阅读说明：本技术 甘油酯低聚物的生产方法和由其形成的产品 (Method for producing oligomer of glyceride and product formed therefrom ) 是由 K.纳拉西姆汉 A.C.霍塔伦 N.T.费尔韦瑟 L.A.赞诺尼 B.A.舒伯特 A.丹宁 于 2020-02-19 设计创作，主要内容包括：本文中总体上公开改进的甘油酯低聚物生产工艺。在一些实施方式中,所公开的工艺提供利用烯烃易位使不饱和甘油酯低聚以生产新颖的支链聚酯组合物的改进的方法。在一些方面中,本公开还提供通过这样的工艺形成的组合物。(An improved glyceride oligomer production process is generally disclosed herein. In some embodiments, the disclosed processes provide an improved method of oligomerizing unsaturated glycerides using olefin metathesis to produce novel branched polyester compositions. In some aspects, the present disclosure also provides compositions formed by such processes.)

1. A method of forming a glyceride polymer, the method comprising:

(a) providing a reaction mixture comprising an unsaturated natural oil glyceride;

(b) introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomerized unsaturated natural oil glycerides, and a first olefin by-product; and

(c) introducing a second amount of an olefin metathesis catalyst to the first product mixture to react the unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product.

2. The method of claim 1, wherein the second product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a third amount of an olefin metathesis catalyst to the second product mixture to react the unreacted unsaturated natural oil glycerides and the second oligomerized unsaturated natural oil glycerides and form a third product mixture comprising third oligomerized unsaturated natural oil glycerides and third olefin byproducts.

3. The method of claim 2, wherein the third product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a fourth amount of an olefin metathesis catalyst to the third product mixture to react the unreacted unsaturated natural oil glycerides and the third oligomerized unsaturated natural oil glycerides and form a fourth product mixture comprising a fourth oligomerized unsaturated natural oil glycerides and a fourth olefin byproduct.

4. A method according to claim 3, wherein the fourth product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a fifth amount of an olefin metathesis catalyst to the fourth product mixture to react the unreacted unsaturated natural oil glycerides and the fourth oligomerized unsaturated natural oil glycerides and form a fifth product mixture comprising the fifth oligomerized unsaturated natural oil glycerides and the fifth olefinic by-product.

5. The method of any of claims 1 to 4, wherein the weight to weight ratio of any two of the first amount of olefin metathesis catalyst, the second amount of olefin metathesis catalyst, the third amount of olefin metathesis catalyst, the fourth amount of olefin metathesis catalyst, and the fifth amount of olefin metathesis catalyst ranges from 1: 10 to 10: 1. or 1: 5 to 5: 1. or 1: 3 to 3: 1. or 1: 2 to 2: 1.

6. a process as claimed in any one of claims 1 to 5 wherein the unsaturated natural oil glycerides comprise glycerides of unsaturated fatty acids selected from: oleic acid, linoleic acid, linolenic acid, vaccenic acid, 9-decenoic acid, 9-undecenoic acid, 9-dodecenoic acid, 9, 12-tridecadienoic acid, 9, 12-tetradecadienoic acid, 9, 12-pentadecenoic acid, 9,12, 15-hexadecatrienoic acid, 9,12,15 heptadecenoic acid, 9,12, 15-octadecatrienoic acid, 11-dodecenoic acid, 11-tridecenoic acid, and 11-tetradecatetraenoic acid.

7. The method of any of claims 1 to 6, wherein the olefin metathesis catalyst comprises an organoruthenium compound, an organoosmium compound, an organotungsten compound, an organomolybdenum compound, or any combination thereof.

8. A process as claimed in any one of claims 1 to 7, wherein the unsaturated natural oil glyceride is derived from a natural oil.

9. A process as claimed in claim 8, wherein the unsaturated natural oil glyceride is derived from a vegetable oil, for example a seed oil.

10. The method of claim 9, wherein the vegetable oil is rapeseed oil, canola 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, canola oil, pennycress oil, camelina oil, linseed oil, castor oil, or any combination thereof.

11. A process as claimed in any one of claims 1 to 10, wherein the molecular weight (M) of the second oligomeric unsaturated natural oil glyceride_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

12. The method of claim 11, wherein the second oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the first oligomeric unsaturated natural oil glyceride_w)。

13. A process as claimed in any one of claims 1 to 12, wherein the third oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 g/mole to 150,000 g/mole, or 5,000 g/mole to 130,000 g/mole, or 6,000 g/mole to 100,000 g/mole, or 7,000 g/moleFrom 50,000 g/mole, or from 8,000 g/mole to 30,000 g/mole, or from 9,000 g/mole to 20,000 g/mole.

14. The method of claim 13, wherein the third oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the second oligomeric unsaturated natural oil glyceride_w)。

15. A process as claimed in any one of claims 1 to 14, wherein the fourth oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

16. The method of claim 15, wherein the fourth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the third oligomeric unsaturated natural oil glyceride_w)。

17. A process as claimed in any one of claims 1 to 13, wherein the fifth oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

18. A method as in claim 17, wherein the fifth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the fourth oligomeric unsaturated natural oil glyceride_w)。

19. The method of any one of claims 1 to 18, further comprising one or more of: removing at least a portion of the first olefinic by-product from the first product mixture, removing at least a portion of the second olefinic by-product from the second product mixture, removing at least a portion of the third olefinic by-product from the third product mixture, removing at least a portion of the fourth olefinic by-product from the fourth product mixture, and removing at least a portion of the fifth olefinic by-product from the fifth product mixture.

20. The method of any one of claims 1 to 19, wherein the olefin metathesis reaction that produces the first, second, third, fourth, or fifth product mixture is conducted at a temperature of no more than 150 ℃, or no more than 140 ℃, or no more than 130 ℃, or no more than 120 ℃, or no more than 110 ℃, or no more than 100 ℃.

21. A method of forming a glyceride polymer, the method comprising:

(a) providing a reaction mixture comprising an unsaturated natural oil glyceride and optionally an initial oligomeric unsaturated natural oil glyceride;

(b) introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and optionally the initial oligomeric unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, first oligomeric unsaturated natural oil glycerides, and a first olefin by-product; and

(c) introducing a second amount of an olefin metathesis catalyst to the first product mixture to react unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product;

wherein the process comprises isomerizing a first oligomeric unsaturated natural oil glyceride.

22. The method of claim 21, wherein the second product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a third amount of an olefin metathesis catalyst to the second product mixture to react the unreacted unsaturated natural oil glycerides and the second oligomerized unsaturated natural oil glycerides and form a third product mixture comprising third oligomerized unsaturated natural oil glycerides and third olefin byproducts;

wherein the process optionally comprises isomerizing a second oligomeric unsaturated natural oil glyceride.

23. The method of claim 22, wherein the third product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a fourth amount of an olefin metathesis catalyst to the third product mixture to react the unreacted unsaturated natural oil glycerides and the third oligomerized unsaturated natural oil glycerides and form a fourth product mixture comprising a fourth oligomerized unsaturated natural oil glycerides and a fourth olefin by-product;

wherein the process optionally comprises isomerizing a third oligomeric unsaturated natural oil glyceride.

24. A method according to claim 23, wherein the fourth product mixture further comprises unreacted unsaturated natural oil glycerides, and the method further comprises introducing a fifth amount of an olefin metathesis catalyst to the fourth product mixture to react the unreacted unsaturated natural oil glycerides and the fourth oligomerized unsaturated natural oil glycerides and form a fifth product mixture comprising fifth oligomerized unsaturated natural oil glycerides and fifth olefinic byproducts;

wherein the process optionally comprises isomerizing a fourth oligomeric unsaturated natural oil glyceride.

25. The method of any of claims 21 to 24, wherein any two of the first amount of olefin metathesis catalyst, the second amount of olefin metathesis catalyst, the third amount of olefin metathesis catalyst, the fourth amount of olefin metathesis catalyst, and the fifth amount of olefin metathesis catalyst have a weight to weight ratio in the range of 1: 10 to 10: 1. or 1: 5 to 5: 1. or 1: 3 to 3: 1. or 1: 2 to 2: 1.

26. a process as claimed in any one of claims 21 to 25, wherein the unsaturated natural oil glycerides comprise glycerides of unsaturated fatty acids selected from: oleic acid, linoleic acid, linolenic acid, vaccenic acid, 9-decenoic acid, 9-undecenoic acid, 9-dodecenoic acid, 9, 12-tridecadienoic acid, 9, 12-tetradecadienoic acid, 9, 12-pentadecenoic acid, 9,12, 15-hexadecatrienoic acid, 9,12,15 heptadecenoic acid, 9,12, 15-octadecatrienoic acid, 11-dodecenoic acid, 11-tridecenoic acid, and 11-tetradecenoic acid.

27. The method of any of claims 21 to 26, wherein the olefin metathesis catalyst comprises an organoruthenium compound, an organoosmium compound, an organotungsten compound, an organomolybdenum compound, or any combination thereof.

28. A process as claimed in any one of claims 21 to 27, wherein the unsaturated natural oil glyceride is derived from a natural oil.

29. A process as claimed in claim 28, wherein the unsaturated natural oil glyceride is derived from a vegetable oil, for example a seed oil.

30. The method of claim 29, wherein the vegetable oil is rapeseed oil, canola 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, canola oil, pennycress oil, camelina oil, linseed oil, castor oil, or any combination thereof.

31. A process as claimed in any one of claims 21 to 30, wherein the molecular weight (M) of the second oligomeric unsaturated natural oil glyceride_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

32. A method as in claim 31, wherein the second oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the first oligomeric unsaturated natural oil glyceride_w)。

33. A process as claimed in any one of claims 21 to 32, wherein the third oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

34. A method as in claim 33, wherein the third oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the second oligomeric unsaturated natural oil glyceride_w)。

35. A process as claimed in any one of claims 21 to 34, wherein the fourth oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

36. A method as in claim 35, wherein the fourth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the third oligomeric unsaturated natural oil glyceride_w)。

37. Such as rightThe method of any of claims 21 to 33, wherein the fifth oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole.

38. A method as in claim 37, wherein the fifth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the fourth oligomeric unsaturated natural oil glyceride_w)。

39. The method of any of claims 21 to 38, further comprising one or more of: removing at least a portion of the first olefinic by-product from the first product mixture, removing at least a portion of the second olefinic by-product from the second product mixture, removing at least a portion of the third olefinic by-product from the third product mixture, removing at least a portion of the fourth olefinic by-product from the fourth product mixture, and removing at least a portion of the fifth olefinic by-product from the fifth product mixture.

40. The method of any one of claims 21 to 39, wherein the olefin metathesis reaction that produces the first, second, third, fourth, or fifth product mixture is conducted at a temperature of no more than 150 ℃, or no more than 140 ℃, or no more than 130 ℃, or no more than 120 ℃, or no more than 110 ℃, or no more than 100 ℃.

41. The process of any one of claims 21 to 40, wherein the isomerization or optional isomerization step comprises heating the first product mixture or one or more of the optional second, third or fourth product mixtures to a temperature of at least 150℃ or at least 155℃ or at least 160℃ or at least 165℃ or at least 170℃.

42. A glyceride polymer formed by the process of any one of claims 1 to 20.

43. A glyceride polymer formed by the process of any one of claims 21 to 41.

Technical Field

An improved glyceride oligomer production process is generally disclosed herein. In some embodiments, the disclosed processes provide an improved method of oligomerizing unsaturated glycerides using olefin metathesis to produce novel branched polyester compositions. In some aspects, the present disclosure also provides compositions formed by such processes.

Background

Branched polyesters have a wide variety of applications. Their high molecular weight and low crystallinity make them attractive for use as plasticizers and rheology modifiers, and the like, in adhesive compositions, personal and consumer care compositions. Such compounds are typically derived from certain short chain dicarboxylic acids such as adipic acid. Thus, such compounds may be unsuitable for certain applications, particularly where it may be desirable for the polyester to contain longer chain hydrophobic moieties.

Self-metathesis of natural oils (unsaturated fatty acid glycerides), such as soybean oil, provides a means to produce branched polyesters with longer chain hydrophobic moieties. Some such methods are disclosed in U.S. patent application publication No. 2013/0344012. However, using such a process, it remains difficult to obtain branched polyester compositions having higher molecular weights, for example, molecular weights corresponding to oligomers containing on average about 5-6 triglycerides or more. Obtaining higher molecular weight oligomers using such processes has many difficulties, including practical limitations on the time and vacuum quality required to drive the reaction toward the production of higher molecular weight oligomers in order to remove the product olefins.

Thus, while self-metathesis using unsaturated fatty acid glycerides provides a useful means of obtaining branched polyesters, there is a continuing need to develop additional processes that will allow practical synthesis of higher weight glyceride oligomers.

Disclosure of Invention

The present disclosure overcomes one or more of the above obstacles by providing higher molecular weight glyceride oligomers and processes and compositions for the production of such compounds.

In a first aspect, the present disclosure provides a method of forming a glyceride polymer, the method comprising: (a) providing a reaction mixture comprising an unsaturated natural oil glyceride; (b) introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomerized unsaturated natural oil glycerides, and a first olefin by-product; and (c) introducing a second amount of an olefin metathesis catalyst to the first product mixture to react unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product.

In a second aspect, the present disclosure provides a method of forming a glyceride polymer, the method comprising: (a) providing a reaction mixture comprising an unsaturated natural oil glyceride and optionally an initial oligomeric unsaturated natural oil glyceride; (b) introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and optionally the initial oligomeric unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomeric unsaturated natural oil glycerides, and a first olefin by-product; and (c) introducing a second amount of an olefin metathesis catalyst to the first product mixture to react unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product; wherein the process comprises isomerizing a first oligomeric unsaturated natural oil glyceride.

In a third aspect, the present disclosure provides a glyceride polymer formed by the method of the first aspect or any embodiment thereof.

In a fourth aspect, the present disclosure provides a glyceride polymer formed by the method of the second aspect or any embodiment thereof.

Further (additional) aspects and embodiments are provided in the foregoing figures, detailed description (detailed description), and claims.

Drawings

The following figures are provided for the purpose of illustrating various embodiments of the compositions and methods disclosed herein. The figures are provided for illustrative purposes only and are not intended to describe any preferred composition or preferred method or to serve as a source of any limitation (source) on the scope of the claimed invention.

FIG. 1 shows a non-limiting embodiment of the process disclosed herein for forming a glyceride polymer.

FIG. 2 shows a non-limiting embodiment of the process disclosed herein for forming a glyceride polymer.

Detailed Description

The following description sets forth various aspects and embodiments of the invention disclosed herein. No particular embodiment is intended to limit the scope of the invention. Rather, the embodiments provide non-limiting examples of various compositions and methods that are included within the scope of the claimed invention. The description should be read from the perspective of one of ordinary skill in the art. Thus, information well known to those skilled in the art is not necessarily included.

Definition of

The following terms and phrases have the meanings indicated below, unless otherwise provided herein. The present disclosure may use other terms and phrases not expressly defined herein. Such other terms and phrases should have the meanings that they would have to one of ordinary skill in the art in the context of this disclosure. In some cases, terms or phrases may 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 vice versa unless explicitly stated to the contrary.

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" includes a single substituent as well as two or more of each substituent, and the like.

As used herein, "for example," "for instance," "such as," or "including" is intended to introduce examples that further clarify more general (superordinate) subject matter. Such examples are provided merely as an aid to understanding the embodiments illustrated in the present disclosure and are not intended to be limiting in any way unless explicitly stated otherwise. Nor do these phrases indicate any type of preference for the disclosed embodiments.

As used herein, "polymer" refers to a substance having a chemical structure comprising a plurality of repeating building units formed of a substance of lower relative molecular mass relative to the molecular mass of the polymer. The term "polymer" includes soluble and/or meltable molecules having a chain of repeating units, and also includes insoluble and infusible networks. As used herein, the term "polymer" may include oligomeric materials having only some (e.g., 3-100) building blocks.

As used herein, "natural oil" refers to an oil obtained from a plant or animal source. The term also includes modified plant or animal sources (e.g., transgenic (genetically modified) plant or animal sources), unless otherwise indicated. Examples of natural oils include, but are not limited to, vegetable oils, algal oils, fish oils, animal fats, tall oils, derivatives of these oils, any combination of these oils, and the like. Representative, non-limiting examples of vegetable oils 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, canola oil, pennycress oil, camelina oil, linseed oil, and castor oil. Representative, non-limiting examples of animal fats include lard, tallow, poultry fat, yellow grease, and fish oil. Tall oil is a by-product of wood pulp manufacture. 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 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 99 wt.% of one or more unsaturated triglycerides, based on the total weight of the natural oil.

The term "natural oil glycerides" refers to glycerides of fatty acids derived from natural oils. Such glycerides include monoacyl, diacyl and triacyl (triglyceride) glycerides. In some embodiments, the natural oil glyceride is a triglyceride. Similarly, the term "unsaturated natural oil glycerides" refers to natural oil glycerides in which at least one of its fatty acid residues comprises unsaturation (unsaturated group). For example, the glycerol ester of oleic acid is an unsaturated natural oil glycerol ester. The term "unsaturated alkenylated natural oil glycerides" refers to unsaturated natural oil glycerides (as defined above) derived via a metathesis reaction with short chain olefins (as defined below). In some cases, the olefination process shortens one or more of the aliphatic chains in the compound. For example, the glyceride of 9-decenoic acid is an unsaturated, alkenylated natural oil glyceride. Similarly, canola oils crotinated (e.g., by 1-butene and/or 2-butene) are unsaturated C's that have been modified by metathesis to contain some short chains₁₀-C₁₅A natural oleyl ester of an ester group.

The term "oligoglyceride moiety" is a moiety comprising two or more (and up to 10 or up to 20) building blocks formed from natural oil glycerides and/or alkenylated natural oil glycerides by olefin metathesis.

As used herein, "metathesis" refers to olefin metathesis. As used herein, "metathesis catalyst" includes any catalyst or catalyst system that catalyzes olefin metathesis reactions.

As used herein, "metathesized" or "metathesizing" refers to the reaction of a feedstock in the presence of a metathesis catalyst to form a "metathesized product," which includes new olefinic compounds, i.e., "metathesized" compounds. Metathesis is not limited to any particular type of olefin metathesis, and may refer to cross-metathesis (i.e., co-metathesis), self-metathesis, ring-opening metathesis polymerization ("ROMP"), ring-closing metathesis ("RCM"), and acyclic diene metathesis ("ADMET"). In some embodiments, metathesizing refers to reacting (self-metathesizing) two triglycerides present in a natural feedstock in the presence of a metathesis catalyst (where each triglyceride has unsaturated carbon-carbon double bonds) to form a new mixture of olefins and esters, which may include triglyceride dimers. Such triglyceride dimers may have more than one olefinic bond, and thus higher (higher) oligomers may also be formed. In addition, in some other embodiments, metathesis may refer to reacting olefins, such as ethylene, and triglycerides with at least one unsaturated carbon-carbon double bond in natural feedstocks to form new olefinic molecules as well as new ester molecules (cross-metathesis).

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

The number of carbon atoms in any group or compound may be expressed as follows: "C_z", which refers to the group of compounds having z carbon atoms; and "C_x-y", refers to a group or compound containing x to y (inclusive) carbon atoms. For example, "C_1-6Alkyl "denotes an alkyl chain having 1 to 6 carbon atoms and includes, for example, but is 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_4-10The olefin "means an olefin molecule having 4 to 10 carbon atoms, and includes, for example, but is 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.

As used herein, the term "short-chain alkene" or "short-chain alkene" refers to C_2-14Range or C_2-12Range or C_2-10Range or C_2-8Any one or combination of unsaturated linear, branched, or cyclic hydrocarbons in the range. Such olefins include alpha-olefins in which an unsaturated carbon-carbon bond is present at one end of the compound. Such olefins also include dienes or trienes. Such olefins also include internal olefins. C_2-6Examples of short chain olefins in the range include, but are not limited to: ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1, 4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene and cyclohexene. C_7-9Non-limiting examples of short chain olefins within the scope include 1, 4-heptadiene, 1-heptene, 3, 6-nonadieneAlkene, 3-nonene, 1,4, 7-octatriene. In certain embodiments, it is preferred to use a mixture of olefins comprising linear and branched low molecular weight olefins in the C4-10 range. In one embodiment, it may be preferred to use a mixture of linear and branched C4 olefins (i.e., a combination of 1-butene, 2-butene, and/or isobutene). In other embodiments, a higher C may be used_11-14And (3) a range.

As used herein, "alkyl" refers to a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, which may be optionally substituted with as many degrees of substitution as are permissible, as described further herein. 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 the alkyl group is indicated by the phrase "C_x-yAlkyl "refers to an alkyl group as defined herein containing x to y (inclusive) carbon atoms. Thus, "C_1-6Alkyl "denotes an alkyl chain having 1 to 6 carbon atoms and includes, for example, but is 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 can be divalent, in which case the group can alternatively be referred to as an "alkylene" group.

As used herein, "alkenyl" refers to a straight or branched chain nonaromatic hydrocarbon having from 2 to 30 carbon atoms and having one or more carbon-carbon double bonds, which may be optionally substituted with as many degrees of substitution as are permitted, as further described herein. Examples of "alkenyl" as used herein include, but are not limited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number of carbon atoms in the alkenyl group is indicated by the phrase "C_x-yAlkenyl "refers to an alkenyl group as defined herein comprising x to y (inclusive) carbon atoms. Thus, "C_2-6Alkenyl "represents an alkenyl chain having 2 to 6 carbon atoms and includes, for example, but is not limited to, ethenyl, 2-propenyl, 2-butenyl and 3-butenyl. In some casesAn "alkenyl" group can be divalent, in which case the group can alternatively be referred to as an "alkenylene" group.

As used herein, "mixed" or "mixture" broadly refers to any combination of a mixture of two or more compositions. The two or more compositions need not have the same physical state; thus, solids may be "mixed" with a liquid, for example, to form a slurry, suspension, or solution. Furthermore, these terms do not require any degree of homogeneity or homogeneity of the composition. Such "mixtures" may be homogeneous or heterogeneous, or may be homogeneous or heterogeneous. Furthermore, the term does not require the use of any particular equipment for effecting mixing, such as an industrial mixer.

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.

As used herein, "comprising" or "includes" or "including" or "comprising of" refers to an open group that means that the group may include additional members (members) in addition to those explicitly recited. For example, the phrase "comprising a" means that a must be present, but that other members may also be present. The terms "comprising," "having," and "containing" have the same meaning as their grammatical variants. In contrast, "consisting of … … (consistency of)" or "consisting of … … (consistency of)" or "consisting of … … (consistency of)" means a closed group. For example, the phrase "consisting of a" means a and only a is present.

As used herein, "or" should be given its broadest reasonable interpretation and should not be limited to the alternative/or configuration. Thus, the phrase "comprising a or B" means that a may be present and B is absent, or B is present and a is absent, or both a and B are present. Further, for example, if A is defined, there may be multiple members such as A₁And A₂Then one or more members of the category may be present at the same time.

Other terms are defined in other parts of this specification, although not included in this subsection.

Methods involving batch catalyst introduction

In at least one aspect, the present disclosure provides a method of forming a glyceride polymer, the method comprising: (a) providing a reaction mixture comprising an unsaturated natural oil glyceride; (b) introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomerized unsaturated natural oil glycerides, and a first olefin by-product; and (c) introducing a second amount of an olefin metathesis catalyst to the first product mixture to react unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product.

Such a process is characterized in that the olefin metathesis catalyst is introduced in two or more batches. Thus, in some embodiments, additional batches of olefin metathesis catalyst may be added. For example, in some embodiments, the second product mixture further comprises unreacted unsaturated natural oil glycerides, and further comprising introducing a third amount of an olefin metathesis catalyst to the second product mixture to react the unreacted unsaturated natural oil glycerides and the second oligomerized unsaturated natural oil glycerides and form a third product mixture comprising a third oligomerized unsaturated natural oil glycerides and a third olefin by-product.

In the same manner, a fourth batch of catalyst may be added. Thus, in some further embodiments, the third product mixture further comprises unreacted unsaturated natural oil glycerides, and further comprising introducing a fourth amount of an olefin metathesis catalyst to the third product mixture to react the unreacted unsaturated natural oil glycerides and the third oligomerized unsaturated natural oil glycerides and form a fourth product mixture comprising a fourth oligomerized unsaturated natural oil glycerides and a fourth olefin by-product.

In the same manner, a fifth batch of catalyst may be added. Thus, in some further embodiments, the fourth product mixture further comprises unreacted unsaturated natural oil glycerides, and further comprising introducing a fifth amount of an olefin metathesis catalyst to the fourth product mixture to react the unreacted unsaturated natural oil glycerides and the fourth oligomerized unsaturated natural oil glycerides and form a fifth product mixture comprising a fifth oligomerized unsaturated natural oil glycerides and a fifth olefinic by-product.

In the embodiments set forth in the preceding paragraph, the amount of olefin metathesis catalyst may vary (or be the same) from one batch to the next. Thus, in some of the preceding embodiments, any two of the first, second, third, fourth, and fifth amounts of olefin metathesis catalyst have a weight to weight ratio ranging from 1: 10 to 10: 1. or 1: 5 to 5: 1. or 1: 3 to 3: 1. or 1: 2 to 2: 1.

typically, the unsaturated natural oil glycerides are derived from one or more natural oils. In some further embodiments, the unsaturated natural oil glycerides are derived from one or more vegetable oils, such as seed oils. Any suitable vegetable oil may be used, including, but not limited to, rapeseed oil, canola 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, canola oil, pennycress oil, camelina oil, linseed oil, castor oil, or any combination thereof. In some embodiments, the vegetable oil is canola oil.

Such seed vegetable oil fatty acid glycerides in which at least one of the hydroxyl groups on the glycerol forms an ester with an unsaturated fatty acid. Such glycerides may be mono-, di-, or tri-glycerides, or any combination thereof. The unsaturated fatty acid moiety can be a naturally occurring unsaturated fatty acid moiety (e.g., oleic acid), or in some other examples it can be an unsaturated fatty acid moiety formed from alkenylating an unsaturated fatty acid (e.g., 9-decenoic acid, which can be formed by reacting an a-olefin with a naturally occurring fatty acid, such as oleic acid). Thus, in some embodiments, the unsaturated natural oil glycerides comprise glycerides of unsaturated fatty acids selected from: oleic acid, linoleic acid, linolenic acid, vaccenic acid (vaccenic acid), 9-decenoic acid, 9-undecenoic acid, 9-dodecenoic acid, 9, 12-tridecadienoic acid, 9, 12-tetradecadienoic acid, 9, 12-pentadecenoic acid, 9,12, 15-hexadecatrienoic acid, 9,12,15 heptadecenoic acid, 9,12, 15-octadecatrienoic acid, 11-dodecenoic acid, 11-tridecenoic acid, and 11-tetradecenoic acid.

As noted above, the unsaturated natural oil glycerides may, in some embodiments, comprise unsaturated, alkenylated natural oil glycerides. The unsaturated alkenylated natural oil glycerides are formed by reacting a second unsaturated natural oil glyceride with a short chain olefin in the presence of a second metathesis catalyst. In some such embodiments, the unsaturated, alkenylated natural oil glycerides have a lower molecular weight than the second unsaturated natural oil glyceride. Any suitable short chain olefin may be used in accordance with the embodiments described above. In some embodiments, the short chain olefin is a C2-8 olefin or a C2-6 olefin. In some such embodiments, the short chain olefin is ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, or 3-hexene. In some such further embodiments, the short chain olefin is ethylene, propylene, 1-butene, 2-butene, or isobutylene. In some embodiments, the short chain olefin is ethylene. In some embodiments, the short chain olefin is propylene. In some embodiments, the short-chain olefin is 1-butene. In some embodiments, the short-chain olefin is 2-butene.

In embodiments where the unsaturated natural oil glycerides comprise unsaturated alkenylated natural oil glycerides, the unsaturated alkenylated natural oil glycerides may comprise any suitable amount of the composition. In some embodiments, the unsaturated natural oil glycerides comprise at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, or at least 20 wt.%, or at least 25 wt.%, each up to 50 wt.%, or 60 wt.%, or 70 wt.%, based on the total weight of unsaturated natural oil glycerides in the composition.

Any suitable olefin metathesis catalyst may be used. In some embodiments, the olefin metathesis catalyst comprises an organoruthenium compound, an organoosmium compound, an organotungsten compound, an organomolybdenum compound, or any combination thereof. In some embodiments, the olefin metathesis catalyst comprises an organoruthenium compound.

Any suitable molecular weight may be achieved at various stages of the process. For example, in some embodiments, the molecular weight (M) of the second oligomeric unsaturated natural oil glyceride_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole. In some such embodiments, the second oligomeric unsaturated natural oil glycerides have a higher molecular weight (M) than the first oligomeric unsaturated natural oil glycerides_w)。

In some further embodiments, the third oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole. In some such embodiments, the third oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the second oligomeric unsaturated natural oil glyceride_w)。

In some further embodiments, the fourth oligomeric unsaturated natural oil glyceride has a molecular weight (M)_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole. At some point in thisIn like embodiments, the fourth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the third oligomeric unsaturated natural oil glyceride_w)。

In some further embodiments, the molecular weight (M) of the fifth oligomeric unsaturated natural oil glyceride_w) In the range of 4,000 to 150,000, or 5,000 to 130,000, or 6,000 to 100,000, or 7,000 to 50,000, or 8,000 to 30,000, or 9,000 to 20,000 g/mole. In some such embodiments, the fifth oligomeric unsaturated natural oil glyceride has a higher molecular weight (M) than the fourth oligomeric unsaturated natural oil glyceride_w)。

As noted above, the oligomerization process produces an olefin by-product. In some cases, it may be desirable to remove at least a portion of this by-product, for example, to drive the reaction toward completion, to mitigate the risk of unwanted side reactions, etc. Thus, in some embodiments of any of the preceding embodiments, one or more of the following additional steps may be introduced: removing at least a portion of the first olefinic by-product from the first product mixture, removing at least a portion of the second olefinic by-product from the second product mixture, removing at least a portion of the third olefinic by-product from the third product mixture, removing at least a portion of the fourth olefinic by-product from the fourth product mixture, and removing at least a portion of the fifth olefinic by-product from the fifth product mixture.

The removal may be carried out by any suitable means, such as venting the reactor, a stripping step, and the like. Various means of removing olefin by-products are described in U.S. patent application publication No.2013/0344012, which is hereby incorporated by reference.

The olefin metathesis reaction can be carried out at any suitable temperature. In some embodiments, the olefin metathesis reaction that produces the first, second, third, fourth, or fifth product mixture is carried out at a temperature of no more than 150 ℃, or no more than 140 ℃, or no more than 130 ℃, or no more than 120 ℃, or no more than 110 ℃, or no more than 100 ℃. In some such embodiments, the reactor temperature is maintained constant from one batch to the next. However, in some other cases, the reactor may be cooled to a lower temperature (e.g., room temperature) between steps.

The methods disclosed herein may include additional chemical and physical treatments of the resulting glyceride copolymers. For example, in some embodiments, the resulting glyceride copolymers are fully or partially hydrogenated, such as diene-selective hydrogenation.

FIG. 1 discloses a non-limiting embodiment of a method 100 of forming a glyceride polymer, comprising: 101 providing a reaction mixture comprising an unsaturated natural oil glyceride; 102 introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomerized unsaturated natural oil glycerides, and a first olefin by-product; and 103 introducing a second amount of an olefin metathesis catalyst to the first product mixture to react unreacted unsaturated natural oil glyceride and the first oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product.

Processes involving isomerization

In at least one aspect, any one or more of the first, second, third or fourth oligomeric unsaturated natural oil glycerides.

The isomerization may be carried out by any suitable means for isomerizing olefinic bonds in the unsaturated product. Suitable methods are described in U.S. patent No.9,382,502, which is hereby incorporated by reference.

FIG. 2 discloses a non-limiting embodiment of a method 200 of forming a glyceride polymer, which includes: 201 providing a reaction mixture comprising unsaturated natural oil glycerides and optionally initial oligomeric unsaturated natural oil glycerides; 202 introducing a first amount of an olefin metathesis catalyst to the reaction mixture to react the unsaturated natural oil glycerides and optionally the initial oligomeric unsaturated natural oil glycerides and form a first product mixture comprising unreacted unsaturated natural oil glycerides, a first oligomeric unsaturated natural oil glycerides, and a first olefin by-product; 203 isomerizing the first oligomeric unsaturated natural oil glyceride; and, 204 introducing a second amount of an olefin metathesis catalyst to the first product mixture to react the unreacted unsaturated natural oil glyceride and the first (isomerized) oligomerized unsaturated natural oil glyceride and form a second product mixture comprising a second oligomerized unsaturated natural oil glyceride and a second olefinic by-product.

Derivation from renewable sources

The compounds used in any of the aspects or embodiments disclosed herein may in certain embodiments be derived from renewable sources, for example from various natural oils or derivatives thereof. These compounds may be produced from such renewable sources using any suitable method.

Olefin metathesis provides a viable means for converting certain natural oil feedstocks into olefins and esters as follows: may be used in a variety of applications or may be further chemically modified and used in a variety of applications. In some embodiments, the composition (or components of the composition) may be formed from a renewable feedstock (e.g., a renewable feedstock formed by a metathesis reaction of a natural oil and/or a fatty acid or fatty ester derivative thereof). When a compound containing a carbon-carbon double bond undergoes a metathesis reaction in the presence of a metathesis catalyst, some or all of the original carbon-carbon double bonds are broken and new carbon-carbon double bonds are formed. The products of such metathesis reactions include carbon-carbon double bonds at various positions, which can provide unsaturated organic compounds having useful chemistries.

A wide range of natural oils or derivatives thereof may be used in such metathesis reactions. Examples of suitable natural oils include, but are not limited to, vegetable oils, algal oils, fish oils, animal fats, tall oils, derivatives of these oils, any combination of these oils, and the like. Representative, non-limiting examples of vegetable oils 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, canola oil, pennycress oil, camelina oil, linseed oil, and castor oil. Representative, non-limiting examples of animal fats include lard, tallow, poultry fat, yellow grease, and fish oil. Tall oil is a by-product of wood pulp manufacture. 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 feedstock comprises at least 50 wt.%, or at least 60 wt.%, or at least 70 wt.%, or at least 80 wt.%, or at least 90 wt.%, or at least 95 wt.%, or at least 97 wt.%, or at least 99 wt.% of one or more unsaturated triglycerides, based on the total weight of the natural oil feedstock.

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

Such natural oils or derivatives thereof comprise esters of various unsaturated fatty acids such as triglycerides. The identity and concentration of such fatty acids varies depending on the oil source and in some cases on the species. In some embodiments, the natural oil comprises one or more esters of oleic acid, linoleic acid, linolenic acid, or any combination thereof. When such fatty acid esters are metathesized, new compounds are formed. For example, in embodiments where metathesis uses certain short-chain olefins such as ethylene, propylene, or 1-butene and where the natural oils include oleates, substantial amounts of 1-decene and 1-decenoic acid (or esters thereof) are formed, among other products.

In some embodiments, the natural oils may be subjected to various pretreatment processes that may facilitate their utility (utility) 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.

In some embodiments, after any optional pretreatment of the natural oil feedstock, the natural oil feedstock is reacted in the presence of a metathesis catalyst in a metathesis reactor. In some other embodiments, an unsaturated ester (e.g., an unsaturated glyceride, such as an unsaturated triglyceride) is reacted in the presence of a metathesis catalyst in a metathesis reactor. These unsaturated esters may be components of the natural oil feedstock or may be derived from other sources, such as esters produced in earlier-performed metathesis reactions.

The conditions for such metathesis reactions, and reactor design and suitable catalysts are as described below with reference to olefin ester metathesis. This discussion is incorporated by reference as if fully set forth herein.

Olefin metathesis

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

In some embodiments, after any optional pretreatment of the natural oil feedstock, the natural oil feedstock is reacted in the presence of a metathesis catalyst in a metathesis reactor. In some other embodiments, an unsaturated ester (e.g., an unsaturated glyceride, such as an unsaturated triglyceride) is reacted in the presence of a metathesis catalyst in a metathesis reactor. These unsaturated esters may be components of the natural oil feedstock or may be derived from other sources, such as esters produced in earlier-performed metathesis reactions. In certain embodiments, the natural oil or unsaturated ester may undergo a self-metathesis reaction with itself in the presence of a metathesis catalyst.

In some embodiments, metathesis includes reacting a natural oil feedstock (or another unsaturated ester) in the presence of a metathesis catalyst. In some such embodiments, metathesizing comprises reacting one or more unsaturated glycerides (e.g., unsaturated triglycerides) in the natural oil feedstock in the presence of a metathesis catalyst. In some embodiments, the unsaturated glyceride comprises one or more esters of oleic acid, linoleic acid, or a combination thereof. In some other embodiments, the unsaturated glyceride is a partially hydrogenated and/or metathesized product of another unsaturated glyceride (as described above).

The metathesis process can be conducted under any conditions sufficient to produce the desired metathesis product. For example, one 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 may be conducted under an inert atmosphere. Similarly, in embodiments where the reactants are supplied as gases, an inert gaseous diluent may be used in the gas stream. In such embodiments, the inert atmosphere or inert gaseous diluent is typically an inert gas, which means that the gas does not interact with the metathesis catalyst to the extent that it substantially interferes with the catalyst. For example, non-limiting examples of inert gases include helium, neon, argon, methane, and nitrogen, used alone or with each other and other inert gases.

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

The metathesis reactions disclosed herein typically occur in the presence of one or more metathesis catalysts. Such methods may use any suitable metathesis catalyst. The metathesis catalyst in this reaction may include any catalyst or catalyst system that catalyzes a metathesis reaction. Any known metathesis catalyst may be used alone or in combination with one or more additional catalysts. Examples of metathesis catalysts and process conditions are set forth in US 2011/0160472, which is incorporated herein by reference in its entirety except as follows: in the event of any inconsistent disclosure or definition from this specification, the disclosure or definition herein shall be read as pre (vail). Many metathesis catalysts described in US 2011/0160472 are currently available from Materia, Inc.

In some embodiments, the metathesis catalyst comprises a Grubbs (Grubbs) type olefin metathesis catalyst and/or an entity (entity) derived therefrom. In some embodiments, the metathesis catalyst comprises a first generation glatiramer-type olefin metathesis catalyst and/or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a second generation glatiramer-type olefin metathesis catalyst and/or entities derived therefrom. In some embodiments, the metathesis catalyst comprises a first generation Hoveyda-Grubbs (Hoveyda-Grubbs) type olefin metathesis catalyst and/or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a second generation hoverda-grubbs type olefin metathesis catalyst and/or entities derived therefrom. In some embodiments, the metathesis catalyst comprises one or more ruthenium carbene metathesis catalysts sold by materiala, inc. of pasadena, california and/or one or more entities derived from such catalysts. Representative metathesis catalysts from materiala, inc. for use in accordance with the present teachings include, but are not limited to, those sold under the following product numbers and combinations thereof: product number C823(CAS number 172222-30-9), product number C848(CAS number 246047-72-3), product number C601(CAS number 203714-71-0), product number C627(CAS number 301224-40-8), product number C571(CAS number 927429-61-6), product number C598(CAS number 802912-44-3), product number C793(CAS number 92742960-5), product number C801(CAS number 194659-03-9), product number C827(CAS number 253688-91-4), product number C884(CAS number 900169-53-1), product number C833(CAS number 1020085-61-3), product number C859(CAS number 832146-68-6), product number C711(CAS number 635679-24-2), product number C933(CAS number 373640-75-6).

In some embodiments, the metathesis catalyst comprises molybdenum and/or tungsten carbene complexes and/or entities derived from such complexes. In some embodiments, the metathesis catalyst comprises a Schrock type olefin metathesis catalyst and/or entities derived therefrom. In some embodiments, the metathesis catalyst comprises a high oxidation state alkylene complex of molybdenum and/or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a high oxidation state alkylene 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 a molybdenum-and/or tungsten-containing alkylene complex of the type described in one or more of the following: (a) angew.chem.int.ed.engl., 2003, 42, 4592-; (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 from this specification, the disclosure or definition herein shall control.

In certain embodiments, the metathesis catalyst is dissolved in a solvent prior to conducting the metathesis reaction. In certain such embodiments, the selected solvent may be selected to be substantially inert with respect 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, and the like; and chlorinated alkanes such as dichloromethane, chloroform, dichloroethane, and the like. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in a solvent prior to conducting the metathesis reaction. Conversely, for example, the catalyst may be slurried with a natural oil or unsaturated ester, wherein the natural oil or unsaturated ester is in a liquid state. Under these conditions, it is possible to eliminate solvent (e.g., toluene) from the process and eliminate downstream olefin losses when separating the solvent. In other embodiments, the metathesis catalyst may be added in solid form (and unpulped) to the natural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may in some cases be a rate-controlling variable, with the temperature being selected to provide the desired product at an acceptable (acceptable) rate. In certain embodiments, the metathesis reaction temperature is greater than-40 ℃ or greater than-20 ℃ or greater than 0 ℃ or greater than 10 ℃. In certain embodiments, the metathesis reaction temperature is less than 200 ℃ or less than 150 ℃ or less than 120 ℃. In some embodiments, the metathesis reaction temperature is between 0 ℃ and 150 ℃ or between 10 ℃ and 120 ℃.

Examples

The following examples set forth certain illustrative embodiments of the compounds, compositions, and methods disclosed herein. These examples should not be construed as limiting in any way. The examples should also not be construed as representing any preferred embodiment or as indicating any direction for further investigation. Unless otherwise indicated, the chemicals used were ACS, reagents or standard grades available from Sigma-Aldrich.

The following examples report the results of molecular weight determination by Gel Permeation Chromatography (GPC) for certain compositions comprising glyceride copolymers. Weight average molecular weight (M)_w) Values were determined using HPLC analysis of the resulting samples using a styrene calibration curve. Typically, chloroform is used as the mobile phase.

Table 1 shows the molecular weight and residence time of the polystyrene standards.

TABLE 1

Example A1-batch (batch) Process with overnight Hold and without THMP

Self-metathesized poly (oil) was prepared by charging canola oil (23kg) to a 30 liter glass reactor. Canola oil was pretreated by bubbling with nitrogen while heating to 200 ℃ for a holding time of 2 hours. The canola oil was cooled to room temperature and stirred overnight with nitrogen sparging. The pre-treated canola oil was then heated to 95 ℃ under nitrogen sparging, followed by addition of a toluene solution of C827 metathesis catalyst (20ppm catalyst relative to the weight of the oil) and stirring for 1 hour. An additional toluene solution of the C827 metathesis catalyst (20ppm catalyst-40 ppm total catalyst relative to the weight of the oil) was added followed by stirring for 1 hour. Additional toluene solution of C827 metathesis catalyst (10 ppm catalyst to 50ppm total catalyst relative to the weight of the oil) was added with stirring for 1 hour. The molecular weight after 5 hours of reaction (50ppm catalyst) was 11,013. The reaction was maintained at 95 ℃ overnight under nitrogen sparge. The next morning an additional toluene solution of the C827 metathesis catalyst (10 ppm catalyst to 60ppm total relative to the weight of the oil) was added followed by stirring for 1 hour. Then, 3.5kg of a sample of the poly oil to which no THMP was added was obtained. The reaction was allowed to cool and was discharged. Further details are set forth in table 2 below.

Example A2-batch Process with overnight Hold and THMP

The process of example a1 was carried out as described above, except that: before the final discharge, the reaction mixture was cooled to 80 ℃, followed by the addition of THMP (5 molar equivalents relative to the total catalyst added, less catalyst removed with 3.5kg of sample) and stirring for 2 hours. Further details are set forth in table 2 below.

Example A3-batch Process with overnight Hold and without THMP

The process of example 1 was carried out as described above with the exception that: the addition of THMP was not performed. The reaction was carried out under a nitrogen blanket. An additional toluene solution of C827 metathesis catalyst (10 ppm catalyst to 60ppm total catalyst relative to the weight of the oil) was added one hour after 50ppm total catalyst was added. The molecular weight after 6 hours of reaction (60ppm catalyst) was 10,912 Da. The reaction was allowed to stand overnight at 95 ℃ under a nitrogen blanket. The next morning an additional toluene solution of the C827 metathesis catalyst (10 ppm catalyst to 70ppm total relative to the weight of the oil) was added followed by stirring for 1 hour. Then, 2.0kg of a sample of the poly oil to which no THMP was added was obtained. The reaction mixture was cooled to 80 ℃ and stirred for 2 hours. The reaction was cooled and discharged. Further details are set forth in table 2 below.

Example A4-batch Process with overnight Hold and THMP

The process of example a3 was carried out as described above, except that: before the final discharge, the reaction mixture was cooled to 80 ℃, followed by the addition of THMP (5 molar equivalents relative to the total catalyst added, less catalyst removed with 3.5kg of sample) and stirring for 2 hours. Further details are set forth in table 2 below.

Example A5-batch Process with overnight Hold and without THMP

A toluene solution of the C827 metathesis catalyst was added at a dosage of 20ppm/20ppm/10ppm (relative to the weight of the oil) every 30 minutes. After stirring for one hour, an additional toluene solution of the C827 metathesis catalyst (10 ppm catalyst-60 ppm total catalyst relative to the weight of the oil) was added. The molecular weight after 8 hours of reaction (60ppm catalyst) was 11,106. The reaction was allowed to stand overnight at 95 ℃ with nitrogen bubbling. The next morning, additional toluene solution of C827 metathesis catalyst (10 ppm catalyst-70 ppm total relative to the weight of oil) was added followed by stirring for 1 hour. The reaction was cooled and discharged. The yield was 0.77kg of poly oil/kg canola oil (after loss of service).

TABLE 2

Example B1-batch Process with heating/Cooling

Self-metathesized poly-oil was prepared by adding canola oil to a 2L glass reactor. Canola oil was pretreated by bubbling with nitrogen while heating to 200 ℃ for a holding time of 2 hours. The canola oil was cooled to room temperature and stirred overnight with nitrogen sparge. The pre-treated canola oil was then heated to 95 ℃ and a toluene solution of the C827 metathesis catalyst (25ppm catalyst relative to the weight of the oil) was then added. Vacuum was applied to 20 torr and stirred for 1 hour. The vacuum was broken by an additional toluene solution of C827 metathesis catalyst (25ppm catalyst-50 ppm total catalyst relative to the weight of oil) followed by stirring under vacuum for 1 hour. The reaction temperature was raised to 180 ℃ with stirring for 1 hour. The reaction was cooled to 95 ℃ under vacuum, then a toluene solution of C827 metathesis catalyst (25ppm catalyst-75 ppm total catalyst relative to the weight of the oil) was added and stirred for 1 hour, then a toluene solution of C827 metathesis catalyst (25ppm catalyst-100 ppm total catalyst relative to the weight of the oil) was added and stirred for 1 hour. The reaction was kept overnight under nitrogen sparge while cooling to room temperature. The reaction mixture was warmed (slow heat) to 85 ℃, followed by addition of THMP (5 molar equivalents relative to total catalyst added) and stirring for 2 hours. The reaction mixture was cooled and discharged into a bucket. Further information is listed in table 3.

Example B2-batch Process with heating/Cooling

The process of example B1 was carried out as described above with the exception that: the catalyst was added dropwise through an addition funnel, targeting a total of 100ppm catalyst at 25 ppm/hour. Further information is listed in table 3.

Example B3-batch Process with heating/Cooling

The process of example B1 was carried out as described above with the exception that: instead of a 2L round bottom (flask), the experiment was carried out in a 2L kettle flask (keytle flash). Further information is listed in table 3.

Example B4-batch Process with heating/Cooling

Self-metathesized poly-oil was prepared by charging canola oil (7500g) to a 10 liter glass reactor. Canola oil was pretreated by bubbling with nitrogen while heating to 200 ℃ for a holding time of 2 hours. The canola oil was cooled to room temperature and stirred overnight with nitrogen sparging. The pre-treated canola oil was then heated to 95 ℃ and a toluene solution of the C827 metathesis catalyst (25ppm catalyst relative to the weight of the oil) was then added. Vacuum was applied to 20 torr and stirred for 1 hour. The vacuum was broken by an additional toluene solution of C827 metathesis catalyst (25ppm catalyst-50 ppm total catalyst relative to the weight of the oil) followed by stirring under vacuum for 1 hour. The reaction temperature was raised to 180 ℃ with stirring for 1 hour. The reaction was cooled to 95 ℃ under vacuum, then a toluene solution of C827 metathesis catalyst (25ppm catalyst, 75ppm total catalyst relative to the weight of oil) was added and stirred for 1 hour, then a toluene solution of C827 metathesis catalyst (25ppm catalyst, 100ppm total catalyst relative to the weight of oil) was added and stirred for 1 hour. The reaction was kept overnight under nitrogen sparge while cooling to room temperature. The reaction mixture was warmed to 85 ℃, followed by addition of THMP (5 molar equivalents relative to total catalyst added) and stirring for 2 hours. The reaction mixture was cooled and discharged into a bucket.

TABLE 3

Example B6-batch Process with overnight Hold and THMP

Self-metathesized poly-oil was prepared by adding canola oil (1000g) to a 2-liter glass reactor. The canola oil was then heated to 95 ℃ and a toluene solution of the C827 metathesis catalyst (25ppm catalyst relative to the weight of the oil) was then added. Vacuum was applied to 20 torr and stirred for 1 hour. The vacuum was broken through an additional toluene solution of C827 metathesis catalyst (25ppm catalyst, 50ppm total catalyst relative to the weight of oil) followed by stirring under vacuum for 1 hour. The reaction temperature was raised to 180 ℃ and stirred for 1 hour. The reaction was cooled to 95 ℃ under vacuum, then a toluene solution of C827 metathesis catalyst (25ppm catalyst, 75ppm total catalyst relative to the weight of oil) was added and stirred for 1 hour, then a toluene solution of C827 metathesis catalyst (25ppm catalyst, 100ppm total catalyst relative to the weight of oil) was added and stirred for 1 hour. The reaction was kept at 95 ℃ overnight under nitrogen sparge. The reaction mixture was cooled to 80 ℃, followed by addition of THMP (25 molar equivalents relative to total catalyst added) and stirring for 2 hours. The reaction mixture was cooled and discharged. Further information is listed in table 4.

Example B7-batch Process with heating/Cooling

The process of example B6 was carried out as described above with the exception that: for the previous 75ppm catalyst addition, N2 bubbling was used instead of vacuum. For the final 25ppm catalyst addition (100ppm total catalyst addition), a 20 torr vacuum was used while the temperature was increased to 180 ℃. Further information is listed in table 4.

Example B8-batch Process with heating/Cooling

The process of example B6 was carried out as described above with the exception that: the experiment was conducted in a 2L kettle flask and an additional 25ppm catalyst (125ppm total catalyst) was added followed by stirring for 1 hour. Further information is listed in table 4.

Example B9-batch Process with heating/Cooling

The process of example B6 was carried out as described above with the exception that: the experiment was carried out in a 2L kettle flask and the temperature was raised to 200 ℃ instead of 180 ℃ followed by stirring for 1 hour. Further information is listed in table 4.

TABLE 4

Example C1-batch Process without overnight Hold

Self-metathesized poly-oil was prepared by adding canola oil (1000g) to a 2-liter glass reactor. The canola oil was then heated to 95 ℃ under a stream of nitrogen, followed by addition of a toluene solution of C827 metathesis catalyst (25ppm catalyst, relative to the weight of the oil) and stirring for 1 hour. The catalyst was added in 1 hour increments (25ppm) for a total of 100ppm of catalyst added. The reaction was cooled and discharged. Further details are provided in table 5.

Example C2-batch Process without overnight Hold

The process of example C1 was carried out as described above with the exception that: the catalyst was added at 30 minute intervals instead of 1 hour 25 ppm. Further information is listed in table 5.

TABLE 5

Example C3-batch Process with overnight Hold

Self-metathesized poly-oil was prepared by charging canola oil (500g) to a1 liter glass reactor. The canola oil was then heated to 95 ℃ under a stream of nitrogen, followed by addition of a toluene solution of C827 metathesis catalyst (25ppm catalyst, relative to the weight of the oil) and stirring for 1 hour. An additional toluene solution of C827 metathesis catalyst (25ppm catalyst, 50ppm total catalyst relative to the weight of oil) was added followed by stirring under nitrogen overnight at 95 ℃. Additional toluene solution of C827 metathesis catalyst (25ppm catalyst, 75ppm total catalyst relative to the weight of oil) was added with stirring for 1 hour, followed by toluene solution of C827 metathesis catalyst (25ppm catalyst, 100ppm total catalyst relative to the weight of oil) and stirred for 1 hour (total reaction time-24 hours). The reaction was cooled and discharged. Further information is listed in table 6.

Example C4-batch Process without overnight Hold

The process of example C1 was performed as described above. Further information is listed in table 6.

TABLE 6

Example D olefin stripping

The crude poly oil was added to the WFE feed flask and processed under full vacuum (Welch belt drive pump) at temperature set points of 180 ℃, 200 ℃, 230 ℃, or 245 ℃ to separate the reacted olefin from the desired poly oil. The product oil was evaluated for residual odor.