TW201402819A - Method of producing isononyl derivatives - Google Patents

Abstract

The present invention relates to a method of producing isononyl derivatives from fermentatively produced isobutene, the higher purity of which improves the method and the properties of the produced isononyl derivatives.

Description

Method for producing isodecyl derivative

The present invention relates to a process for producing an isodecyl derivative, which is specifically isodecyl alcohol (3,5,5-trimethylhexanol as a main product), isodecyl vinyl ether (3, 5,5-trimethylhexyl-1-vinyl ether as main product), isofurfural (3,5,5-trimethylhexanal as main product), isodecanoic acid (3,5,5-trimethyl) Glycidol with 2,2,4,4-tetramethylpentanoic acid as main product), 3,5,5-trimethylhexanoic acid or 2,2,4,4-tetramethylpentanoic acid The ester is isodecylamine (3,5,5-trimethylhexylamine as the main product) and is preferably derived from a source of renewable raw materials.

These isodecyl compounds are important industrial products, especially isodecyl vinyl ethers as copolymers for emulsifying paints, and isodecyl alcohols are of importance as an alcohol component for plasticizers. Isofurfural has a certain degree of scientific importance based on its reactive aldehyde group as an intermediate product and can be converted to isodecanoic acid by oxidation or converted to isodecylamine by reductive amination and converted to A secondary amine and a tertiary amine comprising an isodecyl residue. Esters of isophthalic acid are used as lubricants, and isodecylamine can be used in corrosion protection formulations.

Processes for the production of isodecyl derivatives are known for some time, in particular with reference to Wiley-VCH, Ullmann's Encyclopedia of Industrial Chemistry, 2003, 6th. ed., vol. 6, pp. 497-498, pp. 502-503 and second. The content published on page 33 of the volume. Usually, one of them starts from a dimer of isobutylene in the presence of a transition metal catalyst, and it is reacted by an oxy group or a hydroformylation reaction of a mixture of the same carbon oxide and hydrogen (also known as a synthesis gas). Conversion to the corresponding isofurfural (see Hydrocarbon Processing, April 1973, pages 171 to 173, and Ullmann's Encyclopedia of Industrial Chemistry, 6thed., Wiley-VCH, 2003, Vol. 2, p. 75). Isoamylaldehyde can then be converted to isodecyl vinyl ether by, for example, being oxidized to isodecanoic acid, hydrogenated to isodecyl alcohol, aminated to isodecylamine, or isodecyl alcohol. However, due to the vast importance of the above isodecyl derivatives for industrial chemistry, Alternative methods for making isodecyl derivatives and alternative sources of raw materials are continually seeking further improvements.

The use of renewable raw materials as a starting material for the manufacture of organic chemicals on an industrial scale has gradually become important. On the one hand, oil, natural gas and coal-based resources should be saved. On the other hand, with renewable raw materials, carbon dioxide is tightly integrated into an industrially useful carbon source because it is inexpensive and large. The use of renewable raw materials can be used for industrial preparation of organic chemicals, examples of which include the preparation of citric acid, 1,3-propanediol, levataric acid, succinic acid, lactic acid, and itaconic acid.

Renewable starting materials have not been used in the preparation of isodecyl derivatives. Accordingly, the present invention will provide an improved process for the preparation of one of the isodecyl derivatives, and preferably from a source of renewable raw materials. Here, it must be particularly noted that the use of the isodecyl derivative preferably uses an isomeric non-isobutylene in the preparation of the isodecyl derivative.

This object is achieved by a process for the manufacture of isodecyl derivatives comprising the steps of: a) fermentation of isobutylene; b) dimerization of isobutene to diisobutylene; c) purification of diisobutylene; d) Extension of one carbon atom to give an isodecyl derivative; and e) further derivatization as appropriate.

The present invention relates to a process for producing an isodecyl derivative, which is specifically isodecyl alcohol (3,5,5-trimethylhexanol as a main product), isodecyl vinyl ether (3, 5,5-trimethylhexyl-1-vinyl ether as main product), isofurfural (3,5,5-trimethylhexanal as main product), isodecanoic acid (3,5,5-trimethyl) Glycidol with 2,2,4,4-tetramethylpentanoic acid as main product), 3,5,5-trimethylhexanoic acid or 2,2,4,4-tetramethylpentanoic acid Ester and isodecylamine (3,5,5-trimethylhexylamine) And it is preferably derived from a source of renewable raw materials.

The use of renewable raw materials on the industrial scale as a basis for the manufacture of organic chemicals The beginning of matter has gradually become important. On the one hand, oil, natural gas and coal-based resources should be saved. On the other hand, with renewable raw materials, carbon dioxide is tightly integrated into an industrially useful carbon source because it is inexpensive and large. The use of renewable raw materials can be used for industrial preparation of organic chemicals, examples of which include the preparation of citric acid, 1,3-propanediol, levataric acid, succinic acid, lactic acid, and itaconic acid.

Renewable starting materials have not been used in the preparation of isodecyl derivatives. Therefore, the present invention will An improved method for preparing one of the isodecyl derivatives is provided, and preferably is derived from a source of renewable raw materials. Here, it must be particularly noted that the use of the isodecyl derivative preferably uses an isomeric non-isobutylene in the preparation of the isodecyl derivative.

This object is achieved by a process for the manufacture of isodecyl derivatives comprising the steps of: a) fermentation of isobutylene; b) dimerization of isobutene to diisobutylene; c) purification of diisobutylene; d) Extension of one carbon atom to give an isodecyl derivative; and e) further derivatization as appropriate.

Here, it has surprisingly been found that the isobutene produced by fermentation has a relatively high purity relative to the linear butene isomer, so that subsequent dimerization gives high purity and yield of diisobutylene, which in turn leads to steps. A high purity isodecyl derivative is formed in d).

In a known conventional method, high purity isobutylene is formed on a laboratory scale biochemical. So, but directly from the precursor 3-hydroxyisovaleriate (or 3-hydroxy-3-methylbutyrate), see Gogerty, DS and Bobik, TA published in 2010 on pages 8004 to 8010 of Applied and Environmental Microbiology, which studies the synthesis of isobutene fermentation enzymes in which no significant amount of n-butene isomer is produced in accordance with GC in valuable products. .

The above term "isoindenyl derivative" means a structurally isomeric compound comprising at least one C9-alkyl residue, especially one of the major portions of a 3,5,5-trimethylhexyl residue, and in particular 3,5,5-trimethylhexanol and ether, 3,5,5-trimethylhexyl vinyl ether, 3,5,5-trimethylhexanal, 3,5,5-trimethylhexanoic acid And a glycidyl ester thereof, and 3,5,5-trimethylhexylamine and a secondary amine and a tertiary amine comprising at least one 3,5,5-trimethylhexyl residue. Further, it is preferably a C9 compound containing a 2,2,4,4-tetramethylpentyl structure as a main component.

Carbon dioxide as a by-product formed during fermentation and other inertia as appropriate Sexual gases can optionally be removed in a conventional manner by suitable separation techniques. In most of the embodiments of the present invention, the step of converting isobutylene to diisobutylene can be carried out without first purifying isobutylene, thereby representing a preferred embodiment of the present invention. In this embodiment of the invention, the fermentation step utilizes high selectivity to isobutylene (e.g., C4-olefin). On the other hand, carbon dioxide and other inert gases do not prevent isobutene from being dimerized into diisobutylene. However, in a specific example, carbon dioxide and other inert gases may be suitably separated from isobutylene at the beginning.

The above-mentioned term "fermentation preparation" of isobutylene specifically means that isobutylene is obtained by: - utilizing microorganisms, and preferably derived from renewable raw materials; and/or - utilizing a cell-free enzyme step (cell-free) Enzymatic process), and it is also preferably derived from renewable raw materials.

It is known that isobutylene is not a natural product but is produced during the metabolism of an organism, and such an amount appears to be suitable for industrial use. However, isobutylene derived from naturally occurring microbial systems is very small (see U.S. Patent 4,698,304, and Fukuda, H. et al., 1984, From Agricultural and Biological Chemistry (1984), 48(6), 1679. To 1682 pages). Thus, in the aforementioned known embodiments of the present invention, the fermentation preparation of isobutylene is carried out using modified, non-natural microorganisms and corresponding modified enzymes, respectively. Such a microorganism can be referred to from US Application Publication No. US2011165644 (A1), in which it is discussed in Example 13 that isobutene is synthesized from glucose in a suitable microorganism. Further enzyme reactions are discussed in International Publication No. WO 2012052427 and WO 2011032934, which describe a series of isobutenes

I) acetone to 3-hydroxyisovalerate; and II) 3-hydroxyisovalerate to isobutene and carbon dioxide.

The formation of continuous enzymes is synthesized.

The catalytic decomposition of 3-hydroxyisovalerate to isobutene and carbon dioxide is also discussed in Gogerty, D.S. and Bobik, T.A., published on pages 8004 to 8010 of Applied and Environmental Microbiology, 2010. Here, according to GC, no significant amount of n-butene isomer is produced in the valuable product. In fact, in aqueous solution, the non-enzymatic catalytic system observes that carbon dioxide spontaneously separates from 3-hydroxyisovalerate under the formation of isobutylene, and further reacts with existing water to form a third butanol via an equilibrium reaction (see Pressman, D. and Lucas, HJ, 1940, Journal of the American Chemical Society, pp. 2069-2081).

If the sequence of enzyme synthesis described in I and II is included in a suitable microbial host organism by a non-natural microbial organism, and the microbial host organic system can synthesize acetone from the metabolic precursor or passively from the outside. Or active delivery of acetone to the cells via the cell wall, isobutene with excellent yield can be prepared via a fermentation step. Microbial organic systems which can synthesize acetone from different carbohydrates are known for a long time and are described inter alia in Jones, T. D. and Woods, D. R., 1986, Microb. Reviews, pages 484 to 524. Taylor, D. G. et al., 1980, Journal of General Microbiology, 118, pp. 159-170, describes microbial organisms using acetone as a sole source of carbon and, therefore, acetone can be delivered to cells through the cell wall.

Another possible metabolic pathway is carried out by the following reaction sequence: I) conversion of pyruvate to 2-ethyl decyl lactate; II) conversion of 2-ethyl decyl lactate to 2,3-dihydroxyisoprene Acid; III) conversion of 2,3-dihydroxyisovalerate to 2-oxyisovalerate; IV) conversion of 2-oxyisovalerate to isobutyraldehyde; V) conversion of isobutyraldehyde to isobutanol; VI) Isobutanol is converted to isobutylene.

And it is described in International Publication No. WO 2011076689 and WO 2011076691.

The above term "isobutylene" as used herein refers to 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene as the main product and any of the two compounds mixture.

According to a preferred embodiment of the present invention, there is no advance between step a) and step b) Purification of isobutene, especially without purification, removes linear butene isomers and optionally passive gases such as carbon dioxide and/or nitrogen. "Purification" as used herein specifically, but is not limited to, refers to the following method:

- distillation step (however, this step requires a considerable amount of effort and complexity to separate the linear isobutylene isomers produced in the overall step because the boiling points of the isomers are very close, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, 1978, vol. 4, John Wiley & Sons Inc, pp. 358-360)

- a purification or separation process in which isobutylene is separated by a chemical reaction and increased chemical reactivity, and then converted back to isobutylene. It comprises, for example, adding a reversible proton-catalyzed water to the third butanol or adding methanol to the methyl tertiary butyl ether (see EP 1489062). Via these adducts, isobutene is then regained by a reversible reaction (see Weissermel, Arpe, Industrielle Organische Chemie, VCH Verlagsgesellschaft, 3rd edition, 1988, pp. 74-79).

- a purification or separation process in which isobutylene is separated from the linear butene isomer by suitable physical size exclusion methods and by its tighter spatial molecular structure, for example, by having a suitable pore size Molecular sieves (see International Publication No. WO 2012040859 and Weissermel, Arpe, Industrielle Organische Chemie, VCH Verlagsgesellschaft, 3rd edition, 1988, p. 74).

- Purification or separation method suitable for carbon dioxide removal

According to a preferred embodiment of the invention, the isobutylene is obtained in step a) by means of a trisaccharide, a disaccharide, a monosaccharide, acetone or a mixture thereof. The trisaccharides and disaccharides used above are specifically raffinose, cellobiose, lactose, isomaltose, maltose and sucrose. The monosaccharide used is specifically D-glucose, D-fructose, D-fructose, D-mannose, DL-arabinose. (DL-arabinose) and DL-xylose (DL-xylose). Here, the above trisaccharides, disaccharides and monosaccharides are especially derived from (but are not limited to):

- Digestion and depolymerization of cellulose and hemicellulose using appropriate methods

- Direct extraction from high sugar content plants such as sugar beet, sugar cane, coconut sugar, maple syrup, sorghum, silver date, honey coconut, palm leaf palm and agave

- Depolymerization of hydrolyzed plant starch

- Depolymerization of hydrolyzed animal glycogen

- Direct access to milk from dairy plants

In another preferred embodiment of the invention, the unique renewable feedstock is used in the fermentation preparation of isobutylene. If desired, the carbon source from the source of renewable raw materials can be determined by the test methods described in American Standard Inspection (ASTM) D6866. Here, the ratio of C14 to the C12 carbon isotope can be determined and compared to the isotope ratio of a reference material having 100% of the carbon atoms from the source of renewable raw materials. This test method can also be carried out in a modified form such as a radiocarbon determination method, which is described in Olsson, I. U., 1991, Euro Courses: Advanced Scientific Techniques, volume 1, Issue Sci. Dating Methods, pages 15 to 35.

According to a preferred embodiment of the invention, the fermentation step is carried out at a temperature of from 20 degrees Celsius to 45 degrees Celsius and at atmospheric pressure, wherein the isobutene is released as a gaseous product. An advantage of this embodiment is that the isobutylene obtained therefrom can be used directly or after separation of the inert gas.

Alternatively, according to another preferred embodiment of the present invention, the fermentation step is carried out at a temperature of from 20 degrees Celsius to 45 degrees Celsius and at a pressure of from 1 to 30 bar. In this case, the isobutylene can be a liquid compound and separated directly from the fermentation medium by phase separation. In the preferred embodiment, the separation of the inert gas can be relatively easy.

According to a preferred embodiment, step b) is carried out under acid catalysis. Here, for example, sulfuric acid or acidic ion exchangers are considered (see in Weissermel, Arpe, Industrielle Organische Chemie, VCH Verlagsgesellschaft, 3rd edition, 1988, page 77, and Hydrocarbon Processing, April 1973, What is stated on pages 171 to 173). Alternatively, reference may be made to the methods described in U.S. Patent Nos. 2004/0054246, 4,200,220 (A), 4,447,668 (A) and 5, 777, 372 (A).

The above process further comprises a step c) which is carried out after step b): c) purification of the diisobutylene, and which is preferably carried out by distillation.

Preferably, step c) is carried out to separate the unreacted volatile gas from the diisobutylene, and the resulting diisobutylene is distilled from the triisobutylene or higher isobutylene oligomer (possibly in small amounts) Extracted and purified. According to this, the three isobutylene and the higher difference The butene oligomer can also be refined into a valuable second product.

In a preferred embodiment of the invention, step d) is carried out by conversion to isofurfural in a monoformylation/oxygen reaction.

This reaction is further discussed below: this reaction is preferably carried out by reacting diisobutylene with a synthesis gas to give isodecanoaldehyde, and preferably using a cobalt or rhodium catalyst. Primarily, it mainly includes 3,5,5-trimethylhexanal.

A further derivatization can be carried out according to step e) as appropriate. If isofurfural is formed in step d), an oxidation or reduction step is usually carried out.

Here, the reduction of isodecyl aldehyde can be carried out by hydrogenation reaction in a gas phase or a liquid phase at a metal junction. Preferred catalysts include nickel or copper catalysts.

Oxidation of isodecanoaldehyde is preferably carried out with oxygen at a moderately elevated temperature to produce isononanoic acid containing 3,5,5-trimethylhexanoic acid as the main product (see Weissermel, Arpe). Industrielle Organische Chemie, VCH Verlagsgesellschaft, Third Edition, 1988, pages 143 to 145, and Ullmanns Encyclopädie der technischen Chemie, 4th edition, 1983, Verlag Chemie, volume 9, page 144, and European Patent EP 1854778 A1).

The reductive amination of isodecyl aldehyde is preferably carried out using aqueous ammonia, a primary or secondary amine and hydrogen, and is preferably carried out in the presence of a catalyst such as a nickel or cobalt catalyst. Here, the ratio of the primary, secondary or tertiary isoxamine-based isodecanal to the nitrogen-containing compound is determined.

Isodecyl alcohol can also be converted to isodecylamine by aminolysis. Even if hydrogen is not consumed in this reaction, the above reaction is preferably carried out in the presence of hydrogen, and it is preferably at a nickel or cobalt contact.

A further derivatization step subsequently takes place, in which it is specifically preferred to carry out the vinylation to give isodecyl vinyl ether.

This reaction can be carried out via isopropanol and acetylene according to a preferred embodiment of the invention, and is preferably carried out at a temperature between 150 and 180 degrees Celsius in the presence of an alkali metal oxide. (See Ullmann's Encyclopedia of Industrial Chemistry, 6th ed.. Wiley-VCH, 2003, vol. 38, pp. 79-81).

According to an alternative and also preferred embodiment, the isodecyl alcohol and one of the other carboxylic acid vinyl esters are subjected to a reaction catalyst R-OH+R ¹ -C(O)OCH=CH _{2 which is} known as a vinyl transfer reaction. → RO-CH=CH ₂ +R ¹ -C(O)OH

Wherein R is 3,5,5-trimethylhexyl and R ¹ generally represents a methyl or ethyl group, and a vinyl transfer reagent, for example, vinyl acetate or vinyl propionate can be used (see Ullmanns). Encyclopädie der technischen Chemie, 4th edition, 1983, Verlag Chemie, volume 23, pp. 606-607). In order to cause the chemical equilibrium to proceed towards the desired vinyl ether, an excess of the vinyl transfer reagent R ¹ -C(O)OCH=CH ₂ is typically provided and/or the formed carboxylic acid is removed from the reaction mixture. The continuous or semi-continuous step can be configured, for example, as a reactive distillation (see EP 0 497 340 A2) or as a capillary tube mounted on top of the column, wherein one of the additional distillation columns and a stripping column Connected downstream (see WO 2011/139360 A1 and WO 2011/139361 A1). The vinyl transfer reaction can also be carried out without removing the reactants and the resulting reaction mixture can be separated into a plurality of single components in a separate reprocessed portion (see DE 10 2012 0022 82.4, DE 10 2012 0022 74.3). As the vinyl transfer catalyst, for example, a rhodium or palladium compound is suitable as a vinyl transfer catalyst, and it is a nitrogen or phosphorus-containing ligand which is unmodified or modified with a single or multiple buds (for example, 2.2). '-pyridine or 1,10-phenanthroline is used together. The carboxylic acid obtained as a by-product and relative to the vinyl transfer reagent can be further derivatized or used directly as a valuable product. For example, the corresponding carboxylic acid can be converted to a vinyl ester, which can then be reused as a vinyl transfer reagent for isodecyl alcohol, and the corresponding carboxylic acid can be converted to a monocarboxylic acid ester, a monocarboxylic acid anhydride. A monocarboxylic acid halide monocarboxylic acid amine or a corresponding alcohol according to known methods.

According to an alternative and also preferred embodiment, the vinyltransfer reaction of the above isodecyl alcohol is carried out using a vinyl ether as the vinyl transfer reagent, and moderately modifying the above reaction conditions is practicable. It is preferred to use a non-volatile and viable vinyl ether such as methyl vinyl ether (see GB 1105956, J.E. McKeon, P. Fitton, Tetrahedron 1972, 28(2), 233).

According to an alternative but also preferred embodiment, 3,5,5-trimethylhexanoic acid can be derivatized as a glycidyl ester according to known methods, for example by an epoxy which can be used to modify an alkyd resin. Epichlorohydrin reaction (see Weissermel, Arpe, Industrielle) Organische Chemie, VCH Verlagsgesellschaft, 3rd edition, 1988, page 152 and US Pat. No. 6433217).

Another option is by the reaction of diisobutylene according to a Koch reaction. The structure of the isodecyl skeleton obtained by acid-catalyzed carbonylation (see Arpe, Industrielle Organische Chemie, 6th edition, 2007, p. 154). Here, 2,2,4,4-tetramethylpentanoic acid is substantially formed. Similar to the above description, the further derivative obtained may be the corresponding glycidyl ester or vinyl ether of 2,2,4,4-tetramethylpentanoic acid.

According to the invention described above and in conjunction with the exemplary embodiments, disclosed, claimed and described The synthetic steps described are not subject to special exceptions with respect to their technical content, so that the selection criteria known in the field of application can be used without limitation.

The individual combinations of the components and features of the above embodiments are exemplary, and these teachings Alternatives and substitutions made by the other teachings cited herein are also explicitly considered.

It will be appreciated by those skilled in the art that the changes, modifications, and other embodiments described herein can be practiced without departing from the spirit and scope of the invention. Accordingly, the above description is to be understood as illustrative and not limiting. The use of the terms "comprising" or "comprising" or "comprising" or "comprising" does not exclude other elements or steps, and the indefinite article "a" does not exclude the plural. It is only the fact that a certain number of patents that are described in the different claims are not intended to be profitable. The scope of the invention is defined in the following claims and their equivalents.

Claims (12)

A method for producing an isodecyl derivative comprising the steps of: a) fermentative preparation of isobutylene; b) dimerization of isobutylene to diisobutylene; c) purification of diisobutylene; d) extension by one carbon atom An isodecyl derivative is obtained; and e) is further derivatized as appropriate. The manufacturing method of claim 1, wherein the purification of isobutylene is not performed between the step a) and the step b). The manufacturing method of claim 1 or 2, wherein the isobutylene in the step a) is derived from a trisaccharide, a disaccharide, a monosaccharide, acetone or a mixture thereof. The manufacturing method of claim 1 or 2, wherein the renewable raw material is used for the fermentation preparation of isobutylene. The manufacturing method according to any one of claims 1 to 4, wherein the fermentation step is carried out at a temperature of from 20 degrees Celsius to 45 degrees Celsius and at a pressure of one atmosphere, and the isobutylene is a gas product Released. The manufacturing method according to any one of claims 1 to 4, wherein the fermentation step is carried out at a temperature of from 20 ° C to 45 ° C and at a pressure of 1 to 30 bar. The manufacturing method according to any one of claims 1 to 6, wherein the step b) is carried out under acid catalysis. The manufacturing method according to any one of claims 1 to 7, wherein the step c) is carried out by distillation. The production method according to any one of claims 1 to 8, wherein the step d) is carried out according to a monoformation/oxy group reaction. The method of manufacture according to any one of claims 1 to 9, wherein the step e) comprises an oxidation, reduction, or amination step. The manufacturing method according to any one of claims 1 to 8, wherein the step d) is obtained by acid-catalyzed hydrooxycarbonylation according to a Koch reaction, 2, 2, 4, 4-tetramethylpentanoic acid is a major product. The process of any one of claims 1 to 11, wherein the step e) comprises reacting with acetylene, with epichlorohydrin, with a vinyl carboxylate and/or with one of the vinyl ethers.