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WO1993022270A1 - Acides monocarboxyliques satures, leur preparation et leurs derives - Google Patents

Acides monocarboxyliques satures, leur preparation et leurs derives Download PDF

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Publication number
WO1993022270A1
WO1993022270A1 PCT/EP1993/001134 EP9301134W WO9322270A1 WO 1993022270 A1 WO1993022270 A1 WO 1993022270A1 EP 9301134 W EP9301134 W EP 9301134W WO 9322270 A1 WO9322270 A1 WO 9322270A1
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WO
WIPO (PCT)
Prior art keywords
composition
alkyl groups
linear alkyl
saturated
branched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1993/001134
Other languages
English (en)
Inventor
Johannes Jacobus Keijsper
Roger Stewart Downing
Bernadette Elisabeth Bongenaar-Schlenter
Jan Hofman
David Pappie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Canada Ltd
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Canada Ltd
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Canada Ltd, Shell Internationale Research Maatschappij BV filed Critical Shell Canada Ltd
Publication of WO1993022270A1 publication Critical patent/WO1993022270A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids

Definitions

  • This invention relates to saturated, monocarboxylic acids, the preparation thereof, and the derivatives obtainable therefrom.
  • 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 ⁇ , ⁇ -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.
  • the Koch synthesis appears to be reversible (Retro-Koch) which together with further rearrangement reactions give rise to branched carbox ⁇ ylic acids.
  • 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.
  • the acid composition still comprises many isomers of the desired saturated monocarboxylic acid.
  • 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 are unsatisfactory for purposes where monocarboxylic acid composi- tions are required that comprise isomers being ⁇ ,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,
  • 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.
  • composition may comprise some of the aforementioned “neutrals” and homologues, which, however, by purification may be fully separated.
  • At least one of the substituents R. , R restroom, 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.
  • 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, ⁇ -disubstituted saturated, monocarboxylic acids), and/or, compositions (of the isomeric ⁇ -substituted or ⁇ , ⁇ -disubstituted saturated, monocarboxylic acids) wherein at least 90 %wt of the alkyl groups are n-alkyl groups.
  • compositions of isomeric saturated, monocarboxylic acids containing either 11 or 13 carbon atoms, preferably 11 carbon atoms.
  • 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)
  • 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
  • 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 ⁇ olefins of high purity.
  • SHOP Shell Higher Olefin Process
  • linear olefins having internal unsaturation are suitable as feedstock in the present invention.
  • 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 ⁇ C; or at 210 to 215 °C, corre- sponding respectively to the CIO ⁇ -olefin or C12 ⁇ -olefin.
  • 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)
  • R.. and R naph 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.
  • vinylester compositions are highly appreciated for their ability to provide a low minimum film forming temperature.
  • the vinylester composition of saturated, monocarboxylic acids containing 11 carbon atoms is sufficiently soft (a glass transition temperature, Tg, of below -40 C C) 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.
  • Tg glass transition temperature
  • 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.
  • 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.
  • 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)
  • R. and R naph 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.
  • 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 Hgan0.
  • the effluent was washed twice with an equal amount of water, and the organic frac ⁇ tion was then dried (over MgSO, ) and analysed.
  • the acid composition was converted into the vinylester in a stirred reactor of 300 mL using the following procedure.
  • 12.5 g ZnO was added to 100 mL of the above purified acid composition.
  • 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 ⁇ C at 30 mbar) . The results are produced in Table 1. Examples 2 and 3
  • Example 5 The procedure set out in example la was used, however using a different reaction temperature (respectively 85 and 115 ⁇ C).
  • 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 applying a CO pressure of 50 bar.
  • 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 Hiker0 was maintained at a temperature of 100 ⁇ C 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 ⁇ -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.
  • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention se rapporte à une composition d'acides monocarboxyliques isomères saturés, contenant 11, 12, 13, 14 ou 15 atomes de carbone et répondant à la formule générale (I), dans laquelle R1 et R2 représentent des groupes alkyles linéaires ou ramifiés, basés sur le poids des acides monocarboxyliques isomères saturés, R3 représente hydrogène en une teneur de 1 à 25 % en poids, et un groupe alkyle linéaire ou ramifié en une teneur de 75 à 99 % en poids, au moins 80 % en poids des groupes alkyles étant linéaires. L'invention se rapporte également à leur préparation, à des dérivés obtenus à partir de ces acides, en particulier les vinylesters et les glycidylesters.
PCT/EP1993/001134 1992-05-06 1993-05-04 Acides monocarboxyliques satures, leur preparation et leurs derives Ceased WO1993022270A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92201281 1992-05-06
EP92201281.0 1992-05-06

Publications (1)

Publication Number Publication Date
WO1993022270A1 true WO1993022270A1 (fr) 1993-11-11

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PCT/EP1993/001134 Ceased WO1993022270A1 (fr) 1992-05-06 1993-05-04 Acides monocarboxyliques satures, leur preparation et leurs derives

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AU (1) AU4065993A (fr)
WO (1) WO1993022270A1 (fr)
ZA (1) ZA933123B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000007971A1 (fr) * 1998-08-06 2000-02-17 Exxon Chemical Patents Inc. Acides neocarboxyliques et procede pour leur preparation
US6255262B1 (en) 1998-11-09 2001-07-03 Exxon Chemical Patents Inc. High hydroxyl content glycerol di-esters
GB2385589A (en) * 2000-08-07 2003-08-27 Sofitech Nv Surfactant
DE102012014396A1 (de) 2012-07-13 2014-01-16 Oxea Gmbh Vinylester der Isononansäure ausgehend von 2-Ethylhexanol, Verfahren zu seiner Herstellung sowie seine Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124475A (en) * 1960-10-04 1964-03-10 Metal salt drier compositions
GB1430347A (en) * 1974-02-11 1976-03-31 Mooney Chemicals Metal carboxylate alkoxy alcoholate composition and process
GB1553702A (en) * 1975-05-19 1979-09-26 Inst Elektroswarki Patona Mixtures of poly branched monocarboxylic acids and preparation thereof
EP0010807A1 (fr) * 1978-10-26 1980-05-14 Akzo N.V. Dérivés d'acides monocarboxyliques ramifiés, huiles de graissage pour moteurs, compositions lubrifiantes pour polymères, compositions de cire dans lesquelles sont incorporés ces dérivés et procédé de préparation de ces acides monocarboxyliques ramifiés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124475A (en) * 1960-10-04 1964-03-10 Metal salt drier compositions
GB1430347A (en) * 1974-02-11 1976-03-31 Mooney Chemicals Metal carboxylate alkoxy alcoholate composition and process
GB1553702A (en) * 1975-05-19 1979-09-26 Inst Elektroswarki Patona Mixtures of poly branched monocarboxylic acids and preparation thereof
EP0010807A1 (fr) * 1978-10-26 1980-05-14 Akzo N.V. Dérivés d'acides monocarboxyliques ramifiés, huiles de graissage pour moteurs, compositions lubrifiantes pour polymères, compositions de cire dans lesquelles sont incorporés ces dérivés et procédé de préparation de ces acides monocarboxyliques ramifiés

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000007971A1 (fr) * 1998-08-06 2000-02-17 Exxon Chemical Patents Inc. Acides neocarboxyliques et procede pour leur preparation
US6255262B1 (en) 1998-11-09 2001-07-03 Exxon Chemical Patents Inc. High hydroxyl content glycerol di-esters
GB2385589A (en) * 2000-08-07 2003-08-27 Sofitech Nv Surfactant
US7196041B2 (en) 2000-08-07 2007-03-27 Schlumberger Technology Corporation Surfactant comprising alkali metal salt of 2-methyl oleic acid or 2-ethyl oleic acid
US7576043B2 (en) 2000-08-07 2009-08-18 Schlumberger Technology Corporation Viscoelastic wellbore fluid comprising an anionic surfactant
DE102012014396A1 (de) 2012-07-13 2014-01-16 Oxea Gmbh Vinylester der Isononansäure ausgehend von 2-Ethylhexanol, Verfahren zu seiner Herstellung sowie seine Verwendung
US9334225B2 (en) 2012-07-13 2016-05-10 Oxea Gmbh Vinyl esters of isononanoic acid starting from 2-ethyl hexanol, methods for the production thereof and use thereof

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AU4065993A (en) 1993-11-29
ZA933123B (en) 1993-11-30

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