WO1993022270A1

WO1993022270A1 - Saturated, monocarboxylic acids, the preparation thereof, and derivatives therefrom

Info

Publication number: WO1993022270A1
Application number: PCT/EP1993/001134
Authority: WO
Inventors: Johannes Jacobus Keijsper; Roger Stewart Downing; Bernadette Elisabeth Bongenaar-Schlenter; Jan Hofman; David Pappie
Original assignee: Shell Internationale Research Maatschappij B.V.; Shell Canada Limited
Priority date: 1992-05-06
Filing date: 1993-05-04
Publication date: 1993-11-11
Also published as: AU4065993A; ZA933123B

Abstract

This invention relates to a composition of isomeric saturated, monocarboxylic acids containing either 11, 12, 13, 14 or 15 carbon atoms having general formula (I), wherein R1 and R2 each are branched or linear alkyl groups, based on the weight of the isomeric saturated monocarboxylic acids, R3 is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups, the preparation thereof, and the derivatives obtainable therefrom, in particular the vinylesters and glycidylesters.

Description

SATURATED, MONOCARBOXYLIC ACIDS, THE PREPARATION THEREOF, AND DERIVATIVES THEREFROM

This invention relates to saturated, monocarboxylic acids, the preparation thereof, and the derivatives obtainable therefrom.

The acid catalysed synthesis of (mono)carboxylic acids from i.a. olefins, carbon monoxide and water, known as the Koch synthe- sis, has made these acids commercially available since 1962.

The conditions under which the production plant was operated were quite severe. Pressures in excess of 500 bar, temperatures above 200 ^CC, and highly acidic reaction media (using eg., H-SO, , H-.P0, , HF or Lewis acids as catalysts) requiring a special reactor, were employed. Under these conditions, nearly all olefins and a great number of dienes, unsaturated esters, unsaturated and saturated alcohols and diols, reactive alicyclic compounds, halogenated compounds, certain amines, esters and aldehydes react to form a carboxylic acid. The accepted mechanism for the Koch synthesis starting from an olefin (Angew. Che . Int. Ed. I, 266 (1966)) comprises an initial formation of a carbenium ion (2) by protonation by an acid catalyst (1) , which carbenium ion subsequent to the addition of carbon monoxide gives rise to an acylium cation (3) . When the latter reacts with water, the carboxylic acid is formed, releasing the acid catalyst. The reaction is schematically represented as set out below.

H_£0

It has been realized that isomerization is an important side reaction of the intermediate carbenium ions under the conditions of the Koch synthesis. This isomerization leads via migration and rearrangement reactions to the formation of tertiary or α,α-disub- stituted carbenium ions. The ratio of secondary o-substituted) versus tertiary carboxylic acids hence depends on the relative occurrence of the izo erization reaction versus that of the acyl- ation reaction. Other important side reactions influencing the outcome of the final product composition, are oligomerization, depolymerization, disproportionation and cracking. In addition the Koch synthesis appears to be reversible (Retro-Koch) which together with further rearrangement reactions give rise to branched carbox¬ ylic acids.

Due to the aforementioned (side) reactions occurring in commercial synthesis, the products manufactured and marketed by for instance Shell ("Versatic acids", a trademark), in fact comprise a composition of isomers and homologues of the desired saturated, monocarboxylic acid, as well as non-acidic material (often referred to as "neutrals"). Such composition may be purified, for example by washing to separate the non-acidic material from the carboxylic acids, and/or by distilling to separate the carboxylic products having a higher or lower carbon content than the desired carboxylic acid product. In producing for instance Versatic 9 (an acid containing 9 carbon atoms) from the di er of butylene, it is known that also Versatic 5 and .other carboxylic acids are produced, which homologues normally will be separated from the commercial sample. Alternatively, where the compositions are -used as feedstock to produce certain derivatives, the compositions may be used as such, followed by purification of these derivatives.

Irrespective whether the neutrals and/or homologues are separated from a commercially available acid composition, the acid composition still comprises many isomers of the desired saturated monocarboxylic acid. Especially, the thermodynamically more stable isomers, i.e., the isomers bearing branched alkyl groups attached to the carbon atom next to the carboxylic acid group will be abundant. These commercially available acid compositions, however, are unsatisfactory for purposes where monocarboxylic acid composi- tions are required that comprise isomers being α,o-dialkyl substituted carboxylic acids, the alkyl groups of which are highly linear. These acid compositions are desirable for the production of vinylester derivatives ("VeoVa", a trademark) that upon polymerization have a low glass transition temperature.

The invention provides a composition of isomeric saturated, monocarboxylic acids containing either 11,^"" 12, 13, 14 or 15 carbon atoms having the general formula (I) R,

wherein R.. and R- each are branched or linear alkyl groups, based on the weight of the isomeric saturated monocarboxylic acids R_ is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups.

It is to be understood that the above composition may comprise some of the aforementioned "neutrals" and homologues, which, however, by purification may be fully separated.

Preferably, at least one of the substituents R. , R„, or R, is a methyl group. Such composition is particularly suitable for making vinylester compositions ("VeoVa") or glycidylester compositions (trademark "Cardura") having superior coating proper¬ ties and handling characteristics than their branched counterparts. More preferred are compositions described above, wherein R, for at least 80 %wt, more preferably for at least 85 %wt is a branched or linear alkyl group (i.e., o,α-disubstituted saturated, monocarboxylic acids), and/or, compositions (of the isomeric α-substituted or α,α-disubstituted saturated, monocarboxylic acids) wherein at least 90 %wt of the alkyl groups are n-alkyl groups. In view of availability and processability especially preferred are compositions of isomeric saturated, monocarboxylic acids containing either 11 or 13 carbon atoms, preferably 11 carbon atoms.

In addition the invention provides a process for preparing a composition of isomeric saturated, monocarboxylic acids containing either 11, 12, 13, 14, or 15 carbon atoms having the general formula (I)

wherein R- and R., each are branched or linear alkyl groups, based on the weight of the isomeric saturated monocarboxylic acids R, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups, which process comprises reacting a composition of olefins, carbon monoxide and water in the presence of an acidic catalyst, wherein the composition of olefins comprises olefins containing either 10, 11, 12, 13, or 14 carbon atoms, of which at least 95 %wt are n-alkenes, the ratio by weight of catalyst over olefin is in the range of 0.2 to 10, preferably in the range of 0.5 to 5, the water content in the reactor is less than 13 %wt , preferably less than 12 %wt relative to the weight of the total liquid phase in the reactor, and the reaction is carried out for a period of 0.1 to 4 , preferably 0.2 to 2 hours at a temperature in the range of 40 to 200 ^βC, preferably 50 to 150 ^βC, and a pressure in the range of 5 to 200 bar, preferably 10 to 100 bar.

It is observed that the above conditions are particularly applicable for the continuous production of the acid composition. However, these conditions can easily be adapted for batch produc¬ tion, and such process is also considered within the gist of the present invention.

Using a feedstock different from that discussed above will not result in the desired carboxylic acid composition, but lead to its more highly branched counterpart. A preferred source of feedstock are olefins produced by an ethylene oligomerization process, such as the Shell Higher Olefin Process ("SHOP"), which process results in linear α olefins of high purity. However, also linear olefins having internal unsaturation are suitable as feedstock in the present invention. Preferably, the composition of olefins comprises at least 99 %wt of n-alkenes.

A particular preferred feedstock are olefins prepared by the above SHOP or a similar process, which olefins are the product fraction distillable at 158 to 171 ^βC; or at 210 to 215 °C, corre- sponding respectively to the CIO α-olefin or C12 α-olefin.

As mentioned earlier, the acid composition in accordance to the invention is a very suitably used as intermediate in the production of the corresponding vinylester composition. According¬ ly, the invention further provides a composition of isomeric vinyl- esters of saturated, monocarboxylic acids containing either 11, 12, 13, 14 or 15 carbon atoms in the acid moiety having the general formula (II)

wherein R.. and R„ each are branched or linear alkyl groups, based on the weight of the isomeric vinylesters R, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups. In the application in the environmentally desired, solvent-free coating systems, such vinylester compositions are highly appreciated for their ability to provide a low minimum film forming temperature. Thus, whereas the polymer coating prepared from "VeoVa 11", the vinylester composition of saturated, monocarboxylic acids containing 11 carbon atoms, is sufficiently soft (a glass transition temperature, Tg, of below -40 ^CC) to allow application of the coating without the need to resort to a volatile organic solvent, the resulting coating is sufficiently hard not to be tacky. Application of the vinylester composition in coatings, adhe- sives, lacquers, concrete and others is subject of a separate patent application.

Moreover, the invention provides a process of preparing a composition of isomers of a vinylester of a saturated, monocarbox- ylic acid containing either 11, 12, 13, 14, or 15 carbon atoms of of the present invention, which process comprises reacting the saturated monocarboxylic acid composition of the present invention with acetylene in the presence of a zinc catalyst. Preferably, the zinc catalyst is derived from zinc oxide and the saturated, mono- carboxylic acid composition of the present invention. It is ob¬ served that surprisingly the zinc salt is sufficiently soluble in the acid composition to allow relatively large amounts of zinc to be dissolved. Alternatively, the monocarboxylic acid composition may be prepared by conventional transesterification with vinyl acetate, or reaction in vapor phase of the monocarboxylic acid with acetylene or ethylene.

The invention, furthermore, provides a composition of isomeric glycidylesters of saturated, monocarboxylic acids containing either 11, 12, 13, 14, or 15 carbon atoms in the acid moiety having the general formula (III)

-

wherein R. and R„ each are branched or linear alkyl groups, based on the weight of the isomeric glycidylesters R, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups. Such a glycidylester composition is obtainable by a process comprising the reaction of the saturated, monocarboxylic acid composition of the invention or its alkali metal salt with epi- chlorohydrin (ECH) , optionally in the presence of an alkaline reactant. The glycidylester composition of the saturated, Cll monocarboxylic acid shows similar improvements over its less linear homologues ("Cardura E10", etc.) as the "VeoVa 11" shows over for instance "VeoVa 9", "VeoVa 10", and "VeoVa 911" (Cardura and VeoVa are trademarks).

The saturated monocarboxylic acid composition of the present invention may, next to serving as intermediate in the production of a vinyl or glycidylester composition, also be used in various applications such as in coating systems, as intermediate in ester solvents and in metal extraction.

The invention is further elucidated by the following examples. i will be seen from the below data that carboxylic acid composi¬ tions that are not in accordance with the present invention, upon vinylation, result in vinylester compositions having a structure leading to the polymer having a Tg which is too high. Example la, the Koch reaction A continuously stirred tank reactor with a total volume of ca. 300 mL and a constant working volume (liquid level in the reactor) of ca. 80 mL was maintained at a temperature of 100 °C and a CO pressure of 80 bar. The reactor was continuously supplied with 60 g h of SHOP CIO olefin (> 99 %wt decene, 98 %wt linear components, > 96 %wt o-olefins) and 120 g h of a catalyst composition compris¬ ing BF,/H,P0, in a molar ratio of 1.5, and containing 16 %wt on the total- eight of the catalyst composition of H„0. The effluent was washed twice with an equal amount of water, and the organic frac¬ tion was then dried (over MgSO, ) and analysed. 13 The analysis was conducted with C-NMR spectroscopy, as well as with gas/liquid chromatography (GLC) and combined gas chromato- graphy/mass spectroscopy (GCMS). The "neutrals" fraction was separated from the acid composition by base extraction of the latter of the organic fraction.

Example lb. vinylation

The acid composition was converted into the vinylester in a stirred reactor of 300 mL using the following procedure. Thus, 12.5 g ZnO was added to 100 mL of the above purified acid composition. H„0 was substantially removed by passing N- at 130 ^βC through the mixture. The resulting mixture is then heated to ca. 190 °C and for two hours acetylene (12 Lh) was passed through. Complete conversion was confirmed by GLC and NMR analyses. The vinylester was removed from the reaction mixture by flashing (130 ^βC at 30 mbar) . The results are produced in Table 1. Examples 2 and 3

The procedure set out in example la was used, however using a different reaction temperature (respectively 85 and 115 ^βC). Example 4 The procedure set out in example la was used, however now applying a CO pressure of 50 bar. Example 5

The procedure set out in example la was used, however now using a reaction temperature of 95 ^βC, applying a CO pressure of 70 bar, and using a feed stream of 60 g h olefin and 45 g/h catalyst composition containing 15 %wt of H_0. Example 6

The procedure set out in example la was used, however now using a catalyst composition containing 12 %wt of H„0 and using a feed stream of 45 g/h olefin. Comparative example A

The procedure set out in example la was used, however now using a reaction temperature of 90 ^βC, using a catalyst composition containing 18 %wt of H„0 and using a feed stream of 50 g/h olefin. Due to the low yield of C. . carboxylic acid, the carboxylic acid has not been further analysed ("na"). Comparative example B

The procedure set out in example la was used, however now using a reaction temperature of 145 °C, using a catalyst composi¬ tion containing 12 %wt of H_0 and using a feed stream of 25 g/h olefin and 50 g/h catalyst composition. The yield of C. . carboxylic acid was to low to analyse the content further than that the ratio secondary versus tertiary carboxylic acid was approximately 50:50.

Table 1

A 2 L batch reactor was filled with 1480 g catalyst composi¬ tion comprising BF,/H,P0, in a molar ratio of 1.5, and containing 15 %wt on the total weight of the catalyst composition of H„0 was maintained at a temperature of 100 ^βC and a CO pressure of 100 bar. The reactor was supplied over a period of 3 hours with 677 g of SHOP CIO olefin (> 99 %wt decene, 98 %wt linear components, > 96 %wt α-olefins) after which the reaction was continued for another 1 hour. Then the reactor was cooled and depressurised, and the reactor content was worked up and analysed as described for the effluent in example 1. Example 8

Similar to example 7, a 2 L batch reactor was filled with 1520 g catalyst composition comprising BF,/H_P0, in a molar ratio of 1.5, and containing 9.5 %wt on the total weight of the catalyst composition of H„0 was maintained at a temperature of 85 °C and a CO pressure of 100 bar. The reactor was supplied over a period of 3 hours with 644 g of 1-tetradecene after which the reaction was continued for another 1 hour. Then the reactor was cooled and depressurised, and the reactor content was worked up and analysed as described for the effluent in example 1. Comparative example C

The procedure set out in example 7 is used, however now using a feedstock comprising a C._Q iso olefin (pentene dimer) . In view of excessive side reactions taking place, the reaction was interrupted and the product not further analysed. Comparative example D The procedure, set_out in example 7 is used, however now using a feedstock comprising a C._ iso olefin (pentene dimer) , a tempera¬ ture of 50 ^βC, and an olefin introduction time of 2 hours, without extra reaction time. No linear C.. carboxylic acids were detected in the acid composition. An analysis of the secondary branched versus the tertiary branched C... carboxylic acid has not been carried out. Comparative example E The procedure set out in example 7 is used, however now using a feedstock comprising a mixture of C_-C-_n olefins (60 %wt normal; 25 %wt iso, 10 %wt cyclic), a temperature of 75 "C, and an olefin introduction time of 2 hours, without extra reaction time. Although a respectable conversion of olefin is achieved, the content of the C-₁ carboxylic acids was too low to analyse the composition for secondary or tertiary, linear or branched C.- carboxylic acids. Table 2

C... acid composition, not further analysed.

Claims

C LA I M S

1. A composition of isomeric saturated, monocarboxylic acids containing either 11, 12, 13, 14 or 15 carbon atoms having the general formula (I)

wherein R- and R„ each are branched or linear alkyl groups, based on the weight of the isomeric saturated monocarboxylic acids R_ is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups.

2. A composition as claimed in claim 1, wherein at least one of R. , -, or is a methyl group.

3. A composition as claimed in claim 1 or 2, wherein R, is hydrogen in 1 to 5 %wt and a branched or linear alkyl group in 95 to 99 %wt.

4. A composition as claimed in anyone of claims 1 to 3, wherein at least 95 %wt of the alkyl groups are linear alkyl groups.

5. A composition as claimed in anyone-of claims 1 to 4, wherein the isomeric saturated, monocarboxylic acids contain either 11 carbon atoms or 13 carbon atoms, preferably 11 carbon atoms.

6. A process for preparing the saturated, monocarboxylic acid composition of claim 1, which process comprises reacting a composi¬ tion of olefins, carbon monoxide and water in the presence of an acidic catalyst, wherein the composition of olefins comprises olefins containing either 10, 11, 12, 13, or 14 carbon atoms, of which at least 95 %wt are n-alkenes, the ratio by weight of cata- lyst over olefin is in the range of 0.2 to 10, preferably in the range of 0.5 to 5, the water content in the reactor is less than 8 %wt , preferably less than 7 %wt relative to the weight of the total liquid phase in the reactor, and the reaction is carried out for a period of 0.1 to 4, preferably 0.2 to 2 hours at a temperature in the range of 40 to 200 °C, preferably 50 to 150 °C, and a pressure in the range of 5 to 200 bar, preferably 10 to 100 bar.

7. A composition of isomeric vinylesters of saturated, mono¬ carboxylic acids containing either 11, 12, 13, 14 or 15 carbon atoms in the acid moiety having the general formula (II)

wherein R. and R,. each are branched or linear alkyl groups, based on the weight of the isomeric vinylesters R, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups.

8. A process of preparing the vinylester composition of claim 7, which process comprises reacting a composition of claim 1 with acetylene in the presence of a zinc catalyst.

9. -A composition of isomeric glycidylesters of saturated, mono¬ carboxylic acids containing either 11, 12, 13, 14, or 15 carbon atoms in the acid moiety having the general formula (III)

wherein R. and R„ each are branched or linear alkyl groups, based on the weight of the isomeric glycidylesters R, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt, and wherein at least 80 %wt of the alkyl groups are linear alkyl groups.

10. A process for preparing the glycidylester composition of claim 9, which process comprises reacting a composition as claimed in claim 1 or its alkali metal salt with epichlorohydrin (ECH) , optionally in the presence of an alkaline reactant.