GB2187454A - Process for the production of either an alkylene carbonate, a glycol ether ester or a glycol ether - Google Patents

Process for the production of either an alkylene carbonate, a glycol ether ester or a glycol ether Download PDF

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Publication number
GB2187454A
GB2187454A GB08705119A GB8705119A GB2187454A GB 2187454 A GB2187454 A GB 2187454A GB 08705119 A GB08705119 A GB 08705119A GB 8705119 A GB8705119 A GB 8705119A GB 2187454 A GB2187454 A GB 2187454A
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Prior art keywords
catalyst
glycol ether
process according
production
ester
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GB08705119A
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GB8705119D0 (en
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John Edward Hamlin
Malcolm John Lawrenson
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BP Chemicals Ltd
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BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

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

Abstract

A process for the production of (i) an alkylene carbonate, or (ii) a glycol ether ester, or (iii) a glycol ether by reacting an epoxide with either (i) carbon dioxide, or (ii) an ester of a carboxylic acid or (iii) an alcohol under appropriate reaction conditions in the presence of a catalyst characterised in that the catalyst is [bis(trihydrocarbylphosphine)iminium]MO4 wherein M is either molybdenum or tungsten.

Description

SPECIFICATION Process for the production of either an alkylene carbonate, a glycol ether ester or a glycol ether The present invention relates in general to the catalysed reaction of an epoxide with either (i) carbon dioxide, (ii) an ester of a carboxylic acid, or (iii) an alcohol.
The catalysed reaction of an epoxide with carbon dioxide to produce an alkylene carbonate is well known.
Thus, for example Japanese Patent No.7322702 (Chem. Abs. 1973, Vol.79 at page 284) describes the use of a tertiary phosphine catalyst; UK Patent No. 1,485,925 describes the use of a mixture of a protic substancesuch as water or an alcohol and a nitrogenous base as catalyst and our copending European application publication No.0119840 (BP Case No.5518) describes the use of a trivalent phosphorus-containing compound as catalyst in the presence of an alcohol.
The catalysed reaction of an epoxide with an ester of a carboxylic acid to produce a glycol ether ester is also a well known reaction. Thus, for example, German Offenlegenschrift 2,951,080 describes the use of a zirconium halide catalyst and a cocatalystfrom the group consisting of benzotriazole, N-alkylamides, N-(C1.4-alkyl)pyrrolidones, or primary, secondary ortertiary amines; Japanese Kokai Tokkyo Koho 81 36,431 discloses the use of a calcined hydrotalcite catalyst; our copending European application publication No.
0140545 (BP Case No. 5654) describes the use of an amidine as catalyst and our copending European application publication number 176238 (BP Case No.5865) discloses the use of an insoluble solid acid, for example a phosphoric acid resin, as catalyst.
The catalysed reaction of an epoxide with an alcohol to produce a glycol ether is well known in the art.
Thus, for example, our copending European application publication No. 189247 (BP Case No.5909) describes the use of an anion exchange resin as catalyst.
It is also known from the abstract of a paper entitled "Selective Ethylene Oxide Hydrolysis Catalysed by Oxo-Molybdenum Species" by John R. Briggs for the Climax International Conference on the Chemistryand Uses of Molybdenum, University of Newcastle Upon Tyne, 1st - 5th July, 1985, that ethylene oxide can be hydrolysed selectively to mono-ethylene glycol using as catalyst (PPN)2MO4wherein PPN designates bis(triphenylphosphine)iminium and M is either molybdenum ortungsten.
We have now found that the aforesaid catalysts active forthe selective hydrolysis of ethylene oxide are also active catalysts for the reaction of an epoxide with either (i) carbon dioxide, (ii) an ester of a carboxylic acid, or (iii) an alcohol to produce respectively either (i) an alkylene carbonate, or (ii) a glycol ether ester, or (iii) a glycol ether.
Accordingly, the present invention provides a process for the production of (i) an alkylene carbonate, or (ii) a glycol ether ester, or (iii) a glycol ether by reacting an epoxide with either (i) carbon dioxide, or (ii) an ester of a carboxylic acid or (iii) an alcohol under appropriate reaction conditions in the presence of a catalyst characterisedin thatthe catalyst is [bis(trihydrocarbyl phosphine)im in ium]2MO4 wherein M is either molybdenum ortungsten.
As regards the reaction of an epoxide with carbon dioxide to produce an alkylene carbonate, the reactants and the reaction conditions described in the aforesaid EP-A-01 19840, which is incorporated herein by reference, may be employed.
As regards the reaction of an epoxide with an ester of a carboxylic acid to produce a glycol ether ester, the reactants and the reaction conditions described in the aforesaid EP-A-01 40545, which is incorporated herein by reference, may be employed.
As regards the reaction of an epoxide with an alcohol to produce a glycol ether, the reactants and the reaction conditions disclosed in the aforesaid copending EP-A-1 89247, which is incorporated herein by reference, may be employed, except insofar as the process of the present invention is a homogeneous liquid phase reaction whereas the process ofthe prior application involves the use of an insoluble catalyst.
The catalyst is a [bis(trihydrocarbylphosphine)iminium]2MO4 compound wherein M is either molybdenum ortungsten. The hydrocarbyl group may suitably be either alkyl or aryl or a substituted derivative thereof.
Preferably the hydrocarbyl group is phenyl. Preferabiy M is molybdenum. The catalyst may suitably be prepared by reacting an alkali metal molybdate ortungsten, for example sodium molybdate, with a trihydrocarbylphosphine iminium halide, for example triphenylphosphine iminium chloride in aqueous media, thereby to precipitate the [bis(trihydrocarbylphosphine)iminium]2MO4 compound, and thereafter recovering the precipitate from the aqueous media. Thereafter, the precipitate may be washed, suitablywith water, and dried.
It is preferred to add a promoter. Suitable promoters include compounds having theformula:
wherein in the formula (I) Xis either phosphorus, arsenic or antimony and R1, R2 and R3, which may bethe same or different, are hydrogen or substituted or unsubstituted Ci to C10 alkyl, aryl, alkaryl or alkyl groups.
Furthermore, at least one of the groups R1, R2 or R3 may contain a tertiary X atom. PreferablyX is phosphorus.
Preferably R1, R2 and R3 are either lower alkyl or phenyl groups. Triphenylphosphine is particularly preferred asthe promoter.
Although a solvent may be employed, it is generally preferred to operate in the absence of a solvent.
The invention will now be further illustrated by reference to the following Examples.
The Reaction of Propylene Oxide with Methanol or Ethanol to Produce a GlycolEther Example 1 Propylene oxide (0.5 g; 8.6 mmol) and methanol (0.3 g; 9.4 mmol) were charged into a 1.6 ml micrnrnactor together with (PPN)2MoO4 (0.05 g; 0.04 mmol). The microreactorwas sealed and plunged into an oil bath maintained at 155 -160"C. After 1 hour, the microreactorwas removed and cooled to room temperature. The contents ofthe microreactorwere then removed and analysed by GC.
Example2 Example 1 was repeated except that ethanol was used instead of methanol.
Example 3 Example 1 was repeated exceptthatthe reaction time was increased to 2 hours.
Example 4 Example 2 was repeated exceptthatthe reaction time was increased to 2 hours.
Example 5 Example 2 was repeated excepttriphenylphosphine (0.1 g; 0.4 mmol) was added as catalyst promoter.
Example 6 Example 2 was repeated.
Example 7 Example was repeated exceptthatthe ethanol to propylene oxide molar ratio was increased from 1:1 to 9:1.
Example 8 Example 2 was repeated exceptthatthe ethanol to propylene oxide molar ratio was increased from 1:1 to 9:1.
The results of Examples 1 to 8 are given in Table 1.
Ethoxypropanol is an important solvent. The commerical process for producing ethoxypropanol produces the two isomers 1 -ethoxy-2-propanol (1 EP2) and 2-ethoxy-1 -propanol (2EP1) in the ratio 90:10. Thus, the 95:5 ratio of 1 EP2:2EP1 observed with the (PPN)2MoO4 catalyst represents an important improvement.
TABLE 1 Thereaction of propylene oxide with methanolorethanol Example Time Alcohol Catalyst Alcohol:PO Conversion Product Selectivity(%) (b) ratio ofPO (b.1) (%) 1MP2 2MP1 1EP2 2EP1 high boilers 1 1 MeOH (PPN)2MoO4 1:1 99+ 72.0 6.0 - - 22.0 2 1 MtOH (PPN)2MoO4 1:1 99+ 0.6 - 64.0 3.3 32.1 3 2 MeOH (PPN)2MoO4 1:1 99+ 73.3 6.0 - - 20.7 4 2 MtOH (PPN)2MoO4 1:1 99+ 0.1 - 67.8 4.9 27.2 5 1 MtOH (PPN)2MoO4;PPh3 1:1 99+ - - 66.3 3.9 29.8 6 1 MtOH (PPN)2MoO4 1:1 99+ - - 75.2 4.2 20.6 7 1 MtOH (PPN)2MoO4;PPh3 9:1 99+ - - 62.6 6.5 30.9 8 1 MtOH (PPN)2MoO4 9:1 99+ - - 70.3 5.5 24.2 In Table 1, 1MP2 designates 1-methoxy-2-propanol 2MP1 designates 2-methoxy-1-propanol 1EP2 designates 1-ethoxy-2-propanol 2EP1 designates 2-ethoxy-1-propanol The Reaction of Propylene Oxide with MethylAcetate to Produce Methoxypropylacetate Example9 Methyl acetate (0.49; 5.4 mmol) and propylene oxide (0.49; 5 mmol) were charged into a 1.6 ml microreactortogetherwith (PPN)2MoO4(0.05g; 0.04 mmol). The microreactorwas sealed and plunged into an oil bath maintained at 187"C. After 1 hour the microreactorwas removed from the oil bath and cooled to room temperature. The contents were then removed and analysed by GC.
Example 10 Example 9 was repeated exceptthattriphenylphosphine (0.1 g; 0.4 mmol) was added to the reaction mixture in the microreactor.
Example 11 Example 9 was repeated exceptthat dichloromethane (0.4 ml) was added as solvent.
Example 12 Example 9 was repeated except that acetone (0.4 ml) was added as solvent.
The results of Examples 9 to 12 are given in Table 2.
TABLE 2 Reaction ofPropylene Oxide rPO) with MethylAcetate Example Catalyst Conver- Product Selectivities (%) sion of PO MPA MP DMD MPO high others for boilers 9 (PPN)2MoO4 96 21.4 10.3 0.5 0.5 66.5 0.8 10 (PPN)2MoO4; PPh3 99 29.4 5.9 0.2 0.5 62.4 1.6 11 (PPN)2MoO4; CH2C12 97 7.6 4.7 3.1 1.7 81.8 1.1 12 (PPN)2MoO4; acetone 95 8.5 13.8 1.1 17.7 58.9 IntheaboveTable2: MPA = methoxypropylacetate MP = methoxypropanol DMD = 2,5-dimethyl-1,4-dioxane MPO = methylpentenone In the aforesaid Examples 9 to 12 at least 25% of the reaction product was unreacted methyl acetate.
The Reaction ofPropylene Oxide with Carbon Dioxide to Produce Propylene Carbonate Example 13 Propylene oxide (60.09; 1.03 mmol)was charged into a 300 ml reactortogetherwith (PPN)2MoO4(0.49g; 0.40 mmol). The reactor contents were saturated with carbon dioxide for 1.5 hours and the reactorwassealed (initial pressure 20 bar). The temperature was raised to 130 C and maintained atthis temperature for 6 hours (maximum pressure 50 bar). The reactorwas cooled, vented, and the contents analysed by GC. Conversion of propylene oxide was 45%. Selectivity to propylene carbonate was 97.4%.

Claims (11)

1. A process forthe production of (i) an alkylene carbonate, or (ii) a glycol ether ester, or (iii) a glycol ether by reacting an epoxide with either (i) carbon dioxide, or (ii) an ester of a carboxylic acid or (iii) an alcohol under appropriate reaction conditions in the presence of a catalyst characterisedin that the catalyst is [bis(trihydrocarbylphosphine)iminium]MO4wherein M is either molybdenum ortungsten.
2. A process according to claim 1 wherein in the catalyst M is molybdenum.
3. - A process according to claim 1 wherein in the catalyst M is tungsten.
4. A process according to any one of the preceding claims wherein in the catalyst the hydrocarbyl group is phenyl.
5. A process according to claim 1 wherein the catalyst is [bis(triphenylphosphine)iminium]MoO4.
6. A process according to any one of the preceding claims wherein there is added a promoter which is a compound oftheformula:
wherein intheformula (I) Xis either phosphorus, arsenicorantimony and R1, R2and R3,which may bethe same or different, are hydrogen or substituted or unsubstituted C1 to C10 alkyl, aryl, alkaryl or alkyl groups.
7. A process according to claim 6 wherein X in the formula (I) is phosphorus.
8. A process according to claim 6 wherein the promoter istriphenylphosphine.
9. A process for the production of a glycol ether substantially as hereinbefore described with reference to Examples 1 to 8.
10. A process for the production of a glycol ether ester substantially as herein before described with reference to Examples 9 to 12.
11. A process for the production of an alkylene carbonate substantially as hereinbefore described with reference to Example 13.
GB08705119A 1986-03-08 1987-03-05 Process for the production of either an alkylene carbonate, a glycol ether ester or a glycol ether Withdrawn GB2187454A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950649A1 (en) * 1998-04-16 1999-10-20 Mitsui Chemicals, Inc. A process for preparing oxyalkylene derivatives in the presence of phosphine oxides
US6255537B1 (en) * 1998-04-16 2001-07-03 Mitsui Chemicals, Inc. Process for preparing poly(alkylene oxide)
CN102464521A (en) * 2010-11-04 2012-05-23 中国科学院大连化学物理研究所 Method for synthesizing cyclic carbonate ester in micro reactor system
CN103724315A (en) * 2012-10-12 2014-04-16 中国科学院大连化学物理研究所 Method used for synthesizing cyclic carbonate in enhanced microreactor system

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950649A1 (en) * 1998-04-16 1999-10-20 Mitsui Chemicals, Inc. A process for preparing oxyalkylene derivatives in the presence of phosphine oxides
US6130346A (en) * 1998-04-16 2000-10-10 Mitsui Chemicals, Inc. Process for preparing an organic compound from an oxirane-containing compound in the presence of a tris(triaminophosphoranylideneamino)phosphine oxide
US6255537B1 (en) * 1998-04-16 2001-07-03 Mitsui Chemicals, Inc. Process for preparing poly(alkylene oxide)
CN102464521A (en) * 2010-11-04 2012-05-23 中国科学院大连化学物理研究所 Method for synthesizing cyclic carbonate ester in micro reactor system
CN102464521B (en) * 2010-11-04 2015-03-04 中国科学院大连化学物理研究所 Method for synthesizing cyclic carbonate ester in micro reactor system
CN103724315A (en) * 2012-10-12 2014-04-16 中国科学院大连化学物理研究所 Method used for synthesizing cyclic carbonate in enhanced microreactor system

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GB8605754D0 (en) 1986-04-16

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