SK22194A3 - Method of hydroxycarbonyl lactones - Google Patents

Abstract

The present invention relates to a process for the hydroxycarbonylation of lactones, more precisely of the various valerolactones and their isomers, by reaction with carbon monoxide and water, in order to form the corresponding diacid. More precisely, it consists in reacting carbon monoxide and water with at least one lactone having 5 carbon atoms, the reaction being carried out in the presence of an effective amount of an iridium catalyst and of an iodine-containing or bromine-containing promoter, the promoter/Ir molar ratio being between 0.1/1 and 20/1. This process especially makes it possible to value-enhance gamma-valerolactone to adipic acid.

Description

Method for the hydroxycarbonylation of lactones

Technical field

The invention relates to a process for the hydroxycarbonylation of lactones, in particular various valerolactones and their isomers, by reacting carbon monoxide and water to form the corresponding dicarboxylic acid.

The state of the art

Hydroxycarbonylation and pentenoic acids in the production of adipic acid always produce more or less gamma-valerolactone as a by-product of this reaction.

Commercial evaluation of gamma-valerolactone / or

Thus, 4-methylbutyrolactone represents a significant problem that should be solved in an industrially applicable process for the production of adipic acid by hydroxycarbonylation of pentenoic acids.

In Pat. No.-A-54/092913 discloses a process for preparing dicarboxylic acids by the hydroxycarbonylation of lactones, and in the presence of a rhodium catalyst and an iodinated promoter.

Pat. No. EP-A-0,395,038, published several years after the previous U.S. Pat. discloses a similar process which is characterized by the choice of the temperature range and the carbon monoxide pressure as well as the rapid termination of the reaction as soon as the absorption of the carbon monoxide decreases rapidly, which allows, according to the cited patent. No. 5,199,878, the above-mentioned yields of the linear dicarboxylic acids to be obtained.

SUMMARY OF THE INVENTION

The present invention is characterized by the use of iridium, a catalyst different from that previously described for this reaction.

In particular, the invention relates to a process for the hydroxycarbonylation of at least one lactone having 5 carbon atoms by carbon monoxide and water; its essence is k. . -4 ".

wherein the reaction is carried out in the presence of an effective amount of an iridium catalyst and an iodinated or brominated promoter _, wherein the molar ratio promoter / iridium ranges from 0.1: 1 to 20: 1.

The lactones which can be used in the process according to the invention are in particular gamma-valerolactone / or

4-methylbutyrolactone], delta-valerolactone, 2-methylbutyrolactone, 3-ethylpropiolactone, 2-ethylpropiolactone and 2,3-dimethylpropiolactone.

Of these lactones, gamma-valerolactone is the most interesting due to its constitution in the processes of hydroxycarbonylation of β-pentenoic acids to form adipic acid.

If appropriate, the lactone mixtures mentioned above may be used; the lactones used may contain an amount, but is not critical, of other compounds such as pentenoic acids, valeric acid, adipic acid, 2-methylglutaric acid or 2-ethylsuccinic acid.

In the process according to the invention, various iridium sources can be used for the iridium catalyst.

Examples of such sources of iridium include: metallic iridium; IrO2; Ir2O3;

IrC13; IrCl ₃ .3 H 2 O;

IrBr3; IrBr3.3 Η2θ;

Irl3;

Ir 2 / CO / 4C12; Ir2 / CO / ₄ 12;

Ir 2 / CO / s; ΙΓ4 / CO / 12;

Ir (CO) [P (C 6 H 5) 3] I;

Ir (CO) [P (C 6 H 5) 3] ci;

Ir [P / C 6 H 5/3 J s I;

Hlr [P (C 6 H 5) 3] (CO);

Ir / acac // C 0/2;

[IrCl (cod)] 2, (acac = acetyl lacetonate); ccd = 1,5-cyclooctadiene].

Particularly preferred iridium catalysts are:

[IrCl (cod)] 2, Ir 4 (CO) 12 and Ir (acac) CO 2.

The required amount of catalyst can be varied within a wide range.

in moles

In general, the amount of metal iridium catalyst per liter of reaction mixture

10, gives satisfactory results. However, it is possible to use a low reaction rate

C * ⁴ up to even smaller quantities, maybe speed. perspective.

are not economical

The preferred concentration range of from 5.10 ^-4 to 10 ^- ^ mol / liter.

The iridium in the reaction mixture is in size with

By iodinated or a compound of the brominated promoter conditions is meant in the context of the invention iodine or release hydrogen iodide, hydrogen bromide and bromine which are capable of hydrogen iodide or hydrogen bromide;

the iodine and bromine compounds are in particular up to 10 carbon atoms, the organic reaction of such organic and alkyl iodides and alkyl bromides, the most preferred of which are methyl iodide and methyl bromide.

A preferred promoter / iridium molar ratio is in the range of 1: 1 up to 10: 1.

from

The reaction is carried out in the liquid phase. The temperature at which the reaction is conducted is usually in the range of 100 ^C C and 300 ° C and preferably from 150 ° C to 250 ° C.

The total pressure at said reaction temperature may vary within wide limits. The carbon monoxide partial pressure, measured at 25 ^and C, is usually in the range of 0.05 MPa to 10 MPa, and preferably in the range of 0.1 MPa to 3 MPa.

The carbon monoxide used may be substantially pure or of such technical quality as is commercially available.

Water is required for hydroxycarbonylation of lactones. Typically, the water / lactone molar ratio ranges from 0.01 to

10. Larger amounts are not desirable in view of the observable loss of catalytic activity. The water / lactone molar ratio may be temporarily lower than the minimum amount mentioned above, for example if water is injected continuously, as when added simultaneously with the other components prior to the hydroxycarbonylation reaction.

Preferred is a water / lactone molar ratio ranging from 0.05 to 2, with the above-mentioned remark regarding the minimum value being applied equally.

Another parameter is also important: it is the concentration in o y y

Preferably, the concentration is maintained at a value ranging from

0.01 mol / liter up to and for better efficiency at values from 0.01 mol / liter up to mol / liter.

As mentioned earlier, this concentration may at a given moment be lower than the lower limits given if continuous water injection is performed.

The hydroxycarbonylation reaction of the lactones is carried out either in the lactone itself as the reaction medium or in an incm solvent.

In particular, saturated or unsaturated aliphatic or aromatic carboxylic acids, such as acetic, valeric, containing at most 20 carbon atoms, are well usable as other solvents under the reaction conditions of the carboxylic acids, propionic acid, adipic acid, and phenylacetic acid.

Equally liquid. Mention may be made of butyric acid, pentenoic acid, benzoic acid, in particular hydrocarbons and liquid conditions, benzene, and cyclohexane.

it is possible to saturate their chlorinated derivatives,

As examples toluene, chlorobenzene, dichloromethane, hexane use other aliphatic to such solvents, cycloaliphatic are under reaction solvents is

Mixtures of solvents may also be used.

If the reaction mixture contains another solvent, it comprises from 10% to 99% by volume based on the total volume of the reaction mixture and preferably from 30% to 90% by volume.

The hydroxycarbonylation process according to the invention allows commercial recovery of lactones with 5 carbon atoms, in particular gamma-valerolactone, which is formed in greater or lesser amounts during the hydroxycarbonylation of pentenoic acids. This allows an increase in the overall yield of the adipic acid production process starting from butadiene via pentenoic acids, adipic acid being one of the starting materials in the synthesis of 6,6-polyamides.

Finally, the reaction mixture is worked up by conventional methods used in chemistry to isolate the variously formed, possibly less than optimal, ratios of the reactants, catalyst, promoter and solvent to be determined in advance, generally in general, process, which is realized batchwise, the ratios of the reactants vary.

progressing conversions

The following examples illustrate the invention.

as a function

DETAILED DESCRIPTION OF THE INVENTION

Example

To

50 µl of a argon purged glass round flask was sequentially placed: gamma-valerolactone / VAL / water acetic acid / AcCH / hydrogen bromide / aqueous solution at a concentration of

47% w / w iridiumtrichloride

The glass flask is placed in 12 ml ml cars

20 mmol 2 0 mmol 10 ml 1 mmol 0 23 mmol eklávu.

pre-purged with argon. The autoclave is closed.

place in a furnace that allows mixing and attach the carbon monoxide under pressure. The pressure in the autoclave is set to 0 at the source

MPa

20 ° C. At 10 of this temperature, the pressure MPa is set (which corresponds to the partial use of carbon monoxide 5).

MPa measured at 25 ° C / and this pressure is maintained for h

at 220 ° C.

The autoclave is then cooled and gassed analyzed by gas chromatography (GC) by liquid chromatography (HPLC).

axena mixture with

The following results are obtained:

conversion (EC) / VAL yield of adipic acid (A1), based on 97% of the weight of adipic acid (AL / R Y)

RY

· Kyse ins

RY acids

2-methylglutar (A2)

2-ethylsuccinate (A3)

O 'i

RY acids

9 teenagers

Example n

Example 1 is repeated with the following changes: the total pressure at 220 ° C is 2.8 MPa / min, and the pressure of 1.1 MPa of carbon monoxide corresponds to a partial temperature of 25 ° C / instead of pressure

MPa;

maintaining the temperature at 220 ° C for

The following results are obtained:

Conversion / EC / VAL hr instead of 11 hr.

8%

RY adipic acid (Al)

40%

RY

RY

RY acid acid acid

9¾

0 / □ Ό

14%

2-methylglutar (A2)

2-ethylsuccinic (A3) valeric (A3) linearity / ratio of formed adipic acid to total amount of d-carboxylic acids formed)

7 cu r t / o productivity of the adipic acid formed 53

Example 3

Example 2 is repeated except that it is replaced by gamma-valerolactone, the total carbon monoxide pressure at 25 ° C (PC25 ⁰ ) being 1

The following results are obtained: conversion (LC / VAL yield of adipic acid / Al), referred to converted VAL (CY) to

CY acid acids

2-methylglutar (A2)

2-ethylsuccinic (A3) valeric (? A)

11.8 oh! P and acid of cg. partial

11¾

26%

10%

14% a1

Examples 4 to 9

The example is repeated with the changes shown in the following table summarizing the results obtained.

The abbreviations used in the table correspond to those used in the previous examples.

5 they » 2 •about . "CZ _ CN ABOUT "· n n CN ABOUT OS J * 'ABOUT ABOUT ΙΛ * «Ν > < cn r * with * 4 and about ^WITH > 'OJ M 4 » 4 C CN Λ < Q n <w > < »N r * m · < A X S £ triethylsily Ή N  J -r A 0) 3 ABOUT tí 5 cn A n CN ¹ 0 LA fO • Ό | Q •in 40 •ABOUT • u <0 <0 cq , -q RTJ > CN X X C x i. X X X a. 0 x x .3 o 4th DATE. Σ Σ Σ Σ Σ £ Σ WITH ~ CJ un kO * A <o WHAT UD A U3 about CP U-> (U • * • • * - .. O X about· CN <T CN CN <T CN and '3 Ό CN * H -01 '-I iJ JZ _Ä and Q J2 X 0 r * ÍN A CN Ul Z, Z 22 CN »(J -u «5 about and ABOUT ABOUT A A «j ffl and CN n 3 <3 0 ~ Ή CJ X 0 Φ IN CN 4J S 0 - ABOUT and ABOUT and _T 1 ä. t * · 'i N * SS C * u - £ itn u • c ** < u <  -4 - * 0 <n U 0 w A r * with iO · < • r hl 1 i 3 = N and - 3 CN X 3 3 0 x> j 9 N CM C3 CN CN CN 73 with 0 ^c >> cn n CN m ΓΊ n x CN CN CN ÍN 0 AJ N A / ¼ <- » «** NU and . *> 3 TJ N ** m about .-N <n 0 n 0 m and <* » and O u A at A U CN U A U A at A -t <· about -. Q ¹⁴ and and -i ABOUT ^ 4 ABOUT WHAT - M at U U U at > 4 .-a> · r- - «Q and about 03 and • í - > Ξ CN CM - · - * > 5 ' 't iT. \ C WHAT ch 73 «0 72 73 73 71 75 ITJ .3 • U • U • 0 r- " X -4 X X  u. iu L, u. i. "· - x x

CY U Uliato K Y

Example 10

Example 1 is repeated with the following handles and working conditions:

gamma-vaierolactone / VAL / 110 mmol total amount of water 12 mmol hydrogen iodide / aqueous solution p concentration 57¾ wt. 0.384 mmol [IrCl / cod / 1] 0.156 mmol

The initial water concentration is 1 mol / liter.

The temperature is 200 ° C; the total pressure at this temperature is 5 MPa (equivalent to a carbon monoxide partial pressure of 3 MPa at 25 ° C); the reaction time at this temperature is 1 h.

The following results are obtained:

conversion / EC / VAL16¾ / equivalent of 100¾ water conversion / adipic acid yield / Al / based on converted VAL / CY / 52¾

CY of 2-methylglutaric acid / A2 / 10¾

CY of 2-ethylsuccinic acid / A3 / 3¾

CY valeric acid / PA / 8¾

CY pentene acid n15¾

CY 2-methylbutyric acid 1¾ productivity Al 119 gl ' ¹ h ^-1 linearity Al33¾

Example 11

Example 10 was repeated with 24 mmol of water instead of 12 mmol. The initial water concentration is 2 mol / liter.

The reaction time is 3 h.

The following results are obtained:

Conversion / EC / VAL 17¾ CY of Al 48¾ productivity Al 40 gl ¹ h ^-1 1inearita 74%

Comparative test

Example 2 was repeated with the difference that iridium trichloride was replaced with the same molar amount of rhodium trichloride test for 11 h at temperature

220 ° C to obtain a value comparable to that in Example 2.

They will get these results: conversion / EC / VAL 79% RY acids ad i povej / Al / 51% RY acids 2-methylglutar (A2) 21% RY acids 2-ethylsuccinate (A3) 3% RY acids valerová / PA / 2% productivity A1 14 1 i near i 63% It was found, that linearity is greater with iridium

(Example 2) gl ~ ¹ h ^-1 as with rhodium (77% versus 63%).

Moreover, the rhodium test, even at a much longer reaction time (11 h vs. 2 h), leads to the productivity of adipic acid, which is strikingly Example 2.

Industrial usability

The process according to the invention contributes to the economization of the process of hydroxycarbonylation of 5-carbon lactones, which are useful in the synthesis of adipic acid, one of the starting materials for the production of 6,6-polyamides.

Claims (9)

PATENT CLAIMS has that A process for the hydroxycarbonylation of at least one lactone which: 5 carbon atoms, carbon monoxide and water, characterized in that the reaction is carried out in the presence of an effective amount of an iridium catalyst and an iodinated or brominated promoter, wherein the molar ratio of the promoter / iridium is in the range of 0.1: 1 up to 20: 1. The method of claim 1, wherein the tone is selected from delta-valerolactone and is selected from the group consisting of: 2-methylbutyrolactone, and 2,3-dimethylpropiolactone, and 2-ethylpropiolactone gamma-valerolactone. The method according to claim 1, wherein the lagama-valerolactone, 3-ethylpropiolactone is used. advantage <·> o. Process according to either of Claims 1 and 2, characterized in that the catalyst is selected from the group consisting of: iridium metal iridium IrCls; IrCls HZO; IrBrs; IrBr ₃ Hz 0; Irl3; ΙΓ2 /CO./and C12; Irj / co / s; IRX / what / IT; ir / co / rp / C6H5 / 3] 21; Ir / CO / FP / Ph / 3] 2C1; Ir [P / Ce Ks / 3] 3 I; Hlr [P (C 6 H 5) 3] (CO); Ir / acac // C 0/2; [IrCi / cod / j 2. Ir ₂ / CO / 4I2; from e to moles The process according to any one uses a metal iridium catalyst for one of claims 1 from 10 to ⁴ and preferably 3.'vyznačený by an amount, a liter of the reaction mixture in the range of 5 10 ^"4 to 10" ¹ mole / 1iter. 4. Process according to one of claims 1 to 4, characterized in that an iodine or brominated promoter selected from the group consisting of hydrogen iodide, hydrogen bromide and an organic compound of iodine or bromine which are capable of releasing hydrogen iodide or hydrogen bromide under reaction conditions is used. Process according to one of Claims 1 to 5, characterized in that a promoter / iridium molar ratio of from 1: 1 to 10: 1 is used. Process according to any one of claims 1 to 6, characterized in that the reaction is carried out in the liquid phase, at a temperature in the range of from 100 ° C to 300 ° C and preferably in the range of from 150 ° C to 250 ° C and at partial temperature. carbon monoxide pressure, measured at 25 ° C, in the range of 0.1 M 2 and up to 8 MPa. Method according to one of Claims 1 to 7, characterized in that a water / lactone molar ratio is used in the range of C01 to 10 and preferably in the range of 0.05 to 2. Process according to one of Claims 1 to 8, characterized in that the hydroxycarbonylation reaction of the lactenes is carried out in the medium of the respective lactone which forms the liquid reaction medium e. The process according to any one of claims 1 to 8, wherein the hydroxycarbonylation reaction of the lactones is carried out in another group selected from the group consisting of a solvent selected from saturated or containing at most 20 aliphatic or cycloaliphatic hydrocarbons and their chlorinated derivatives which: 11. Method according to claim 10, characterized by a disintegrant in an amount of 10% by weight. that 99% vol. % of mixtures, and preferably in the range of 30% and based on