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Title:
PROCESS FOR REACTING CARBOXYLIC ACIDS AND ESTERS
Document Type and Number:
WIPO Patent Application WO/2002/018328
Kind Code:
A1
Abstract:
The present invention relates to a process for making esters and amides, typically being peroxy acid precursors, using a spinning disc reactor. The invention also relates to a process for making specific halide-containing hydrocarbons using a spinning disc reactor. The invention also relates to a combined process for making specific first carboxylic acid halides and then peroxyacid precursors, using a spinning disc reactor. The invention also relates to transesterification using a spinning disc reactor.

Inventors:
Burns, Michael Eugene (7132 Valley Falls Court Hamilton, OH, 45011, US)
Gibson, Michael Steven (448 Windfern Forest Cincinnati, OH, 45245, US)
York, David William (10 Ladywell, Newcastle Upon Tyne Ponteland, Tyne and Wear NE20 9TB, GB)
Application Number:
PCT/US2001/026662
Publication Date:
March 07, 2002
Filing Date:
August 27, 2001
Export Citation:
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Assignee:
THE PROCTER & GAMBLE COMPANY (One Procter & Gamble Plaza Cincinnati, OH, 45202, US)
International Classes:
C07C51/60; C07C67/08; C07C231/02; C07C303/22; C07C303/32; C07C233/47; C07C309/42; (IPC1-7): C07C303/22; C07C51/60; C07C67/08; C07C67/14; C07C231/02
Domestic Patent References:
WO2000048728A1
Foreign References:
FR612315A
CH306127A
US5523434A
Attorney, Agent or Firm:
Reed, David T. (The Procter & Gamble Company 5299 Spring Grove Avenue Cincinnati, OH, 45217-1087, US)
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Claims:
WHAT IS CLAIMED IS:
1. A process for making esters or amides, typically esteror amidebased peroxyacid precursors, by reacting a carboxylic acid or derivative thereof (reactant) with an free or substituted hydroxy groupcontaining compound or an free or substituted amine containing compound (reactant) to form an ester or amide bond, whereby this reaction is done by use of a spinning disc reactor.
2. A process as in claim 1 whereby the carboxylic acid derivative is a carboxylic acid halide, preferably carboxylic acid chloride, preferably an amide substituted alkyl carboxylic acid chloride.
3. A process as in claim 1 or 2 whereby the hydroxygroup containing compound is an aromatic compound, preferably phenol or derivative thereof, or the aminecontaining compound is a heterocyclic compound, preferably a lactam, valerolactam or caprolactam.
4. A process as in any of claims 1 to 3 whereby the hydroxycontaining group is a phenol sulphonic acid or salt thereof and the carboxylic acid derivative is an amide substituted alkyl carboxylic acid chloride, preferably a Nnonanoyl6aminocaproic acid chloride.
5. A process as in any of claims 1 to 4 whereby the spinning disc reactor is cooled, preferably the disc of the reactor is cooled.
6. A process as in any preceding claim whereby a solvent and/or processing aid is added to the reaction, preferably including an alkaline agent, preferably including a hydroxide solution.
7. A process as in any preceding claim whereby said reactants, and optionally solvent and process aids, are introduced onto the disc at the centre or close to the centre of the disc.
8. A process as in any preceding claim whereby the rotation speed of the disc is from 1000 to 2000rpm.
9. Process for making of hydrocarbon halides by reacting a halogen donor or halide donor (reactant) with a hydrocarbon (reactant), whereby a spinning disc reactor is used.
10. Process as in claim 9 whereby the hydrocarbon is an alpha olefin or derivative thereof, or a carboxylic acid or derivative thereof and the halide donor is a chloride or bromide donor or the halogen donor is a chorine radical donor or bromine radical donor.
11. Process as in claim 10 whereby the alpha olefin or derivative thereof is reacted with a gaseous halide donor or halogen donor.
12. Process comprising the process of claim 9 and the process of claim 1, whereby in a first step, the process as in claim 9 is used, whereby a carboxylic acid halide is formed by use of a spinning disc rector and in a second step, the process of claim 1 is used, whereby the carboxylic acid halide of the first step is reacted with free or substituted hydroxy groupcontaining compound or an free or substituted amine containing compound by use of a spinning disc reactor.
13. Process as in claim 12 whereby the first and second step are performed in the same spinning disc reactor and the reactants of the first step are introduced at the centre or close to the centre of the disc and the free or substituted hydroxy groupcontaining compound or an free or substituted aminecontaining compound is introduced at the edge of the spinning disc.
14. Process according to any preceding claim whereby either at least one of the reactants and the reaction product or all reactants are present in different phases or are only partially mixable or nonmixable or only partially soluble or nonsoluble in one another.
15. Process for transesterification of an ester by reacting it with a compound comprising a hydroxy group or carboxylic acid group using a spinning disc reactor, to form another ester.
16. A process of claim 15 whereby a fatty acid C1C5 alkyl ester, preferably a fatty acid methyl or ethyl ester, is reacted with a sugar, preferably sucrose.
Description:
PROCESS FOR REACTING CARBOXYLIC ACIDS AND ESTERS TECHNICAL FIELD The present invention relates to a process for making esters and amides, typically being peroxy acid precursors, using a spinning disc reactor. The invention also relates to a process for making specific halide-containing hydrocarbons using a spinning disc reactor.

The invention also relates to a combined process for making first specific carboxylic acid halides and then peroxyacid precursors, using a spinning disc reactor. The invention also relates to transesterification reactions using a spinning disc reactor.

BACKGROUND Many synthesis routes for organic compounds suffer from side-reactions and from the formation of undesired by-products. Also, starting materials are not always reacted completely and the unreacted material is not always easy to remove and often remains in the reaction product as contamination. Depending on the type of reaction, the formation of by-products and the (in) completeness of reactions can mostly be controlled by selecting the correct reaction conditions, such as reaction time, temperature, pH, solvents, catalysts.

Acylation of alcohols or amines by use of a carboxylic acid can sometimes be very slow or incomplete. Acylation of alcohols or amines by use of carboxylic acid halides, such as acid chlorides, is much faster, but still side reactions such as the formation of the carboxylic acid can occur. An example of such a reaction is the formation of peroxy acid (bleach) precursors from alkyl carboxylic acid chlorides and alcohols or amines. For example, US5,523,434 describes such a reaction process and describes how the pH and temperature have to be controlled within very specific boundaries to get a satisfactory amount of product and to avoid the formation of too much by-products.

Of course, to activate the acylation of alcohols and amines by using acid halides, these acid halides have to be prepared first, typically in a separate step. Also this reaction suffers from side reactions and the formation of by products.

Another problem with the above reactions is that often phase separation occurs, either between reactants, or between starting material and reaction products, which results in incomplete mixing and an incomplete reaction.

The inventors have found that the process for making esters and amides, such as peroxy acid precursors esters and amides, by acylation of amines or alcohols, but also the formation of halide-containing compounds, can be done much more effectively and efficiently by use of a spinning disc reactor. The use of the spinning disc reactor ensures optimum mixing of reactants, improved mass transfer rate and larger reaction surface area, and this not only makes the reactions much faster, but also ensures a more complete and reliable reaction of reactants. Also, the use of the spinning disc reactor reduces the amount of by-products formed. It also minimises negative effects of process condition variations and thus allows more flexibility in reaction conditions. For example, in the reaction of acylation of alcohols or amines with carboxylic acid halides, much less carboxylic acid by product is formed.

Also, it has been found that the formation of halides, for example carboxylic acid halides mentioned above, can be done much more effectively and efficiently by use of a spinning disc reactor, reducing the amount of by-products formed and minimises negative effects of process condition variations and thus allows more flexibility in reaction conditions.

It also be found that transesterification reactions can be done much more effectively, with improved selectivity, when a spinning disc reactor is used.

SUMMARY OF THE INVENTION

The invention relates to processes using a spinning disc reactor, for making products of carboxylic acid, such as acid halides; processes for making other halides; processes for making esters and amides of carboxylic acids or derivatives thereof, namely typically bleach precursor esters or amides; and processes for transesterification.

In particular, a process is provided for making esters or amides, typically being peroxyacid precursors, by reacting a carboxylic acid or derivative thereof (reactant) with an free or substituted hydroxy group-containing compound or an free or substituted amine-containing compound (reactant) to form an ester or amide binding, whereby this reaction is done by use of a spinning disc reactor.

DETAILED DESCRIPTION OF THE INVENTION Spinning disc reactor The spinning disc reactor for use in the processes of the invention is a reactor with one or more discs or plates which can spin or rotate, typically around a vertical axis, and typically being enclosed by reactor walls, and which allows the introduction of reactants onto the disc such that they can react with one another and which ensures the reactants are moved over the disc, typically along the radial direction, typically towards the edge of the disc, by centrifugal forces and optionally also by gravity.

For example spinning disc reactors are described in R. Jachuck, C. Ramshaw, K Boodhoo and J Dalgleish, Process Intensification: the opportunity presented by spinning disk reactor technology, Inst. of Chem. Eng. Symp. Ser. 1997, 141, 417-424 and in J. Dalglish, R. Jachuck, C. Ramshaw, Photo-initiated polymerisation using spinning disc reactor, Third International Conference on PI, Antwerp 25-27 October 1999 and in Jachuck, R. J. and Ramshaw, C., 1995, Process Intensification: spinning disc polymeriser, IchemE Research Event-First European Conference for Young Researchers in Chemical Engineering.

The speed of rotation of the disc and the speed of introduction of the reactants onto the disc can be adjusted to suit each specific process. For example, depending on the reaction time required, the viscosity of the mixture of reactants, the rotation speed is adjusted, to thus create the required film of each reactant and the required residence time on the disc.

Of course, the speed of rotation and the speed of introduction of the reactants are interdependent as well. Moreover, the exact speed of rotation will also depend on the size of the disc and reactor. In general, preferred speeds of rotation of the disc or discs is above 100rpm, more preferably 1000 to 2000 rpm. Typical residence times, for example for the preferred ester and amide formation reactions herein, are between 1 and 15 seconds or even 2 and 10 seconds.

As described in the disclosures mentioned above, it may be beneficial that a number of discs in a layered, levelled structure are used or one or more discs which sloop stepwise, so that a'cascading effect'is achieved, which results in localised mixing of the ingredients at the points were the film is interrupted (e. g. at the step point).

It may be beneficial that the disc or discs are cooled to control exothermic reactions taking place on the surface of the disc (s). Because the spinning disc reactor is particularly useful to perform exothermic reactions, the spinning disc reactor and/or the disc are typically cooled to temperatures around 0°C to 50°C.

Some of the benefits of the use of the spinning disc reactor herein are the improved mass transfer rate, due to shear developed on the disc, and improved reaction surface area, on the disc.

It is clear that the main requirement is that at least one liquid is present, to be able to form the liquid film on the reactor. Because the use of the spinning disc, reactor results in an improved surface area for reaction, on the disc, the spinning disc is not only useful for liquid-liquid reactions, but also particularly useful for liquid-gas reactions. One or more

of the reactants can thus be gaseous and brought in contact with the reactant on the disc, by introducing the gas in the reactor.

More preferred however is that the reactants are all in liquid form, for example solutions of the reactant in a solvent.

Because of the benefits of the use of the spinning disc reactor as set out herein and because this results in very homogenous mixing of reactants, it is possible to use a solid reactant, but this is not preferred.

Thus, the reactants described herein after are typically made into a liquid state, by adjusting the temperature or typically by dissolving the reactants in a suitable solvent.

Processes which benefit in particular form the use of the spinning disc reactor are processes whereby either the reactants or at least one of the reactants and the reaction product are present in different phases or are not or only partially mixable or soluble in one another; for example, processes whereby the reactants are liquid and whereby, when the spinning disc is not used, phase separation occurs prior or during the reaction, or where complex solution systems and even emulsifiers are required to form a mixture or solution.

Process aids may be added during the process, typically by making these also in a liquid state by adjusting the temperature or typically by dissolving this aid in a suitable solvent.

Also, in many of the reactions of the invention, as described herein, a gas is formed during the reaction. The use of the spinning disc reactor ensures an effective and efficient means to remove or disengage this gas from the liquid reaction mixtures.

ACYLATION REACTION In a first embodiment, the invention relates to a process for making compounds having an ester or amide bound preferably such compounds which can form peroxyacids, so called

peroxyacid precursors. The acylation process herein includes the step of reacting a carboxylic acid or derivative thereof with an free or substituted hydroxy group-containing compound or an free or substituted amine-containing compound to form an ester or amide binding, by use of a spinning disc reactor.

Preferred carboxylic acid derivatives are carboxylic acid halides, such as chlorides and bromides. When such acid halides are used, generally a halide acid such as HCl is formed. The spinning disc ensures that such reaction by-products are efficiently and effectively disengaged from the reaction process/mixture.

Included herein are reactions of fatty acid, preferably fatty acid chlorides and fatty alcohols to form wax esters, typically C8-C26 or even C12-C22 fatty acid and fatty alcohols.

Typical carboxylic acid and derivatives thereof useful to form the precursors herein are known in the art. Preferred carboxylic acid and derivatives have carbon chains with at least 4 carbon atoms, preferably at least 7 or even at least 9 and preferably up to 30 or even up to 20 or even up to 16. Preferred are in particular amide substituted alkyl carboxylic acids and derivatives thereof.

US5523434 for example described reactions of acylation with acid derivatives, forming bleach precursors, which are highly preferred reactions to be performed in the spinning disc reactor.

Thus, highly preferred carboxylic acids are amide substituted alkyl carboxylic acids precursor compounds general formulae: Rl-CO-NR3-R2 COOM or Rl-NR3-CO-R2 COOM wherein RI is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms,

and R3 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and M is hydrogen or a derivative group, for example a halide such as chloride. Preferably, R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms total. Highly preferred examples of this type are acid chlorides of N-nonanoyl-aminocaproic acid and are acid chlorides of N-nonanoyl-aminocaproic acid.

Other preferred carboxylic acids or derivatives thereof are 3,5,5-tri-methyl hexanoyl carboxylic acid and nonanoyl carboxylic acid or halides thereof.

The hydroxy-containing compound or reactant and the amine-containing compound or reactant can be any compound known in the art, preferably being such that they form a so- called leaving group which is sufficiently reactive for a perhydrolysis reaction to occur, breaking the bonding between said leaving group and the carbonyl group of the acyl derived from the carboxylic acid, resulting in the formation of a peracid.

Preferred hydroxy or amine containing compounds or reactants are compound which form upon reaction with the carboxylic acid or derivative thereof one of the following groups:

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups The preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+, -N+(R3)4X- and O<--N(R3)3 and most preferably -SO3-M+ and -CO2-M+ wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator

and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Highly preferred are hydroxy compounds having an aromatic ring, such as phenol or phenol substituents and highly preferred phenol sulphonic acid or phenol sulphonate salts.

Also highly preferred are amine compounds having a heterocyclic group, preferably comprising the amine, preferably lactam or caprolactam or valero lactam.

FORMATION OF HALIDE HYDROCARBONS An other embodiment of the present invention is a process for making of hydrocarbon halides by reacting a halide donor or halogen donor with a hydrocarbon, whereby a spinning disc reactor is used.

Any suitable hydrocarbon can be used herein. Preferred hydrocarbons include the carboxylic acids described in the previous section, which are thus formed in the acid halide compound.

Also preferred are hydrocarbons comprising a double bond.

Preferred hydrocarbons are alpha olefins or derivatives thereof. Preferred for example is a reaction of alpha olefins with bromide donors to produce alkyl bromides. These compounds are useful to produce amines and substituted amines. These are for example useful to react with the carboxylic acids or derivatives thereof mentioned in the previous section, or can be useful to form amine oxides or can be useful per se as surfactants.

When alpha olefins are reacted, a mixture of primary and secondary halide compounds are typically obtained. To reduce the formation of secondary halide compounds, it is preferred that the reaction is performed by first reacting an alpha-olefin with ozone and reacting the reaction product (olefin ozonide) with the halide or halogen donor.

The halide donor and halogen donor may be any compound known in the art; preferred are chloride and bromide donors, most preferably chloride donors, in particular when carboxylic acids are reacted, and also preferred are halogen radical donors such as bromine radical donors.

Highly preferred are halogen acids such as HI, HBr or more preferably HCI, and highly 'preferred is for example SOC12- TRANS-ESTERIFICATION REACTION In addition to the esterification reaction described above, a preferred embodiment of the present invention is a process for transesterification by reacting: an ester and a compound having a hydroxy group, typically by adding also a base ; or an ester and an acid, typically by addition of an additional acid.

A preferred reaction is the transesterification of an ester derived from an organic acid having at least 6 carbon atoms, preferably 6 to 26 or even 8 to 24 or even 12 to 22 carbon atoms, and a C1-C5 alcohol. Highly preferred are reactions of one or more fatty acid methyl esters or one or more fatty acid ethyl esters.

Also a preferred reaction is the formation of a so-called wax ester (or fatty fatty ester) by transesterification of a fatty acid alkyl ester (typically ethyl or methyl) with a fatty alcohol.

The transesterification is preferably done by reacting an ester with of compound having at least 5 carbon atoms and a free hydroxy group. Preferred herein are polyols. More preferred even are sugars, preferably glucose or more preferably sucrose.

Highly preferred is the formation (by transesterification) of fatty acid esters of sugar or sugar alcohols, preferably polyesters of sugar or sugar alcohols, whereby more than one of the hydroxy group of the sugar is reacted with a fatty acid. Preferred may be that

substantially all hydroxy groups of the sugar or sugar alcohol are reacted to form ester bonds. Preferred are fatty acids or mixtures thereof with 8 to 22 carbon atoms or even 10 to 22 carbon atoms. Preferred may be saturated fatty acids or hardened fatty acids.

Preferred may be also that The process of transesterification by use of the spinning disc reactor of the invention is preferably used to produce non-digestible fatty acid sugar esters as for example described in US4005195, US 3600186, EP666713-A and EP236288.

The by-product, for example a compound having a free hydroxy group, typically methanol or ethanol as described above, can be removed from the reaction product by any means, or even during the process in the spinning disc reactor. For example, if the by-product is methanol, the temperature of the spinning disc reactor can be adjusted such that the methanol evaporates from the disc during the reaction, which reduces the back reaction.

EXAMPLES OF PREPARATION A solution of N-nonanoyl-6-aminocaproic acid in diethylether is introduced onto the disc of the spinning disc reactor through a pipe directly above the centre of a disc, having a rotation speed of 1500rpm. Simultaneously, through another pipe, thionlychloride is introduced onto the centre of the disc of the spinning disc reactor.

The flow rate of both reagents is adjusted to ensure a 1: 1 molar ratio at the centre of the disc and a residence time of the mixture of reagents and reaction product on the disc of about 5 seconds. The disc and the reactor are cooled to ensure a temperature between 10°C and 25°C. The resulting product is lead from the edge of the disc to a vessel under the disc, from where it is collected for further processing (including optional purification and analysis).

In a second step, the N-nonanoyl-6-aminocaproic acid chloride is dissolved in diethylether and introduced onto a disc as above; also an aqueous solution of sodium phenolsulphonate, having a pH of 9 by introduction of sodium hydroxide, is introduced onto the disc as above. Again, the flow rate of both reagents is adjusted to ensure a 1: 1 molar ratio at the centre of the disc and a residence time of the mixture of reagents and reaction product on the disc of about 5 seconds. The disc and the reactor are cooled to ensure a temperature between 10°C and 25°C. The resulting product is lead from the edge of the disc to a vessel under the disc and collected from the vessel for further processing (including optional purification and analysis).