Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1996-07-17
1998-03-03
Geist, Gary
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568678, 568680, C07C 3122
Patent
active
057236968
DESCRIPTION:
BRIEF SUMMARY
This is the U.S. National Stage Application of PCT/EP95/00248 filed Jan. 24, 1995 now WO95/21210 published Aug. 10, 1995.
The present invention relates to a process of preparing polymers of glycerol in which glycerol, or its derivatives glycidol, glycerol carbonate or isopropylidene glycerol (or 2,2-dimethyl-1,3-dioxolane-4-methanol) are polymerized in the presence of an effective amount of a catalyst.
Such a process is known from British Patent Specification GB-A-1,205,163 (Eastman Kodak Comp.) in which glycerol is condensed at 200.degree. C. to 280.degree. C. in the presence of an alkaline catalyst, such as the alkali metal or alkaline earth metal oxides, hydroxides, bicarbonates, carbonates and salts of fatty acids.
In Japanese Patent Application JP-A-61/238,749 (Nippon Oils and Fats Co. Ltd.) a process has been described of manufacturing polyglycerol with only small amounts of cyclic polymerization products. In this process glycerol is condensed at 240.degree. C.-260.degree. C. after addition of 0.1-5% by weight of alkali catalyst and the same amount of an aluminium oxide comprising adsorbent. Examples of the adsorbent of the aluminium oxide type are activated alumina, zeolite, synthetic adsorbents and activated clays. The zeolite should contain 5% by weight or more of aluminium oxide, but no more indication has been given about the type of the zeolite than that it was manufactured by Mizusawa Kagaku.
In our pending European Patent Application EP 93200356.9 (Unilever) we have described a process of polymerizing glycerol in the presence of an acid zeolite having an average pore size of at least 0.6 nm, in which process preponderantly cyclic polymers are formed. In comparative examples, glycerol is heated to polymerization temperature in the presence of zeolite Y in the sodium form, sodium mordenite or an acidic beta zeolite in the presence of sodium hydroxide, but in all these cases no polymer was formed.
In further investigations as to the role of catalysts in the polymerization of glycerol or its derivatives glycidol, glycerol carbonate and isopropylidene glycerol, it has been found that polymers of glycerol with an appreciable percentage of linear oligomers are obtained if glycerol or the said derivatives are polymerized in the presence of an effective amount of a catalyst, selected from the group consisting of: cesium fluoride impregnated on alumina, potassium fluoride impregnated on alumina, rubidium fluoride impregnated on alumina, zirconium oxide, cesium ions exchanged zeolite and rubidium ions exchanged zeolite. Preferably the alumina on which the RbF, CsF and/or KF has been impregnated is gamma-alumina. The zirconium oxide is preferably zirconium dioxide. The zeolite preferably is an Y-type zeolite or a zeolite beta.
Zeolites are crystalline alumina silicates of alkali metals or alkaline earth metals, represented by the general formula contained in the zeolite. Particularly the so-called Y-zeolites and zeolites beta, which had been subjected to a cation exchange with cesium or rubidium ions appeared to be very effective catalysts in the polymerization of glycerol or its said derivatives. This is surprising, since the sodium form of the zeolites appeared to be inactive in the polymerization of glycerol. The preparation of rubidium (RbY) or cesium ion-exchanged zeolite Y (CsY) is effected in a manner known per se, such as for example described in Bull. Chem. Soc. Japan 59 (6), 1761-1765 (1986).
Also zeolites which have been subjected to cation exchange and impregnation by a mixture of rubidium and/or cesium ions and potassium ions may be used.
The alumina impregnated with rubidium fluoride and/or cesium fluoride and/or potassium fluoride is prepared in a manner known per se, for example as described in Bull. Soc. Chem. Japan 55 (8), 2504-2507 (1982). Also mixtures of rubidium or cesium and potassium fluoride may be used and the amount of fluoride may vary from 0.1 to 1.0 mole of CsF or KF, or more, impregnated on 100 g of alumina. The alumina preferably is gamma-alumina. The zirconium oxide may b
Eshuis Johan Jan W.
Laan Johannes Arie M.
Minihan Alan Reginald
Roberts Glyn
Geist Gary
Padmanabhan Sreeni
Unichema Chemie B.V.
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