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WO1997001523A1 - Decomposition of cycloalkyl ethers - Google Patents

Decomposition of cycloalkyl ethers Download PDF

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Publication number
WO1997001523A1
WO1997001523A1 PCT/SE1996/000851 SE9600851W WO9701523A1 WO 1997001523 A1 WO1997001523 A1 WO 1997001523A1 SE 9600851 W SE9600851 W SE 9600851W WO 9701523 A1 WO9701523 A1 WO 9701523A1
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Prior art keywords
process according
ofthe
cyclic
aldehyde
decomposition
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PCT/SE1996/000851
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French (fr)
Inventor
Börje WICKBERG
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Perstorp Ab
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Priority to AU63246/96A priority Critical patent/AU6324696A/en
Publication of WO1997001523A1 publication Critical patent/WO1997001523A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings

Definitions

  • the present invention refers to a process for decomposition of a cyclic alkyl ether, which in its cyclic structure comprises a 1 ,3-dioxa group.
  • Such cyclic diethers are reaction products between at least one alcohol and at least one aldehyde and are substantially cyclic acetals, such as 1 ,3-dioxolanes, 1 ,3-dioxanes and 1 ,3,5-trioxepanes, whereby acetal designates an organic dialkoxy compound (alkyl diether) - R ⁇ mpps Chemie-Lexikon 8. Aufl. 1981 - and whereby cyclic acetal accordingly designates an organic cyclic dialkoxy compound (cyclic alkyl diether).
  • Di, tri and polyalcohols having a neopentyl structure such as neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol are normally synthesised in an alkali catalysed aldolcondensation of formaldehyde and a second aldehyde. Yielded aldolaldehyde is then reduced to corresponding alcohol by means of a so called Cannizzaro reaction with a further amount of formaldehyde in the presence of a strong base. The reaction can alternatively be carried out by means of catalytic hydration. The synthesis as well as a recovery of obtained reaction product yield normally secondary products such as acetals.
  • a neopentyl structure such as neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol are normally synthesised in an alkali catalysed ald
  • the syntheses yield primarily linear acetals, which when exposed to acidic treatment, for instance when passing an ion exchanger, during the recovery are transformed into cyclic acetals, such as 1 ,3-dioxanes.
  • This kind of synthesis can be exemplified by below processes, wherein pentaerythritol and neopentyl glycol are synthesised.
  • Pentaerythritol can for instance be synthesised in an aldolcondensation according to above, wherein 3 moles of formaldehyde and 1 mole of isobutyric aldehyde are reacted to yield trimethylolacetaldehyde, followed by a Cannizzaro reaction with 1 further mole of formaldehyde in the presence of 1 equivalent of sodium hydroxide or potassium hydroxide.
  • Neopentyl glycol can be synthesised accordingly by aldolcondensation of 1 mole of formaldehyde and 1 mole of isobutyric aldehyde yielding hydroxypivaldehyde, which then is reduced by means of 1 further mole of formaldehyde according to above or by catalytic hydration.
  • Cyclic acetals are also yielded during recovery if a synthesised di, tri or polyalcohol under acidic conditions is in contact with an aldehyde. This occurs for instance during an evaporation procedure, wherein water and excess of aldehyde, such as formaldehyde, are evaporated. Formation of acetals occurs when a 1 ,3-diol structure in the di, tri or polyalcohol reacts with for instance formaldehyde to corresponding 1 ,3-dioxane.
  • Cyclic 1 ,3-diethers as disclosed above are also yielded during other polyalcohol syntheses, such as acid catalysed etherification, as disclosed in for instance the U.S. Patent 3,673,226.
  • Cyclic diethers such as acetals can also be obtained by direct reaction between a di, tri or polyalcohol and an aldehyde. These reactions can be exemplified by 1 ,3-dioxolane (glycol formal) which is yielded when a mixture comprising formaldehyde, ethylene glycol and an acid catalyst is heated and by 1 ,3,5-trioxepane, a cyclic glycol formal having 2 oxymethylene groups, which is yielded when a mixture of 1 ,3-dioxolane, formaldehyde and an acid catalyst is heated. Glycerol can similarly yield acetals, such as 4-hydroxymethyl- l ,3- dioxolane and 5-hydroxy- l ,3-dioxane
  • Linear acetals are normally easy to decomposed, for instance by treating a diluted aqueous solution with a strong acid, optionally in the presence of a lower alcohol added to improve the solubility of the acetal.
  • Cyclic acetals comprising a 1 ,3-dioxa group are, however, normally very difficult to decompose. This is especially valid for acetals wherein included di, tri or polyalcohol is 2- or 2,2-substituted.
  • An acetal having a 1 ,3-dioxa group is thermodynamically favoured by a very stable structure.
  • the present invention refers to a process for decomposition of cyclic acetals being difficult to decompose as discussed above.
  • the process comprises above disclosed acidic decomposition and a simultaneously performed catalytic hydrogenation, whereby liberated aldehyde is removed from the equilibrium by means of a reaction yielding corresponding alcohol, such as formaldehyde yielding methanol, according to reaction scheme (B) below, which is a continuation of reaction scheme (A):
  • the invention is suitable for processing of for instance secondary product mixture obtained during a di, tri or polyalcohol synthesis and/or during processing of thereby obtained reaction solutions and mixtures, which secondary product mixture comprises at least one of said cyclic diethers, cyclic acetals, being difficult to decompose and which diether comprises a 1 ,3-dioxa group.
  • the decomposition process according to the invention can of course also be used for decomposition of said diethers obtained or produced by other means.
  • the decomposition increases, in case the di, tri or polyalcohol yielded from the decomposition is the same product as the one used in the original synthesis, the yield of said original synthesis.
  • the liberated di, tri or polyalcohol can also be used as raw material in the original synthesis. In such a case, the decomposition also increases the yield in that the liberated alcohol can be re-circulated.
  • Decomposition of cyclic formals yields methanol.
  • Methanol can after recovery be used in for instance the production of formaldehyde, which is an important raw material in the production of a large number of di, tri and polyalcohols as disclosed above.
  • Decomposition of cyclic acetals of higher aldehydes yields higher alcohols.
  • Such a higher alcohol is, should it contain two or more hydroxyl groups, of the same importance as component in for instance esters, polyesters, ethers, polyethers, polyurethanes, synthetic lubricants and similar monomeric or polymeric products as said liberated di, tri or polyalcohols.
  • a cyclic alkyl ether which in its cyclic structure comprises a 1 ,3 -dioxa group, such as cyclic diethers of the acetal type
  • an aqueous solution or an aqueous suspension comprising at least one cyclic diether is pH adjusted to a pH value of 1-6, preferably 1-4.
  • the solution or suspension is then in the presence of at least one metallic catalyst and during inlet of hydrogen heated to a reaction temperature of 100-200°C, preferably 120- 180°C. whereby the cyclic diether is decomposed and included alcohol and aldehyde are liberated and whereby the aldehyde through catalytic hydrogenation reacts to corresponding alcohol
  • the aqueous solution or aqueous suspension has in preferred embodiments a water content of 25-95, preferably 40-80, per cent by weight and the solution or suspension is pH adjusted to said pH value by an acid having a pKa value of at most 5. Hydrogen is preferably let in continuously during decomposition and hydrogenation, which reactions preferably are performed under a pressure of 10-150, such as 30-80, bar.
  • Various embodiments of the invention employ as catalyst one or more metals and/or metal oxides selected from the group consisting of rhodium, ruthenium, platinum and palladium deposited on an inert support, preferably activated carbon.
  • the amount of catalytically active metal or metal oxide deposited on the support is suitably 0. 1-50, such as 0.5-20, per cent by weight of the total weight of the catalyst.
  • the catalyst can furthermore be employed as a powder or as granules and added in an amount of 0.01-10, preferably 0. 1-1 , per cent by weight, calculated on the water-free substances, defined as 100 minus the water content, of the aqueous solution or aqueous suspension.
  • the decomposition is according to various embodiments carried out either in batches, whereby the catalyst preferably is employed as a powder, or as a continuos process, whereby the catalyst preferably consists of granules.
  • the catalyst is in a batch-by-batch decomposition suitably added in an amount of 0.05-5%, preferably 0. 1-1%, calculated as defined above.
  • Cyclic diethers suitable to decompose by means of the process according to the present invention are for instance dioxetanes, dioxolanes, dioxanes and trioxepanes, all comprising a 1 ,3-dioxa group, whereby one or more carbon atoms can be hydroxy, alkanyl, hyrdroxyalkanyl, alkenyl, hydroxyalkenyl, alkynyl, hydroxyalkynyl, aryl or hydroxyaryl substituted.
  • R j , R 2 , R 3 , R 4 , R 5 and R 6 independently are hydrogen, hydroxyl, alkanyl, alkenyl, alkynyl, aryl, hydroxy substituted alkanyl, hydroxy substituted alkenyl, hydroxy substituted alkynyl or hydroxy substituted aryl.
  • Formula (I) and (II) above include reaction products between an aldehyde and an di, tri or polyalcohol having a 1 ,3-diol structure.
  • Formula (I) and Formula (II) furthermore include reaction products between for instance formaldehyde and neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane or pentaerythritol, such as 4-hydroxymethyl- l ,3-dioxolane, 5-hydroxy- l ,3-dioxane, 5-ethyl-5-hydroxymethyl- 1 ,3 -dioxane, 5, 5-di(hydroxymethyl)- 1 ,3 -dioxane and 5, 5-dimethyl- 1 ,3 -dioxane.
  • a cyclic diether comprising a 1 ,3-dioxa group, which ether is a reaction product between an aldehyde, preferably formaldehyde, and a dimer, trimer or polymer of said di, tri and polyalcohols, such as ditrimethylolpropane, ditrimethylolethane, diglycerol, dipentaerythritol, tripentaerythritol and polypentaerythritol, can advantageously be decomposed using the process according to the present invention.
  • Said cyclic diethers can be a part of or yielded from various secondary product mixtures obtained during the synthesis and/or recovery of a di, tri or polyalcohol, such as neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol and/or a dimer, trimer or polymer thereof.
  • a di, tri or polyalcohol such as neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol and/or a dimer, trimer or polymer thereof.
  • Example 1 Recovery as decomposition and catalytic hydrogenation of cyclic acetals in a secondary product mixture obtained during synthesising of ditrimethylolpropane.
  • Example 2. Decomposition and catalytic hydrogenation of a synthesised cyclic diether (cyclic formal), whereby a high degree of transformation is determined.
  • Yielded trimethylolpropane and its dimer can by means of processes known in the art, such as low pressure distillation, be recovered.

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

Abstract

Process for decomposition of a cyclic alkyl ether, which in its cyclic structure comprises a 1,3-dioxa group. These cyclic diethers of acetal type are reaction products between at least one aldehyde and at least one alcohol. An aqueous solution or aqueous suspension comprising at least one cyclic diether is pH adjusted to a pH value of 1-6. The solution or the suspension is then, in the presence of at least one metallic catalyst and during inlet of hydrogen, heated to a reaction temperature of 100-200 °C. The cyclic alkyl ether is decomposed, whereby alcohol and aldehyde are liberated. The aldehyde reacts further through catalytic hydrogenation yielding corresponding alcohol.

Description

DECOMPOSITION OF CYCLOALKYL ETHERS
The present invention refers to a process for decomposition of a cyclic alkyl ether, which in its cyclic structure comprises a 1 ,3-dioxa group. Such cyclic diethers are reaction products between at least one alcohol and at least one aldehyde and are substantially cyclic acetals, such as 1 ,3-dioxolanes, 1 ,3-dioxanes and 1 ,3,5-trioxepanes, whereby acetal designates an organic dialkoxy compound (alkyl diether) - Rόmpps Chemie-Lexikon 8. Aufl. 1981 - and whereby cyclic acetal accordingly designates an organic cyclic dialkoxy compound (cyclic alkyl diether).
Di, tri and polyalcohols having a neopentyl structure, such as neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol are normally synthesised in an alkali catalysed aldolcondensation of formaldehyde and a second aldehyde. Yielded aldolaldehyde is then reduced to corresponding alcohol by means of a so called Cannizzaro reaction with a further amount of formaldehyde in the presence of a strong base. The reaction can alternatively be carried out by means of catalytic hydration. The synthesis as well as a recovery of obtained reaction product yield normally secondary products such as acetals. The syntheses yield primarily linear acetals, which when exposed to acidic treatment, for instance when passing an ion exchanger, during the recovery are transformed into cyclic acetals, such as 1 ,3-dioxanes. This kind of synthesis can be exemplified by below processes, wherein pentaerythritol and neopentyl glycol are synthesised.
Pentaerythritol can for instance be synthesised in an aldolcondensation according to above, wherein 3 moles of formaldehyde and 1 mole of isobutyric aldehyde are reacted to yield trimethylolacetaldehyde, followed by a Cannizzaro reaction with 1 further mole of formaldehyde in the presence of 1 equivalent of sodium hydroxide or potassium hydroxide. The synthesis yields as a secondary product for instance bis-pentaerythritolformal (formal = formaldehyde acetal), which during recovery under acidic conditions is transformed into 5.5-dimethanol- l ,3-dioxane and pentaerythritol.
Neopentyl glycol can be synthesised accordingly by aldolcondensation of 1 mole of formaldehyde and 1 mole of isobutyric aldehyde yielding hydroxypivaldehyde, which then is reduced by means of 1 further mole of formaldehyde according to above or by catalytic hydration. Cyclic acetals are also yielded during recovery if a synthesised di, tri or polyalcohol under acidic conditions is in contact with an aldehyde. This occurs for instance during an evaporation procedure, wherein water and excess of aldehyde, such as formaldehyde, are evaporated. Formation of acetals occurs when a 1 ,3-diol structure in the di, tri or polyalcohol reacts with for instance formaldehyde to corresponding 1 ,3-dioxane.
Cyclic 1 ,3-diethers as disclosed above are also yielded during other polyalcohol syntheses, such as acid catalysed etherification, as disclosed in for instance the U.S. Patent 3,673,226.
Cyclic diethers such as acetals can also be obtained by direct reaction between a di, tri or polyalcohol and an aldehyde. These reactions can be exemplified by 1 ,3-dioxolane (glycol formal) which is yielded when a mixture comprising formaldehyde, ethylene glycol and an acid catalyst is heated and by 1 ,3,5-trioxepane, a cyclic glycol formal having 2 oxymethylene groups, which is yielded when a mixture of 1 ,3-dioxolane, formaldehyde and an acid catalyst is heated. Glycerol can similarly yield acetals, such as 4-hydroxymethyl- l ,3- dioxolane and 5-hydroxy- l ,3-dioxane
Linear acetals are normally easy to decomposed, for instance by treating a diluted aqueous solution with a strong acid, optionally in the presence of a lower alcohol added to improve the solubility of the acetal. Cyclic acetals comprising a 1 ,3-dioxa group are, however, normally very difficult to decompose. This is especially valid for acetals wherein included di, tri or polyalcohol is 2- or 2,2-substituted. An acetal having a 1 ,3-dioxa group is thermodynamically favoured by a very stable structure.
Acetals and alcohols included therein are thoroughly discussed in for instance Houben-Weyl: Methoden der Organischen Chemie - 4 Aufl. , Alkohole, Teil 1 , "Herstellung von Alkoholen aus Acetalen" page 295-309. Above discussed cyclic acetals, which are very difficult to decompose, are discussed on page 299.
Decomposition of cyclic acetals according to above results in an equilibrium, wherein decomposition of the acetal yielding alcohol and aldehyde and wherein liberated aldehyde and alcohol under acidic conditions react to cyclic acetal. The equilibrium is strongly . displaced towards the acetal formation according to reaction scheme (A) below:
Figure imgf000005_0001
wherein Rj and R2 can be H, OH, alkanyl, alkenyl, alkynyl, aryl, etc. and wherein R3 can be H, alkanyl, alkenyl, alkynyl, aryl, etc.
The present invention refers to a process for decomposition of cyclic acetals being difficult to decompose as discussed above. The process comprises above disclosed acidic decomposition and a simultaneously performed catalytic hydrogenation, whereby liberated aldehyde is removed from the equilibrium by means of a reaction yielding corresponding alcohol, such as formaldehyde yielding methanol, according to reaction scheme (B) below, which is a continuation of reaction scheme (A):
Figure imgf000005_0002
It will thus be possible to liberate the di, tri or polyalcohol, which then can be recovered from the reaction mixture by conventional processing procedures.
The invention is suitable for processing of for instance secondary product mixture obtained during a di, tri or polyalcohol synthesis and/or during processing of thereby obtained reaction solutions and mixtures, which secondary product mixture comprises at least one of said cyclic diethers, cyclic acetals, being difficult to decompose and which diether comprises a 1 ,3-dioxa group. The decomposition process according to the invention can of course also be used for decomposition of said diethers obtained or produced by other means.
The decomposition increases, in case the di, tri or polyalcohol yielded from the decomposition is the same product as the one used in the original synthesis, the yield of said original synthesis. The liberated di, tri or polyalcohol can also be used as raw material in the original synthesis. In such a case, the decomposition also increases the yield in that the liberated alcohol can be re-circulated.
Decomposition of cyclic formals (acetals wherein the aldehyde is formaldehyde) yields methanol. Methanol can after recovery be used in for instance the production of formaldehyde, which is an important raw material in the production of a large number of di, tri and polyalcohols as disclosed above. Decomposition of cyclic acetals of higher aldehydes yields higher alcohols. Such a higher alcohol is, should it contain two or more hydroxyl groups, of the same importance as component in for instance esters, polyesters, ethers, polyethers, polyurethanes, synthetic lubricants and similar monomeric or polymeric products as said liberated di, tri or polyalcohols.
The process, according to the present invention, for decomposition of a cyclic alkyl ether, which in its cyclic structure comprises a 1 ,3 -dioxa group, such as cyclic diethers of the acetal type, is characterised in that an aqueous solution or an aqueous suspension comprising at least one cyclic diether, as disclosed above, is pH adjusted to a pH value of 1-6, preferably 1-4. The solution or suspension is then in the presence of at least one metallic catalyst and during inlet of hydrogen heated to a reaction temperature of 100-200°C, preferably 120- 180°C. whereby the cyclic diether is decomposed and included alcohol and aldehyde are liberated and whereby the aldehyde through catalytic hydrogenation reacts to corresponding alcohol
The aqueous solution or aqueous suspension has in preferred embodiments a water content of 25-95, preferably 40-80, per cent by weight and the solution or suspension is pH adjusted to said pH value by an acid having a pKa value of at most 5. Hydrogen is preferably let in continuously during decomposition and hydrogenation, which reactions preferably are performed under a pressure of 10-150, such as 30-80, bar.
Various embodiments of the invention employ as catalyst one or more metals and/or metal oxides selected from the group consisting of rhodium, ruthenium, platinum and palladium deposited on an inert support, preferably activated carbon. The amount of catalytically active metal or metal oxide deposited on the support is suitably 0. 1-50, such as 0.5-20, per cent by weight of the total weight of the catalyst. The catalyst can furthermore be employed as a powder or as granules and added in an amount of 0.01-10, preferably 0. 1-1 , per cent by weight, calculated on the water-free substances, defined as 100 minus the water content, of the aqueous solution or aqueous suspension.
The decomposition is according to various embodiments carried out either in batches, whereby the catalyst preferably is employed as a powder, or as a continuos process, whereby the catalyst preferably consists of granules. The catalyst is in a batch-by-batch decomposition suitably added in an amount of 0.05-5%, preferably 0. 1-1%, calculated as defined above. Cyclic diethers suitable to decompose by means of the process according to the present invention are for instance dioxetanes, dioxolanes, dioxanes and trioxepanes, all comprising a 1 ,3-dioxa group, whereby one or more carbon atoms can be hydroxy, alkanyl, hyrdroxyalkanyl, alkenyl, hydroxyalkenyl, alkynyl, hydroxyalkynyl, aryl or hydroxyaryl substituted. Especially suitable are 1 ,3-dioxolanes and 1 ,3-dioxanes of general Formula (I) and (II)
Figure imgf000007_0001
wherein Rj, R2, R3, R4, R5 and R6 independently are hydrogen, hydroxyl, alkanyl, alkenyl, alkynyl, aryl, hydroxy substituted alkanyl, hydroxy substituted alkenyl, hydroxy substituted alkynyl or hydroxy substituted aryl.
Formula (I) and (II) above include reaction products between an aldehyde and an di, tri or polyalcohol having a 1 ,3-diol structure. Formula (I) and Formula (II) furthermore include reaction products between for instance formaldehyde and neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane or pentaerythritol, such as 4-hydroxymethyl- l ,3-dioxolane, 5-hydroxy- l ,3-dioxane, 5-ethyl-5-hydroxymethyl- 1 ,3 -dioxane, 5, 5-di(hydroxymethyl)- 1 ,3 -dioxane and 5, 5-dimethyl- 1 ,3 -dioxane.
A cyclic diether comprising a 1 ,3-dioxa group, which ether is a reaction product between an aldehyde, preferably formaldehyde, and a dimer, trimer or polymer of said di, tri and polyalcohols, such as ditrimethylolpropane, ditrimethylolethane, diglycerol, dipentaerythritol, tripentaerythritol and polypentaerythritol, can advantageously be decomposed using the process according to the present invention.
Said cyclic diethers can be a part of or yielded from various secondary product mixtures obtained during the synthesis and/or recovery of a di, tri or polyalcohol, such as neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol and/or a dimer, trimer or polymer thereof. The invention will be further explained by embodiment Examples 1 and 2, wherein cyclic acetals (cyclic diethers) are decomposed using the process according to the present invention.
Example 1 : Recovery as decomposition and catalytic hydrogenation of cyclic acetals in a secondary product mixture obtained during synthesising of ditrimethylolpropane. Example 2. Decomposition and catalytic hydrogenation of a synthesised cyclic diether (cyclic formal), whereby a high degree of transformation is determined.
EXAMPLE 1
A not processed secondary product mixture from a ditrimethylolpropane synthesis was evaporated at 1 mbar and 250°C and a remainder having below composition was obtained:
Cyclic acetals 28%
Ditrimethylolpropane 10%
Tritrimethylolpropane 7%
Unidentified organic compounds 48%
Sodium salt 7%
4.0 g of above composition, 10.0 g of a 0.07% aqueous solution of H2SO4 and 20.5 g of a powder catalyst consisting of 5% metallic ruthenium on activated carbon were charged in an autoclave provided with a magnetic stirrer. The autoclave was sealed and hydrogen let in to maintain a pressure of 67 bar. The temperature was adjusted to 130°C. Acidic acetal decomposition and catalytic hydrogenation were allowed to continue for 3.5 hours at 130°C and at a pressure of 67 bar. The autoclave was then opened and obtained reaction mixture analysed.
Below composition was obtained:
Trimethylolpropane 24%
Ditrimethylolpropane 25%
Tritrimethylolpropane 7%
Unidentified organic compounds 37%o
Sodium salt 7% The experiment shows that cyclic acetals are decomposed and that trimethylolpropane and its dimer are yielded. Yielded dimer can be derived from decomposition of high molecular acetals included in the figure giving the percentage cyclic acetals and probably in the figure giving the percentage unidentified organic compounds (this figure has decreased by > 10%).
Yielded trimethylolpropane and its dimer can by means of processes known in the art, such as low pressure distillation, be recovered.
EXAMPLE 2
10.0 g of 5-ethyl-5-hydroxymethyl- l ,3-dioxane (cyclic formal of trimethylol¬ propane), 100.0 ml of a 0. 1%> aqueous solution of H-,SO4 and 10. 1 g of a powder catalyst consisting of 5% metallic ruthenium on activated carbon were charged in an autoclave provided with a magnetic stirrer. The autoclave was sealed and hydrogen let in to maintain a pressure of 37 bar. The temperature was adjusted to 155°C. Acidic acetal decomposition and catalytic hydrogenation were allowed to continue for 3 hours at 155°C and at a pressure of 37 bar. The autoclave was then opened and obtained reaction mixture analysed.
The analysis evidenced a 98% transformation into trimethylolpropane and methanol of the start material.

Claims

1. Process for decomposition of a cyclic alkyl ether which in the cyclic structure comprises a 1,3-dioxa group, which cyclic diether is a reaction product between at least one alcohol and at least one aldehyde ch a racterised i n, that an aqueous solution or an aqueous suspension comprising at least one cyclic diether is pH adjusted to a pH value of 1 to 6, preferably 1 to 4, after which the aqueous solution or the aqueous suspension in presence of at least one metallic catalyst and during inlet of hydrogen is heated to a reaction temperature of 100°C to 200°C, preferably 120°C to 180°C, whereby the diether is decomposed and alcohol and aldehyde included therein are liberated and whereby the aldehyde through catalytic hydrogenation reacts to corresponding alcohol.
2. Process according to Claim 1 cha racterised i n, that the aqueous solution or aqueous suspension has a water content of 25 to 95, preferably 40 to 80, per cent by weight.
3. Process according to Claim 1 or 2 characterised i n, that the aqueous solution or aqueous suspension is pH adjusted by addition of an acid having a pKa value of at most 5.
4. Process according to any ofthe Claims 1-3 ch aracterised i n, that hydrogen is let in continuously during decomposition and hydrogenation.
5. Process according to any ofthe Claims 1-4 ch a ra cterised i n, that decomposition and hydrogenation are carried out at a pressure of 10 to 150, preferably 30 to 80, bar.
6. Process according to any ofthe Claims 1-5 ch a racterised i n, that the catalyst comprises rhodium, ruthenium, platinum and/or palladium and/or an oxide thereof.
7. Process according to any ofthe Claims 1-6 cha racterised i n, that the catalyst is a powder or a granulate.
8. Process according to any ofthe Claims 1-7 chara cteris ed i n, that the catalyst consists of a catalytically active metal or metal oxide deposited on a catalytically inert support.
9. Process according to Claim 8 cha ra c te rised i n, that the catalytically inert support is activated carbon.
10. Process according to Claim 8 or 9 ch ara c terised i n, that the catalytically active metal or metal oxide constitutes 0.1-50, preferably 0.5-20, per cent by weight ofthe total weight ofthe catalyst.
11. Process according to any ofthe Claims 1-10 cha ra c te rised in, that the catalyst is added in an amount of 0.01-10, preferably 0.05-5 and most preferably 0.1-1, per cent by weight, calculated on water-free substances in the aqueous solution or aqueous suspension.
12. Process according to any ofthe Claims 1-11 characterised in, that the cyclic diether is a dioxetane, dioxolane, dioxane or trioxepane, whereby one or more carbon atoms optionally is hydroxy, alkanyl, hydroxyalkanyl, alkenyl, hydroxyalkenyl, alkynyl, hydroxyalkynyl, aryl and/or hydroxyaryl substituted.
13. Process according to any ofthe Claims 1-12 cha ra c t e rised i n, that the cyclic diether is a reaction product between an aldehyde and an di, tri or polyalcohol having a 1,3-diol structure.
14. Process according to any ofthe Claims 1-13 characterised in, that the cyclic diether is a reaction product between formaldehyde and neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol or a dimer, trimer or polymer thereof.
15. Process according to any ofthe Claims 1-14 c h a ra cterised i n, that the cyclic diether is of Formula (I) or Formula (II)
Figure imgf000012_0001
wherein Rj, R2, R3, R4, R5 and R6 independently is hydroxyl, alkanyl, alkenyl, alkynyl, aryl, hydroxy substituted alkanyl, hydroxy substituted alkenyl, hydroxy substituted alkynyl or hydroxy substituted aryl and R7 is hydrogen, alkanyl, alkenyl, alkynyl or aryl.
16. Process according to any ofthe Claims 1-15 c h a ra cterised in, that the cyclic diether is 4-hydroxymethyl-l,3-dioxolane, 5-hydroxy-l,3-dioxane, 5-ethyl-5-hydroxymethyl- 1 ,3 -dioxane, 5,5-di(hydroxymethyl)- 1 ,3-dioxane or 5, 5-dimethyl- 1,3 -dioxane.
17. Process according to any ofthe Claims 1-16 c h a racterised i n, that the cyclic diether is a part of or yielded in at least one secondary product mixture obtained during synthesising and/or recovery of neopentyl glycol. trimethylolpropane, trimethylolethane, pentaerythritol or a dimer, trimer or polymer thereof.
PCT/SE1996/000851 1995-06-29 1996-06-27 Decomposition of cycloalkyl ethers WO1997001523A1 (en)

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WO2010006688A2 (en) 2008-07-15 2010-01-21 Oxea Deutschland Gmbh Process for obtaining neopentyl glycol by cracking high boilers occurring in the production process
WO2010075616A1 (en) * 2009-01-05 2010-07-08 Serviço Nacional De Aprendizagem Industrial-Senai/Dr-Ba Process for purifying light-coloured glycerol from biodiesel transesterification
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US6232512B1 (en) 1998-09-04 2001-05-15 Degussa-Huls Ag Method for reducing the content of acetals or ketals in alcohol-containing reaction mixtures
US6265623B1 (en) 1998-09-04 2001-07-24 Perstorp Specialty Chemicals Ab Process for the reductive cleavage of linear and cyclic acetals especially formals
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