MANUFACTURING PROCESS FOR THE PREPARATION OF α-BRANCHED
CARBOXYLIC ACIDS HAVING A DECREASED CONTENT OF
BETA-BRANCHED ISOMERS
The present invention relates to a manufacturing process for the preparation of α-branched carboxylic acids having a decreased content of beta-branched isomers . More in particular the invention relates to the preparation of aliphatic tertiary saturated carboxylic acids or α, α-branched saturated carboxylic acids, which contain from 8 to 25 carbon atoms and which contain a decreased content of so-called blocking β-alkyl-branched isomers.
It is generally known from e.g. US 2,831,877, US 2,876,241, US 3,053,869, US 2,967,873 and US 3,061,621 that mixtures of saturated α-branched carboxylic acids can be produced, starting from mono-olefins, carbon monoxide and water, in the presence of a strong acid.
From e.g. H van Hoorn and G C Vegter, Dynamic modulus measurements as a tool in the development of paint base materials FATIPEC, Euro Continental Congress 9, Pleniere p. 51-60 (1968); Rheol Acta 10, p. 208-212 (1971); H van Hoorn, The influence of side group structure on the glass transition temperature of isomeric vinyl ester polymers, the relation between the final coating film properties and the iso er distribution in starting branched carboxylic acids, was known. In such mixtures of α-branched carboxylic acids, significant proportions of blocking methyl-branched carboxylic acid isomers were found, the properties of which have been found to antagonize the attractive properties of other α-branched saturated carboxylic acid
constituents of said mixtures, when applied in the form of derivatives such as glycidyl esters or vinyl esters in the coating industry.
More in particular the conventionally produced branched carboxylic acid mixtures had been found to cause a too high hardness of the final coating of films, which was disadvantageous and therefore undesired for certain applications, due to the presence of significant proportions of blocking β-alkyl-branched isomers. Therefore there is a still growing need for aliphatic tertiary saturated carboxylic acids, which gives rise to softer coating films, formed from their derivatives, such as glycidyl esters or vinyl esters, and which will be further referred to as "softer α, α-branched saturated carboxylic acids".
With the term "blocking β-alkyl-branched isomers" as used throughout the specification is meant that these isomers have a β-alkyl branched structure.
An object of the present invention is to provide such softer α, α-branched saturated carboxylic acids in order to attain more attractive properties of coatings derived therefrom.
Another object of the present invention is to provide an economically attractive process for the manufacture of said "softer α, α-branched saturated carboxylic acids".
As a result of extensive research and experimentation a process giving the branched carboxylic acids aimed at, has surprisingly been found.
Accordingly, the invention relates to a manufacturing process for the preparation of α, α-branched saturated carboxylic acids, by reacting a mono-olefin or a precursor thereof, with carbon monoxide in the presence of a strong acid catalyst characterized in that the starting olefin is an oligomer containing from 7 to 25 carbon atoms and preferably from 8 to 17 carbon
atoms, that the acid catalyst is composed of BF3/H3PO4 in a molar ratio of BF3:H3Pθ4 in the range of from 0.5:1.0 to 5.0:1.0, or of CF3SO3H, that the weight ratio of the catalyst relative to the mono-olefin is in the range of from 2.0:1 to 15:1, that the reaction is carried out at a temperature in the range of from 30 to 130 °C, that the carbon monoxide pressure is in the range of 20 to 200 bar.
More preferably the starting olefin contains from 9 to 13 carbon atoms.
Still more preferably the starting olefin has been derived from an alkylene having from 2 to 12 carbon atoms and more preferably from 2 to 6 carbon atoms.
It has been surprisingly found that other strong acid catalyst systems, such as BF3/H2SO4/H2O, could not be used.
According to a more preferred embodiment, using a BF3/H3PO4 catalyst, the molar ratio between BF3 and H3PO4 is in the range 1:1 to 3:1. Preferably the reaction temperature is in the range of from 60 to 100 °C and the carbon monoxide pressure is in the range of from 50 to 100 bar. The preferred water/dry catalyst weight ratio during the reaction is in the range of from 1:4 to 1:50 and more preferably from 1:5 to 1:30.
Preferably the weight ratio of the catalyst relative to the mono-olefin is in the range of from 3:1 to 10:1.
Preferred catalyst systems are composed of CF3SO3H or
BF3/H3PO4 with water contents in the range from 3 to 13 wt% and more preferably from 5 to 11 wt%, relative to the total weight of the wet catalyst system.
The starting mono-olefin can be an oligomer of ethylene, propylene, butylene, isobutylene,
(iso) pentenes, (iso) hexenes, and mixtures thereof, and is more preferably a mixture of trimers of propylene .
It will be appreciated that the starting mono-olefins actually consist of mixtures of oligomers of several olefin isomers, showing varying proportions of each of the mono-olefin constituents.
Usual reaction times of the present process are within the range of from 10 to 150 minutes. Preferred reaction times are within the range of from 10 to 120 minutes.
It will be appreciated that the process of the present invention can be carried out as batch process, semi-batch and continuous process.
Precursors for olefins which can be suitably used are e.g. alcohols, esters, or carboxylic acids. It will be appreciated that in case of application of e.g. an alcohol precursor for an olefin, the co-produced water forms a part of the total water amount as specified hereinbefore . It has been surprisingly found that mixtures of α, α-branched saturated carboxylic acids, comprising higher proportions of so-called non-blocking isomers, highly branched isomers and of low branched isomers and lower proportions of so-called blocking isomers, could be prepared in a reliable, reproducible way and starting from relatively cheap mono-olefins .
A preferred embodiment of the present manufacturing process is carried out starting from Cg-Ci2 mono-olefins giving rise to the following typical examples of e.g. C9 based VERSATIC-10 acid in the final reaction product (VERSATIC is a trade mark) .
Non-blocking i somer
Blocking isomer
Highly branched isomer
It will be appreciated that the proportion of each of these types of isomers in the total mixture may vary depending on the specific reaction/catalyst conditions .
Typical proportions of highly branched isomers, blocking isomers, non-blocking isomers and low-branched isomers are in the ranges of from 4 to 9 wt%, from 2 to 6 wt%, from 60 to 80 wt% and from 15 to 25 wt% respectively, the sum of the weight of the components being 100%, and are deviating significantly from the isomer distribution in conventional C]_Q o, α-branched sturated carboxylic acids (from 1 to 3 wt%, from 31 to 33 wt%, from 51 to 53 wt% and from 14 to 16 wt% respectively, the sum or the components being 100%) .
It will be appreciated that the hereinbefore specified softer α, α-branched saturated carboxylic acid composition forms another aspect of the present invention .
Said softer α, α-branched saturated carboxylic acid compositions are characterized by specific absorptions in their ^C NMR spectra and specific signals in their gas
chromatograms as compared with the prior art α, α-branched saturated acids.
Characteristic GLC data are depicted in figures 1 and 2 and are listed hereafter: Commercial VERSATIC-10 acid
soft α, α-branched carboxylic acids, containing 10 carbon atoms (AA10 acid)
13c NMR conditions: Bruker AMX-500 spectrometer
The sample consisted of 2.3 g of VERSATIC-10 and of soft α, α-branched carboxylic acids, containing 10 carbon atoms (AA10 acid) dissolved in 2.3 g CDCI3 to which 50 mg Cr (acac)3 was added. The applied gas chromatography conditions were as follows :
Column DB]_ 60 *0.32 mm ID, film thickness 0.25μ, active phase is 100% dimethyl polysiloxane .
Temperature profile: 2 min . at 40 °C, 5 °C/min. to 280 °C.
So total analysis time is 50 minutes.
Injection temperature: 275 °C
Detector temperature: 325 °C (F/D)
Injection volume: lμl Split ratio: 1:40
The acid mixtures initially obtained can be purified by methods known per se, such as destination.
It will be appreciated that the softer α, α-branched saturated carboxylic acids can be converted by known methods in their derivatives such as salts, esters, acid halides and more in particular glycidyl esters or vinyl esters, which can be used as attractive starting materials in the coating industry.
The invention is further illustrated by the following examples, however without restricting its scope to these embodiments . Examples A-H + comp. ex.
A 250 ml Hastelloy C autoclave is loaded with 18.79 g water and 171.5 g CF3SO3H. Consequently, the water content of this catalyst system amounts to 9.9 wt% . The autoclave is equipped with a manometer, a magnetic stirrer, a heating mantel and inlets for CO and olefins . The catalyst CF3SO3H and water are heated to 90 °C and
carbon monoxide is introduced to give a pressure of 80 bar (at 90 °C) . Hereafter 43.7 g propylene trimer (PT3) (corresponding to 0.35 mol) is dosed by means of a pressure pump in the course of 60 minutes. The temperature rises to 94 °C and the pressure needs to be adjusted to 80 bar by adding CO. The Koch reaction is allowed to react for 40 more minutes.
Subsequently the reaction mixture is poured over ca . 150 g ice in a separation funnel. A separation into two layers takes place. The lower catalyst layer is removed and the upper organic layer is washed twice with ca . 50 g water. 50.4 g of a reaction product is obtained which yields in 51.3 wt% of "soft" α, α-branched carboxylic acid, containing 10 carbon atoms (AA10 acid) . The process conditions of several batch experiments are shown in Table 1.
The composition of the V10 in the reaction product (referred to as A) is shown in Table 2, the other entries are the results of experiments analogous to the one described.
Table 1
Process conditions batch-wise AA-10 acid synthesis
(a) H3PO4/BF3/H2O cat.
(b) Cf3S03H
(c) BF3/H2SO4/H2O 1.5/1.16/3 mol. rat. 1.5/1/1
Table 2 Isomer distribution of soft AA-10 acid
It will be appreciated that the isomer distributions as shown for acid products A-G in Table 2, differ considerably from the indicated prior art VERSATIC-10 acid distribution, whereas the mixture H does not substantially differ from said prior art acid composition. Example J
A 250 ml Hastelloy C autoclave is continuously fed with 3.6 g/minute of a catalyst system, which consists of BF3/H3P04/water in the molar ratio 1.5/1/1.23 and
0.9 g/minute propylene trimer (PT3) for 16 hours.
Consequently the water content of pure catalyst system amounts to 10.0 wt% . The autoclave is equipped with a manometer, a mechanically driven stirrer, a heating mantel, inlets for CO, catalyst and olefins and a dip-tube for the continuous withdrawing of the product/catalyst mixture.
The temperature in the autoclave is 104 °C and the carbon monoxide pressure of 78 bar is regulated via a back-pressure .
Subsequently the reaction mixture is poured over ice in a separation funnel. A separation into two layers takes place. The lower catalyst rich layer is removed and the upper organic layer is washed with water. 1178.8 g of a reaction product is obtained which yields 44.4 wt% of "soft" α, α-branched carboxylic acids, containing 10 carbon atoms (AA10 acid) . The composition of the V10 in the reaction product is shown in Table 3.
Table 3
Isomer distribution of soft AA10 acid made in a continuous process