for homopolymerizing ω-amino acids or ω-amino esters to produce polyamides.

[0067] Derived from renewable sources

[0068] As indicated above, certain compounds employed in the various aspects or embodiments disclosed herein may in certain embodiments be obtained from renewable sources, such as various natural oils or their derivatives. Any suitable method may be used to manufacture these compounds from such renewable sources.

[0069] Olefin metathesis provides some natural oil feedstock being converted into a kind of possible means of following ester and alkene: it can be used in various applications, or can be further chemically modified and used in various applications.In some embodiments, composition (or the component of composition) can be formed by renewable raw materials, such as the renewable raw materials formed by the metathesis reaction of natural oil and / or their fatty acid or fatty ester derivative.When the compound containing carbon-carbon double bond carries out metathesis reaction under the existence of metathesis catalyst, some or all of original carbon-carbon double bond are broken, and new carbon-carbon double bond is formed.The product of such metathesis reaction is included in the carbon-carbon double bond in different positions, and this can provide the undersaturated organic compound with useful chemical property.

[0070] In such metathesis reaction, a wide range of natural oils or derivatives thereof can be used.The example of suitable natural oil includes, but is not limited to, vegetable oil, algae oil, fish oil, animal fat, tallow oil, the derivative of these oils, the combination of any one in these oils etc.The representative non-limiting examples of vegetable oil include rapeseed oil (canola oil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil, iris oil, camelina oil and castor oil.The representative non-limiting examples of animal fat include lard, tallow, poultry fat, yellow grease and fish oil.Tall oil is the by-product of wood pulp manufacturing.In some embodiments, the natural oil or natural oil raw material include one or more unsaturated glycerides (for example, unsaturated triglycerides). In some such embodiments, the natural oil feedstock comprises at least 50 weight percent, or at least 60 weight percent, or at least 70 weight percent, or at least 80 weight percent, or at least 90 weight percent, or at least 95 weight percent, or at least 97 weight percent, or at least 99 weight percent of one or more unsaturated triglycerides, based on the total weight of the natural oil feedstock.

[0071] The natural oil may comprise canola or soybean oil, such as refined, bleached, and deodorized soybean oil (i.e., RBD soybean oil). Soybean oil typically comprises about 95% by weight (wt%) or greater (e.g., 99% by weight or greater) of fatty acid triglycerides. The primary fatty acids in the polyol esters of soybean oil include, but are not limited to, saturated fatty acids such as palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated fatty acids such as oleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), and linolenic acid (9,12,15-octadecatrienoic acid).

[0072] Such natural oil or its derivatives contain esters of multiple unsaturated fatty acids such as triglycerides. The identity (identity) and concentration of such fatty acids depend on the oil source and in some cases depend on kind and change. In some embodiments, the natural oil comprises one or more following esters: oleic acid, linoleic acid, linolenic acid or its arbitrary combination. When such fatty acid ester is metathesized, new compounds are formed. For example, in the embodiment where the metathesis uses some short chain alkenes such as ethene, propylene, or 1-butene and wherein the natural oil comprises an oleic ester, a certain amount of 1-decene and 1-decenoic acid (or its ester) and other products are formed.

[0073] In some embodiments, the natural oils may be subjected to various pretreatment processes, which may enhance their utility for use in certain metathesis reactions. Useful pretreatment methods are described in U.S. Patent Application Publication Nos. 2011 / 0113679, 2014 / 0275595, and 2014 / 0275681, all three of which are hereby incorporated by reference as if fully set forth herein.

[0074] In some embodiments, after any optional pretreatment of the natural oil feedstock, the natural oil feedstock is reacted in a metathesis reactor in the presence of a metathesis catalyst. In some other embodiments, unsaturated esters (e.g., unsaturated glycerides such as unsaturated triglycerides) are reacted in a metathesis reactor in the presence of a metathesis catalyst. These unsaturated esters may be components of the natural oil feedstock or may be derived from other sources, for example, from esters produced in a previously performed metathesis reaction.

[0075] Conditions for such metathesis reactions, as well as reactor designs, and suitable catalysts are as described below with reference to the metathesis of olefin esters. That discussion is incorporated by reference as if fully set forth herein.

[0076] Olefin metathesis

[0077] In some embodiments, one or more of the unsaturated monomers can be produced by metathesis of a natural oil or a natural oil derivative. The term "metathesis" can refer to a variety of different reactions, including, but not limited to, cross-metathesis, self-metathesis, ring-opening metathesis, ring-opening metathesis polymerization ("ROMP"), ring-closing metathesis ("RCM"), and acyclic diene metathesis ("ADMET"). Any suitable metathesis reaction can be used, depending on the desired product or product mixture.

[0078] In some embodiments, after any optional pre-treatment of the natural oil feedstock, the natural oil feedstock is reacted in a metathesis reactor in the presence of a metathesis catalyst. In some other embodiments, unsaturated esters (for example, unsaturated glycerides such as unsaturated triglycerides) are reacted in a metathesis reactor in the presence of a metathesis catalyst. These unsaturated esters can be components of the natural oil feedstock, or can be derived from other sources, for example, from the ester produced in the metathesis reaction previously carried out. In certain embodiments, in the presence of a metathesis catalyst, the natural oil or unsaturated ester can be subjected to a self-metathesis reaction with itself.

[0079] In some embodiments, the metathesis comprises reacting natural oil feedstock (or other unsaturated ester) in the presence of a metathesis catalyst. In some such embodiments, the metathesis comprises reacting one or more unsaturated glycerides (for example, unsaturated triglycerides) in the natural oil feedstock in the presence of a metathesis catalyst. In some embodiments, the unsaturated glycerides comprise one or more esters: oleic acid, linoleic acid, linoleic acid or a combination thereof. In some other embodiments, the unsaturated glycerides are the product of partial hydrogenation and / or metathesis of other unsaturated glycerides (as described above).

[0080] The metathesis process can be carried out under any conditions suitable for producing the desired metathesis product. For example, those skilled in the art can select stoichiometry, atmosphere, solvent, temperature and pressure to produce the desired product and minimize undesirable by-products. In some embodiments, the metathesis process can be carried out under an inert atmosphere. Similarly, in the embodiment in which reagent is used as a gas supply, an inert gaseous diluent can be used in a gas stream. In such an embodiment, the inert atmosphere or inert gaseous diluent are typically inert gases, meaning that the gas does not interact with the metathesis catalyst and hinders catalysis to a significant extent. For example, the non-limiting examples of inert gases include helium, neon, argon and nitrogen, which are used individually or together with each other and other inert gases.

[0081] The design of the reactor for the metathesis reaction may vary depending on a variety of factors including, but not limited to, the scale of the reaction, the reaction conditions (heat, pressure, etc.), the identity of the catalyst, the identity of the materials reacted in the reactor, and the nature of the feedstocks employed. Suitable reactors can be designed by those skilled in the art depending on the relevant factors and incorporated into refining processes such as those disclosed herein.

[0082] The metathesis reactions disclosed herein generally occur in the presence of one or more metathesis catalysts. Such processes can employ any suitable metathesis catalyst. The metathesis catalyst in the reaction can comprise any catalyst or catalyst system that catalyzes a metathesis reaction. Any known metathesis catalyst can be used, either alone or in combination with one or more additional catalysts. Examples of metathesis catalysts and process conditions are described in US 2011 / 0160472, which is incorporated herein by reference in its entirety, except to the extent that the disclosure or definitions in US 2011 / 0160472 are inconsistent with any disclosure or definitions in this specification, in which case the disclosure or definitions herein shall control. Many of the metathesis catalysts described in US 2011 / 0160472 are currently available from Materia, Inc. (Pasadena, Calif.).

[0083] In some embodiments, the metathesis catalyst comprises a Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a first-generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a second-generation Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a first-generation Hoveyda-Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a second-generation Hoveyda-Grubbs-type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises one or more ruthenium carbene metathesis catalysts sold by Materia, Inc. of Pasadena, California, and / or one or more entities derived therefrom. Representative metathesis catalysts from Materia, Inc. for use in accordance with the present teachings include, but are not limited to, those sold under the following product numbers: Product No. C823 (CAS No. 172222-30-9), Product No. C848 (CAS No. 246047-72-3), Product No. C601 (CAS No. 203714-71-0), Product No. C627 (CAS No. 301224-40-8), Product No. C571 (CAS No. 927429-61-6), Product No. C598 (CAS No. 802912-44-3), Product No. C793 (CAS No. 927429-60-5), Product No. C801 (CAS No. 194659-03-9), Product No. C827 (CAS No. 301224-40-8), and combinations thereof. No.253688-91-4), Product No.C884 (CAS No.900169-53-1), Product No.C833 (CAS No.1020085-61-3), Product No.C859 (CAS No.832146-68-6), Product No.C711 (CAS No.635679-24-2), Product No.C933 (CAS No.373640-75-6).

[0084] In some embodiments, the metathesis catalyst comprises molybdenum and / or tungsten carbene complex and / or an entity derived from such complex. In some embodiments, the metathesis catalyst comprises Schrock type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a high oxidation state alkylidene complex of molybdenum and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a high oxidation state alkylidene complex of tungsten and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises molybdenum (VI). In some embodiments, the metathesis catalyst comprises tungsten (VI). In some embodiments, the metathesis catalyst comprises an alkylidene complex containing molybdenum and / or tungsten of the type described in one or more of: (a) Angew. Chem. Int. Ed. Engl., 2003, 42, 4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and / or (c) Chem. Rev., 2009, 109, 3211-3226, each of which is incorporated herein by reference in its entirety, except as follows: In the event of any inconsistent disclosure or definition with this specification, the disclosure or definition in this specification shall be deemed to prevail.

[0085] In certain embodiments, before carrying out the metathesis reaction, the metathesis catalyst is dissolved in a solvent. In certain such embodiments, the selected solvent may be selected to be substantially inert to the metathesis catalyst. For example, substantially inert solvents include without limitation aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic solvents including pentane, hexane, heptane, cyclohexane, etc.; and chlorinated alkanes such as dichloromethane, chloroform, dichloroethane, etc. In some embodiments, the solvent includes toluene.

[0086] In other embodiments, before carrying out the metathesis reaction, the metathesis catalyst is not dissolved in a solvent. The catalyst can be slurried in the natural oil or unsaturated ester instead, wherein the natural oil or unsaturated ester are in a liquid state. Under these conditions, solvent (for example, toluene) and downstream olefin losses when separating the solvent can be eliminated from the technique. In other embodiments, the metathesis catalyst can be added to the natural oil or unsaturated ester (for example, as an auger feed) in solid form (and not slurried).

[0087] In some cases, the metathesis reaction temperature can be a variable that controls the rate, wherein the temperature is selected to provide the desired product at an acceptable rate. In certain embodiments, the metathesis reaction temperature is greater than -40°C, or greater than -20°C, or greater than 0°C, or greater than 10°C. In certain embodiments, the metathesis reaction temperature is less than 200°C, or less than 150°C, or less than 120°C. In some embodiments, the metathesis reaction temperature is between 0°C and 150°C, or between 10°C and 120°C.

[0088] Example

[0089] The following examples show certain illustrative embodiments of the compounds, compositions, and methods disclosed herein. These examples should not be considered restrictive in any way. The examples should not be considered to represent any preferred embodiments or to indicate any direction for further research.

[0090] Example 1 - Synthesis of 9-decenoic acid

[0091] 9-Decenoic acid methyl ester (DAME) is obtained by butenolysis of palm oil (1-butene), followed by separation of the glycerides from the alkenes, transesterification of the glycerides with methanol, and separation of DAME from other esters.

[0092] A 5-L 5-neck round-bottom flask is equipped with a mechanical stirrer, an addition funnel, a condenser, a thermocouple, and a stopper. 1106g of DAME, 540mL of water, and 300mL of isopropyl alcohol are added to the flask. Nitrogen is passed through the headspace of the flask for 15 minutes. Potassium hydroxide aqueous solution (10M, 660mL) is added over 5 minutes. The mixture slowly becomes homogeneous and the temperature reaches up to 55°C. The reaction mixture is stirred for 4 hours at a temperature of approximately 30°C. The mixture is placed in a water-bath. While the temperature is kept below 40°C, aqueous concentrated hydrochloric acid (37%, 600mL) is divided into multiple parts and added over 1 hour until the pH is 1-2. The organic layer is washed with saturated NaCl (3x 250mL), dried over Na2SO4, vacuum filtered, and concentrated under reduced pressure. The product is distilled (2 torrs, 140°C) to obtain 957g of the product as a colorless liquid.

[0093] Example 2 - Synthesis of 10-bromodecanoic acid

[0094] A 500-mL 3-neck round-bottom flask was equipped with a thermocouple, a gas dispersion tube, and a magnetic stirring bar. The experimental equipment also included a dry trap for separating the reaction mixture (water) from a hydrobromic acid valve bottle (a fine compressed gas cylinder, lecture bottle) and a scrubber. 50 g of 9-decenoic acid from Example 1, 125 mL of toluene, and 0.75 g of benzoyl peroxide were added to the reaction flask. The solution was placed in an ice-water bath and cooled to approximately 5° C. Hydrobromic acid was bubbled through the mixture for approximately 1.25 hours while maintaining the temperature at 5-15° C. No exotherm was observed during the last few minutes of addition, and 33.3 g of HBr was absorbed. The mixture was washed with 50 mL of water and then brine. The organic phase was dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator (10 torr, 55° C.). The resulting oil was cooled to obtain an oily solid (73 g). The material was treated with 50 mL of hexane and filtered. The filter cake was washed with 2x20 mL hexanes and dried in air to give a solid white product (30 g). The mother liquor was cooled in an ice bath for 2 hours to produce a second batch of product (17.5 g). These two batches were combined to give 47.5 g of product. The yield was 64%. 1 H NMR chemical shifts are as follows (relative to TMS): 1.28-1.39 (m, 10H), 1.58-1.61 (m, 2H), 1.79-1.86 (m, 2H), 2.30-2.34 (m, 2H), 3.36-3.39 (m, 2H), 11.45-11.50 (b, 1H).

[0095] Example 3 - Synthesis of 10-aminodecanoic acid

[0096] To a 250-mL round-bottom flask was added 5.0 g of 10-bromodecanoic acid from Example 2 and 100 mL of ammonium hydroxide (28% in water). The suspension was stirred at 20° C. for 3 hours. The suspension was heated to 45° C. for 15 minutes. The mixture was then stirred at ambient temperature for 2 hours and then filtered. The filter cake was washed with water and 50% isopropyl alcohol. The resulting solid was dried in vacuo to obtain a white powder (approximately 1 g). 1 HNMR chemical shifts are as follows (relative to TMS): 1.35 (s, 10H), 1.63-1.70 (m, 4H), 2.05-2.07 (m, 2H), 2.36-2.40 (m, 2H), 3.03-3.07 (m, 2H), 11.75 (approximately, s, 1H).

[0097] Example 4 - Polymerization

[0098] A few mg of 10-aminodecanoic acid from Example 3 were polymerized via melt polymerization at 220° C. An opaque solid was obtained.

Claims

1. A method for producing polyamide from natural oils, the method comprising: 9-decenoic acid is provided, wherein providing the 9-decenoic acid comprises obtaining the 9-decenoic acid from a natural oil composition by the following process: Providing a natural oil composition comprising an unsaturated natural fatty acid ester having a carbon-carbon double bond between the 9th and 10th carbon atoms counted from the ester group; reacting the unsaturated natural fatty acid ester with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid ester and 1-decene; and converting the 9-decenoic acid ester into 9-decenoic acid; reacting 9-decenoic acid with a brominating agent to form 10-bromodecanoic acid; reacting 10-bromodecanoic acid with an aminating agent to form 10-aminodecanoic acid; and polymerizing 10-aminodecanoic acid to form a polyamide-10 polymer, The metathesis catalyst is slurried with the natural oil or unsaturated ester or added to the natural oil or unsaturated ester in solid form.

2. the method for claim 1, wherein said unsaturated natural fatty acid ester is unsaturated natural fatty acid C 1-8 Alkyl esters, and wherein the 9-decenoic acid ester is 9-decenoic acid C 1-8 Alkyl esters.

3. The method of claim 2, wherein the unsaturated natural fatty acid ester is an unsaturated natural fatty acid methyl ester, and wherein the 9-decenoic acid ester is methyl 9-decenoate.

4. The method of claim 1, wherein the unsaturated natural fatty acid ester is an unsaturated natural fatty acid glyceride, and wherein the 9-decenoic acid ester is 9-decenoic acid glyceride.

5. The method of any one of claims 2 to 4, wherein the unsaturated natural fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid.

6. The method of claim 5, wherein the unsaturated natural fatty acid is selected from the group consisting of oleic acid, linoleic acid, and α-linolenic acid.

7. The method of any one of claims 2-6, wherein converting the 9-decenoic acid ester to 9-decenoic acid comprises hydrolyzing the 9-decenoic acid ester to form 9-decenoic acid.

8. The method of any one of claims 2-6, wherein converting the 9-decenoic acid ester into 9-decenoic acid comprises: saponifying the 9-decenoic acid ester to form a 9-decenoate anion; and The 9-decenoate anion is acidified to form 9-decenoic acid.

9. The method of claim 4, wherein converting the 9-decenoic acid ester to 9-decenoic acid comprises: Make the 9-decenoic acid glyceride and C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 esters; and The 9-decenoic acid C 1-8 The ester is converted to 9-decenoic acid.

10. The method of claim 9, wherein said C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol.

11. The method of claim 10, wherein said C 1-8 The monohydric alkanol is methanol.

12. The method of any one of claims 9 to 11, wherein the unsaturated natural fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid.

13. The method of claim 12, wherein the unsaturated natural fatty acid is selected from the group consisting of oleic acid, linoleic acid, and alpha-linolenic acid.

14. The method of any one of claims 9 to 13, wherein the 9-decenoic acid C 1-8 The conversion of the ester into 9-decenoic acid comprises converting the 9-decenoic acid C 1-8 The ester is hydrolyzed to form 9-decenoic acid.

15. The method of any one of claims 9 to 13, wherein the 9-decenoic acid C 1-8 The conversion of the ester to 9-decenoic acid involves: The 9-decenoic acid C 1-8 saponification of the ester to form a 9-decenoate anion; and The 9-decenoate anion is acidified to form 9-decenoic acid.

16. The process of any one of claims 3 to 15, wherein the short chain alpha olefin is selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene.

17. The process of claim 16, wherein the short chain alpha olefin is selected from the group consisting of ethylene, propylene, and 1-butene.

18. The process of any one of claims 1 to 17, wherein the brominating agent is hydrobromic acid.

19. The process of any one of claims 1 to 18, wherein the aminating agent is ammonia.

20. A method for producing polyamide from natural oils, the method comprising: Provide 9-decenoic acid C 1-8 Alkyl esters, wherein 9-decenoic acid C 1-8 Alkyl esters include 9-decenoic acid C obtained from natural oil compositions 1-8 alkyl esters; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 alkyl esters; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 alkyl esters; The 10-aminodecanoic acid C 1-8 conversion of the alkyl ester to 10-aminodecanoic acid; and polymerizing 10-aminodecanoic acid to form a polyamide-10 polymer, The metathesis catalyst is slurried with the natural oil or unsaturated ester, or added to the natural oil or unsaturated ester in a solid form.

21. The method of claim 20, wherein 9-decenoic acid C is obtained from a natural oil 1-8 Alkyl esters include: Provides unsaturated natural fatty acids including C 1-8 natural oil compositions of alkyl esters; and The unsaturated natural fatty acid C 1-8 Alkyl esters react with short-chain α-olefins in the presence of a metathesis catalyst to form 9-decenoic acid C 1-8 Alkyl esters and 1-decene.

22. The method of claim 21, wherein: The unsaturated natural fatty acid C 1-8 The alkyl ester is an unsaturated natural fatty acid methyl ester; the 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester; the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate; and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

23. The method of claim 20, wherein 9-decenoic acid C is obtained from a natural oil 1-8 Alkyl esters include: Providing a natural oil composition comprising unsaturated natural fatty acid glycerides; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and Make the 9-decenoic acid glyceride and C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 ester.

24. The method of claim 23, wherein said C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol.

25. The method of claim 24, wherein said C 1-8 The monohydric alkanol is methanol.

26. The method of claim 22, wherein obtaining methyl 9-decenoate from a natural oil comprises: Providing a natural oil composition comprising unsaturated natural fatty acid glycerides; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and Make the 9-decenoic acid glyceride and C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 Alkyl esters.

27. The method of claim 26, wherein said C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol.

28. The method of claim 26, wherein said C 1-8 The monohydric alkanol is methanol, and the 9-decenoic acid C 1-8 The alkyl ester is methyl 9-decenoate.

29. The method of any one of claims 21-28, wherein the unsaturated natural fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid.

30. The method of claim 29, wherein the unsaturated natural fatty acid is selected from the group consisting of oleic acid, linoleic acid, and alpha-linolenic acid.

31. The process of any one of claims 21-30, wherein the short chain alpha olefin is selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene.

32. The process of claim 31 wherein the short chain alpha olefin is selected from the group consisting of ethylene, propylene, and 1-butene.

33. The method of any one of claims 20 to 32, wherein the 10-aminodecanoic acid C 1-8 The conversion of the alkyl ester into 10-aminodecanoic acid comprises converting the 10-aminodecanoic acid C 1-8 The alkyl ester is hydrolyzed to form 10-aminodecanoic acid.

34. The method of claim 33, wherein 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester, the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate, and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

35. The method of any one of claims 20-30, wherein the 10-aminodecanoic acid C 1-8 The conversion of the alkyl ester to 10-aminodecanoic acid involves: The 10-aminodecanoic acid C 1-8 saponification of the alkyl ester to form the 10-aminodecanoate anion; and The 10-aminodecanoate anion is acidified to form 10-aminodecanoic acid.

36. The method of claim 35, wherein 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester, the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate, and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

37. The process of any one of claims 20 to 36, wherein the brominating agent is hydrobromic acid.

38. The process of any one of claims 20-37, wherein the aminating agent is ammonia.

39. A method for producing a polyamide from a natural oil, the method comprising: Provide 9-decenoic acid C 1-8 Alkyl esters, wherein 9-decenoic acid C 1-8 Alkyl esters include 9-decenoic acid C obtained from natural oil compositions 1-8 alkyl esters; 9-decenoic acid C 1-8 The alkyl ester reacts with a brominating agent to form 10-bromodecanoic acid C 1-8 alkyl esters; 10-bromodecanoic acid C 1-8 The alkyl ester reacts with an aminating agent to form 10-aminodecanoic acid C 1-8 alkyl esters; and 10-aminodecanoic acid C 1-8 The alkyl ester is polymerized to form the polyamide-10 polymer.

40. The method of claim 39, wherein 9-decenoic acid C is obtained from a natural oil 1-8 Alkyl esters include: Provides unsaturated natural fatty acids including C 1-8 natural oil compositions of alkyl esters; and The unsaturated natural fatty acid C 1-8 Alkyl esters react with short-chain α-olefins in the presence of a metathesis catalyst to form 9-decenoic acid C 1-8 Alkyl esters and 1-decene.

41. The method of claim 40, wherein: The unsaturated natural fatty acid C 1-8 The alkyl ester is an unsaturated natural fatty acid methyl ester; the 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester; the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate; and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

42. The method of claim 39, wherein 9-decenoic acid C is obtained from a natural oil 1-8 Alkyl esters include: Providing a natural oil composition comprising unsaturated natural fatty acid glycerides; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and Make the 9-decenoic acid glyceride and C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 ester.

43. The method of claim 42, wherein said C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol.

44. The method of claim 43, wherein said C 1-8 The monohydric alkanol is methanol.

45. The method of claim 41, wherein obtaining methyl 9-decenoate from a natural oil comprises: Providing a natural oil composition comprising unsaturated natural fatty acid glycerides; reacting the unsaturated natural fatty acid glyceride with a short chain α-olefin in the presence of a metathesis catalyst to form 9-decenoic acid glyceride and 1-decene; and Make the 9-decenoic acid glyceride and C 1-8 Monoalkanol reacts to form 9-decenoic acid C 1-8 Alkyl esters.

46. ​​The method of claim 45, wherein said C 1-8 The monohydric alkanol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, neopentyl alcohol, hexanol, heptanol, octanol, and 2-ethylhexanol.

47. The method of claim 45, wherein said C 1-8 The monohydric alkanol is methanol, and the 9-decenoic acid C 1-8 The alkyl ester is methyl 9-decenoate.

48. The method of any one of claims 40-47, wherein the unsaturated natural fatty acid is selected from the group consisting of myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, elaidic acid, and alpha-linolenic acid.

49. The method of claim 48, wherein the unsaturated natural fatty acid is selected from the group consisting of oleic acid, linoleic acid, and alpha-linolenic acid.

50. The process of any one of claims 40-49, wherein the short chain alpha olefin is selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene.

51. The method of claim 50, wherein the short chain alpha olefin is selected from the group consisting of: ethylene, propylene, and 1-butene.

52. The method of any one of claims 39-51, wherein 9-decenoic acid C 1-8 The alkyl ester is 9-decenoic acid methyl ester, the 10-bromodecanoic acid C 1-8 The alkyl ester is methyl 10-bromodecanoate, and the 10-aminodecanoic acid C 1-8 The alkyl ester was methyl 10-aminodecanoate.

53. The process of any one of claims 39-52, wherein the brominating agent is hydrobromic acid.

54. The method of any one of claims 39-53, wherein the aminating agent is ammonia.