Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
  • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds

Definitions

• the invention relates to a process for the manufacture of quaternary carboxylic acids. More in particular the invention relates to a process for the manufacture of quaternary carboxylic acids from higher linear olefins by means of a Koch synthesis using carbon monoxide as reagent and a solid acid catalyst.
• the cationic resin was specified to have an acidity of at least equivalent to that of a 65 wt% sulphuric acid. It will be appreciated by an average person skilled in the art that said process can only be performed in two steps, i.e. one step comprising contacting the solid catalyst with olefin/CO feed and a subsequent step contacting the catalyst with water feed, and that stoichio- metric amounts of branched olefin and water will not lead to the desired products in an acceptable yield. Moreover, said process cannot produce more than 1 mole of converted olefin per mole active proton on the solid catalyst in one cycle of two steps.
• EP-A-0249976 was known a process for the manufacture of branched carboxylic acids, by catalytic conversion of olefins with carbon monoxide and water in the presence of zeolites as catalysts at temperatures of from 200 to 500 °C and at pressures of 200 to 700 bar.
• zeolites of the pentasil type are used as catalysts. According to the exemplified embodiments only high temperatures (300 °C) and pressures (300-500 bar) are used. It will be appreciated that said disclosed reaction conditions will give rise to higher operation costs due to required measures as to safety and environment.
• An object of the present invention is providing an alternative efficient one step manufacturing process for quaternary carboxylic acids, which process starts from linear olefins containing 5 or more carbon atoms, and which uses a solid catalyst system under relatively mild conditions on the one hand and which shows economically acceptable conversion and economically acceptable selectivity to quaternary carboxylic acids on the other hand.
• each symbol R represents a radical having 1 to 10 carbon atoms. More preferably the total number of carbon atoms in the trialkylacetic acids ranges from 5 to 19 and most preferably from 5 to 14 carbon atoms and most preferably from 9 to 13.
• linear olefin or a precursor thereof as used throughout the present specification is meant that the specified linear olefin itself as well as alcohols, esters or ethers, from which the specific olefin can be easily derived, can be used as starting materials for the present manufacturing process, which makes this process much more flexible than conventional prior art processes.
• linear olefins containing from 5 to 15 carbon atoms and more preferably from 5 to 10 carbon atoms or precursors therefor, can be converted by the present process into quaternary carboxylic acids aimed at.
• An important advantage of the present process is that it can be operated as one step or one reactor process showing an economically acceptable combination of conversion degree and selectivity.
• the catalyst to be used for the process of the present invention is a solid acidic ion exchanger showing strong acid behaviour. It is preferably selected from the group consisting of sulfonated resins and more preferably sulfonated copolymers of styrene and divinylbenzene, copolymers of vinylnaphthalene and divinylbenzene, copolymers of styrene and methacrylic acid resins, phenolic based resins, sulfonated poly (tetrafluoro- ethylene) and sulfonated siloxane polymers and sulfonated cellulose derivatives.
• the resin is treated to give a sulfonic acid cation-exchange resin capable of providing sufficient protons, i.e. the resin having an acid strength equi- valent to at least 65 wt% sulphuric acid and preferably to at least 70 wt% sulphuric acid.
• Catalyst solid resins comprising sulfonic acid groups and derived from copolymers from styrene-divinyl- benzene, copolymers from vinylnaphthalene-divinyl benzene or derived from (tetrafluoroethylene) polymers or from siloxane polymers are preferred.
• AMBERLYST NAFION or DELOXAN catalysts
• NAFION NAFION
• DELOXAN are Trade Marks
• styrene-divinylbenzene copolymer based catalyst such as the AMBERLYST type catalysts. More preferably AMBERLYST 38 catalyst is used.
• the reaction temperature in the batch reactor is in the range of from 25 °C to 200 °C and preferably from 100 to 150 °C.
• the pressure in the reactor is in the range of from 1 to 200 bar and preferably from 50 to 100 bar.
• polar non-coordinating organic solvents can be used chemically inert polar organic solvents such as carboxylic acids or derivatives thereof and more in particular esters, or an optionally substituted sulfolane (preferably sulfolane) .
• a quaternary acid is present in the continuous reactor and preferably a CSTR reactor.
• the carboxylic acid to be produced can be used as solvent.
• the CSTR reactor is filled with solvent and catalyst with a catalyst/solvent wt ratio of in the range of from 0.01 to 0.5 w/w solid/liquid and preferably 0.2- 0.3 w/w.
• the other respective reactants are introduced into the reactor and reaction mixture is heated to the desired 5-30 mmol/reaction temperature.
• a catalyst/solvent ratio up to 0.95 w/w (solid/liquid) and preferably in the range of from 0.4 to 0.8.
• the feed of starting olefin is in the range of from
• the water/olefin molar ratio or the molar ratio of the respective precursors therefor is in the range of from 0.5 to 2 mole/mole and preferably about 1 and the CO/olefin molar ratio is in the range of from 0.5 to 1000 mole/mole and preferably from 1 to 100.
• AMBERLYST 38 was dried overnight in an oven at 100 °C and a sample of 15.3 g dry AMBERLYST was loaded in a 250 ml autoclave together with 49.9 g branched C ] _ ] _ acids
• a sample of the product mixture was analyzed by means of gas chromatography .
• the concentrated carboxylic acid mixture was analyzed by means of gas chromatography .
• the total product mixture contained 14 C% carboxylic acids other than branched C ⁇ acids (VERSATIC 11 acids) used as solvent. This corresponds to a yield in non-C ⁇ carboxylic acid of 46 C%, based on feed.
• the extracted fraction contained 94 C% of branched C 9 acids (VERSATIC 9 acids), after renormalization to exclude the branched C ⁇ _ ⁇ _ acids (VERSATIC 11 acids) used as solvent.
• Example 2 2-pentanol in VERSATIC 11 acids
• AMBERLYST 38 was dried overnight in an oven at 100 °C and a sample of 15.2 g dry AMBERLYST was loaded in a 250 ml autoclave together with 51.7 g branched C ⁇ _ ⁇ _ acids
• the total product mixture contained 14 C% carboxylic acids other than branched C ⁇ _ ⁇ _ acids (VERSATIC 11 acids) used as solvent. This corresponds to a yield in non-C]_ ⁇ carboxylic acid of 71 C%, based on feed.
• the extracted fraction contained 85 C% of branched Cg acids (VERSATIC 6) , after renormalization to exclude the branched C ⁇ _ ⁇ _ acids (VERSATIC 11 acids) used as solvent.
• Example 3 2-pentanol in VERSATIC 5 acids
• AMBERLYST 38 was dried overnight in an oven at 100 °C and a sample of 16.5 g dry AMBERLYST was loaded in a 250 ml autoclave together with 57.4 g pivalic acid as solvent and 80 bar CO.
• the autoclave was heated up to 150 °C and kept under constant pressure by means of the use of a constant back-pressure regulator and a constant gas flow of 1.351 CO/h.
• 2-pentanol was continuously fed to the autoclave at a rate of 1.63 ml/h (15.1 mmol/h) during 21.0 h.
• the autoclave was then cooled to room temperature, depressurized and unloaded.
• the reaction product was analyzed as described in example 1.
• the total product mixture contained 14 C% carboxylic acids other than pivalic acid used as solvent. This corresponds to a yield in carboxylic acid (other than pivalic acid) of 54 C%, based on feed.
• the extracted fraction contained 82 C% of branched Cg acids (VERSATIC 6 acids), after renormalization to exclude the pivalic acid used as solvent.
• AMBERLYST 38 was dried overnight in an oven at 100 °C and a sample of 15.4 g dry AMBERLYST was loaded in a 250 ml autoclave together with 54.1 g branched C ⁇ _ ⁇ _ acids
• the autoclave was heated up to 150 °C and kept under constant pressure by means of the use of a constant back-pressure regulator and a constant gas flow of 1.351 CO/h.
• Di- isobutyl-carbinol (DIBC) was continuously fed to the autoclave at a rate of 2.25 ml/h (12.6 mmol/h) during 17.0 h.
• DIBC Di- isobutyl-carbinol
• the autoclave was then cooled to room temperature, depressurized and unloaded.
• the reaction product was analyzed as described in example 1.
• the total product mixture contained 15 C% carboxylic acids other than branched C ⁇ acids (VERSATIC 11 acids) used as solvent.

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• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1999
  • 1999-09-01 TW TW088115042A patent/TW491834B/zh not_active IP Right Cessation
  • 1999-09-15 WO PCT/EP1999/006998 patent/WO2000017146A1/en not_active Ceased
  • 1999-09-15 CA CA002344451A patent/CA2344451C/en not_active Expired - Fee Related
  • 1999-09-15 AU AU59806/99A patent/AU5980699A/en not_active Abandoned
  • 1999-09-15 JP JP2000574056A patent/JP2002526464A/ja active Pending
  • 1999-09-15 KR KR1020017003447A patent/KR100618260B1/ko not_active Expired - Fee Related
  • 1999-09-15 CN CNB998111929A patent/CN1134396C/zh not_active Expired - Fee Related
  • 1999-09-15 BR BR9913968-5A patent/BR9913968A/pt not_active Application Discontinuation
  • 1999-09-15 EP EP99969406A patent/EP1115684B1/en not_active Expired - Lifetime
  • 1999-09-15 DE DE69904615T patent/DE69904615T2/de not_active Expired - Lifetime
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