+

WO1992000947A1 - Esterification amelioree de polyols d'oxyhydrocarbures ainsi que de leurs ethers, et produits obtenus - Google Patents

Esterification amelioree de polyols d'oxyhydrocarbures ainsi que de leurs ethers, et produits obtenus Download PDF

Info

Publication number
WO1992000947A1
WO1992000947A1 PCT/US1991/004877 US9104877W WO9200947A1 WO 1992000947 A1 WO1992000947 A1 WO 1992000947A1 US 9104877 W US9104877 W US 9104877W WO 9200947 A1 WO9200947 A1 WO 9200947A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
sorbitan
amount
esters
reaction
Prior art date
Application number
PCT/US1991/004877
Other languages
English (en)
Inventor
Norman Milstein
Original Assignee
Henkel Corporation
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 Henkel Corporation filed Critical Henkel Corporation
Publication of WO1992000947A1 publication Critical patent/WO1992000947A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • This invention relates to processes for the esterification of oxyhydrocarbon polyols and ethers of these polyols.
  • "Oxyhydrocarbon polyols" are defined for purposes of this application as compounds that contain only hydrogen, carbon, and oxygen as elements, with at least as many carbon-oxygen single bonds as carbon atoms and with at least half of the oxygen atoms attached to a hydrogen atom.
  • the invention also relates to esters of oxyhydrocarbon polyols and their ethers, these esters having improved properties, particularly lighter color.
  • Oxyhydrocarbon polyols are generally derived from natural sources. Common examples are cellulose and numerous sugars and polysaccharides. Commercial materials of this type almost always include a variety of molecular types, including some that may still be of unknown or inexactly known chemical structure.
  • the ethers and esters of oxyhydrocarbon polyols are generally not natural products, but some of them have been familiar commercial products for the last several decades and can be prepared by various well known methods, which generally require the use of elevated temperature and acid or basic catalysis. Under such conditions, even in the practical absence of oxygen, it is generally known that all or almost all readily and economically available mixtures of oxyhydrocarbon polyols, their ethers, and/or their esters are susceptible to development of color to various degrees. (In the presence of oxygen, color development is even more pronounced.) Development of color is generally undesirable, because for most uses colorless or at least very slightly colored oxyhydrocarbon polyol esters are preferred.
  • a variety of chemical bleaching processes using reagents such as hydrogen peroxide, other peroxides, and hypochlorites, and/or sorptive processes, using sorbents such as activated carbon and diatomaceous earth, are known for eliminating or reducing the color developed in esterifying practical, economically available mixtures of oxyhydrocarbon polyols and/or their ethers with one another and/or with other naturally occurring impurities, but all of these methods have some disadvantages.
  • sorbitan monoesters usually contain an average degree of esterification substantially greater than 1 and contain some esters of sorbitol and/ or of isosorbide as well as those of sorbitan.
  • Some commonly used filtration aids and/or sorbents such as diatomaceous earth, although they lighten the color of freshly treated sorbitan esters, produce products that rapidly darken during storage after treatment.
  • one object of the present invention is to provide light colored esters of oxyhydrocarbon polyols and their ethers without any need for chemical bleaching and/or for treatment with sorbents that increase the tendency of the product esters to darken during storage.
  • a fatty acid product more resistant to discoloration on standing may be made by distillation in the presence of an antioxidant and a reducing agent; the latter may be sodium borohydride.
  • the reducing agent is a water-compatible one, i.e., one which retains its reducing power when in contact with or in solution in water and does not undergo any dangerous reaction, such as evolution of hydrogen or other flammable gas(es), with water when the reducing agent is in contact with or in solution in water.
  • an effective amount of reducing agent is defined to be any amount that causes a detectable reduction in product color, compared to a product made under esterification conditions otherwise identical except for the absence of reducing agent.
  • the amount of reducing agent is correlated with the amount of "reducing sugar" present in the mixture including oxyhydrocarbon polyol(s) and/or ether(s) thereof to be esterified.
  • the amount of "reducing sugar” can be measured by methods known in the art, preferably by the method described in connection with the working examples below.
  • the amount of reducing agent to be used during a process according to this invention is preferably at least sufficient stoichiometrically to reduce all the "reducing sugar" present in the mixture to be esterified, or, increasingly more preferably, a 9, 14, or 25 % excess of reducing agent over this stoichiometric amount is used.
  • the amount of reducing agent used is not more than the amount which will provide a 50 % excess, or more preferably a 35 % excess, over the ⁇ toichiometric amount noted above.
  • the reducing agent used be "reaction stable", which is defined to mean herein that if the reducing agent is mixed with the materials normally used for a esterification reaction, except for any polyol mixture, and is exposed to the temperatures used for a normal esterification for the time normally required, the reducing power of the reducing agent will not diminish to less than one half of its original value.
  • Preferable reducing agents for use in the process include sodium, potassium, and lithium borohydrides; calcium, barium, and magnesium borohydrides; lithium aluminum borohydride; and quaternary ammonium and tertiary amine borohydrides.
  • Sodium borohydride is most preferred, because it is the most water-compatible of the preferred group. Mixed as well as single types of reducing agents may be used.
  • a process according to this invention may be combined with conventional chemical bleaching and/or sorptive color reduction processes applied to the crude ester product, if needed or desired for further improvements.
  • one of the advantages of a process according to this invention is that the need for such post synthesis color reduction treatment is often eliminated by use of a process according to this invention, and avoidance of any such post treatment often results in a more stable product, as has been generally noted above and will be specifically illustrated below.
  • One particularly preferred specific embodiment of the invention is the manufacture of sorbitan esters, starting with commercial grade sorbitol as a raw material.
  • This process requires two distinct steps: (i) cyclizing the straight carbon chain of sorbitol to the carbocyclic ring of sorbitan and (ii) replacing some of the hydrogen atoms from the -OH groups in either sorbitan or sorbitol with acyl groups.
  • These two steps can be performed in either order, but it has been generally preferred commercially in the prior art to esterify first under alkaline conditions, then cyclize, and finally neutralize the products.
  • U. S. Patent 4,297,290 teaches cyclizing first under partial vacuum, then esterifying the resulting sorbitan.
  • hypophosphorous acid and/or hypophosphite ions as the catalyst during the cyclization step of the process, rather than the soap type catalysts generally preferred commercially in the prior art.
  • sodium or potassium hydroxide is preferred as catalyst for the esterification stage, with sodium hydroxide generally more preferred, except that when the product esters are to be ethoxylated, potassium hydroxide catalyst for the esterification stage is preferred.
  • One advantageous characteristic of the process of cyclizing sorbitol at atmospheric pressure is that the degree of cyclization can be readily controlled by monitoring the amount of water distilled from the reaction mixture. It is preferred in operating according to this process to select a particular degree of cyclization or dehydration of the sorbitol starting material that is desired, to carry out the cyclization reaction in apparatus which causes the water formed during the reaction to distill from the reaction mixture and be readily measurable by volume and/or mass as the reaction progresses, and then to observe the amount of water distilled during the cyclization and discontinue the cyclization reaction when the desired amount of water, including any amount originally present in or added along with the principal reagents, has been collected.
  • Preferred temperatures are 200 - 220o C for the esterification reaction and 160 - 170o C for the cyclization reaction when the latter is performed first. If the cyclization is performed predominantly after esterifying sorbitol, it is preferred that the temperature during cyclization not exceed 235o C.
  • the fatty acid used to manufacture sorbitan esters will almost always contain some acids other than those which are most common and give their name to the mixture. While most such impurities cause little difficulty in processing, it has been found that acyl groups that contain three or more carbon-carbon double or triple bonds have much greater likelihoods of producing a dark color than do acyl groups with two or fewer such unsaturated bonds. Accordingly, it is increas ingly more preferred that the acid mixtures used in a process according to this invention for making sorbitan esters contain not more than 8, 3, or 1 number percent of acyl groups with three or more carbon-carbon double or triple bonds.
  • all steps in a process for making sorbitan esters according to this invention be carried out in the substantial absence of oxygen whenever the temperature of the reagents exceeds 90, or more preferably, 25o C.
  • a protective atmosphere of nitrogen or other inert gas is used to achieve such absence of oxygen. It is increasingly more preferable for the concentration of oxygen in any gas in contact with the hot reagents to be no greater than 0.9, 0.2, 0.03, and 0.005 w/o.
  • sorbitan esters after making and filtering them with a high surface area absorbent, preferably an alkaline earth metal and/or alkali metal sili cate material with a specific surface area of at least 125, more preferably at least 270, still more preferably at least 400, square meters per gram.
  • a high surface area absorbent preferably an alkaline earth metal and/or alkali metal sili cate material with a specific surface area of at least 125, more preferably at least 270, still more preferably at least 400, square meters per gram.
  • the most preferred absorbent is KagnesolTM 30/40, a magnesium silicate sol that is commercially available from Reagent Chemical and Research, Inc., Houston, Texas, USA.
  • Typical, non-limiting conditions of treatment e.g., could be stirring the ester product together with 0.5 w/o of MagnesolTM 30/40 for one hour at 100o C.
  • the haze temperature of the product can often be raised by 20, 40, or even as much as 75o C.
  • Products treated in this way are superior in haze resistance to all commercial sorbitan monoester products compared against them.
  • sorbitan monooleate with a haze point greater than 200o C sorbitan monostearate with a haze point greater than 140o C
  • sorbitan monolaurate with a haze point greater than 150o C have all been prepared in this way. (All of these nominally "mono" esters of sorbitan are actually mixtures including substantial amounts of di- or even higher esters, along with some unesterified polyol.)
  • antioxidants include butylated hydroxy toluene (“BHT”), butylated hydroxy anisole (“BHA”), vitamin E and other tocopherols, and tertiary butyl hydroquinone (“TBHQ”), with BHA most preferred.
  • BHT butylated hydroxy toluene
  • BHA butylated hydroxy anisole
  • TBHQ tertiary butyl hydroquinone
  • a second particularly preferred embodiment of the invention is represented by the transesterification of fatty acid esters of low molecular weight alcohols with ⁇ - and/or ⁇ -etherified glucosides, for example reaction of ⁇ -methyl glucoside with methyl oleate to form ⁇ -methyl glucoside dioleate.
  • a combination of a base preferably a relatively weak base such as an alkali metal carbonate salt, more preferably potassium carbonate because of its greater solubility than sodium carbonate, and hypophosphite ion from hypophosphorous acid or one of its salts, preferably from sodium dihydrogen hypophosphite, be used to promote the reaction.
  • a base preferably a relatively weak base such as an alkali metal carbonate salt, more preferably potassium carbonate because of its greater solubility than sodium carbonate
  • hypophosphite ion from hypophosphorous acid or one of its salts preferably from sodium dihydrogen hypophosphite
  • Hypophosphite ion is believed to catalyze the transesterification reaction itself and is preferred to most other catalysts known for this purpose because of its ability to act as a reducing agent, supplementing the other reducing agents that may be, and preferably are, used in accordance with the embodiment of this invention involving treatment with reducing agents to purify starting materials from reducing sugars.
  • the amount of carbonate ion used is from 0.2 to 5, more preferably from 0.8 to 1.7, w/o of the amount of oxyhydrocarbon polyol ester reacted, and the amount of hypophosphite ions is from 0.04 to 1.3, more preferably from 0.2 to 0.7, w/o of the amount of oxyhydrocarbon polyol ether reacted.
  • the temperature during transesterification is not allowed to exceed 190, or more preferably 180, degrees C.
  • this usually means that a partial vacuum during transesterification is needed to drive the reaction by distilling off methanol or other lower alcohol from the fatty acid ester used.
  • Reaction under adequate vacuum is substantially complete, so that the amount of fatty acid ester with a lower alcohol to be used should be determined by stoichiometric calculation to produce the desired average degree of esterification of the glucoside ether reacted.
  • a mixture of molecules with different degrees of esterification, including some unesterified glucoside ether will be the actual reaction product.
  • This method is adapted from one given in the British Pharmacopoeia.
  • the reducing sugars or other reducing impurities present react with the Benedict solution to produce cuprous oxide.
  • the cuprous oxide is reacted with an excess of standard iodine solution.
  • the remaining iodine is titrated with sodium thiosulfate solution to an end point with starch indicator. All reagents specified should be of conventional purity for analytical work.
  • the raw materials and quantities used are as follows: ⁇ -methyl glucoside 145.5 g Water 145.5 g Potassium carbonate sesquihydrate 3.8 g Sodium borohydride 0.075 g Water 15 g Sodium hypophosphite 0.84 g
  • the ⁇ -methyl glucoside used is HorizonTM STA MEG 106 brand from Staley Chemical Co.; the methyl oleate is EmeryTM type 2303.
  • the amount of sodium borohydride is calculated to give a 25 % excess over the amount needed to reduce all the "reducing sugar" in the quantity of ⁇ -methyl glucoside used, as determined by the analytical method noted above on a sample of the same lot of ⁇ -methyl glucoside.
  • the amounts of potassium carbonate and sodium borohydride used are dissolved and/or suspended in the separately listed 15 g of water, immediately before being added to the reaction mixture.
  • the synthesis is performed in a four necked flask equipped with an agitator/stirrer, thermometer, inlet for nitrogen, outlet to a vacuum pump, and a condenser set for distillation. To avoid contamination, the stirrer shaft is lubricated with ⁇ -methyl glucoside dioleate.
  • the reagents are charged separately to the flask at room temperature after a nitrogen atmosphere had been established therein, in the order listed above, except that the already noted solution/suspension of potassium carbonate and sodium borohydride is added in one step.
  • the reaction slurry is then heated with constant agitation at atmospheric pressure to 180o C. During heating, the reaction mixture becomes viscous and foamy, but at about 150o C, the viscosity begins to diminish rather sharply.
  • the temperature is raised over the course of about 65 min to 165o C.
  • the amount of distillate primarily water, is monitored at intervals during the reaction, in order to determine how much cyclization has occurred.
  • 143 g of distillate is collected.
  • only 10 g of distillate is collected, and over the next 35 minutes only 2.5 g of distillate is collected.
  • the vapor temperature reaches a high of 115o C at about the time that the flask contents temperature reaches 165o C but then falls, remaining within the range of 98 - 105o C for the last 85 minutes while the flask is at 165o C.
  • the temperature of the flask contents is then raised to 170o C over a period of 15 min and is maintained there for the next 200 min.
  • the vapor temperature during this period falls slowly from 105o C to a final value of 93o C, under a slight vacuum maintained during the final 25 min, while the distillate collection rate falls from about 15 to about 8 g per hour.
  • the flask contents are then allowed to cool.
  • the cooled reaction mixture as described above is reheated to 72o C while still under a nitrogen atmosphere, and after this 1.8 g of 50 aqueous H 3 PO 2 and 13.2 g of aqueous KOH are added to the contents.
  • the temperature of the flask contents is then raised over 45 min to 210o C and maintained there for 240 min, during which time 49 g of additional distillate is collected.
  • An amount of 3.9 g of 75 % aqueous H 3 PO 4 is then added to neutralize the remaining potassium hydroxide.
  • the product has an Acid No. of 10.00, a Saponification No. of 149.2, a Hydroxyl No. of 238.1, and a melting point of 52.8 - 53.4o C.
  • the yield is 1002 g of product.
  • Example 2 This is the same as Example 2, except that the initial cyclizing-anhydrization reaction is performed at 120o C and at a pressure of only 6 - 7 millibars for 110 min (without any measurement of the amount of water distilled off from the reaction mixture) in accordance with the general teachings of Stockburger, U. S. Patent 4,297,290 column 3 lines 13 - 19.
  • the yield is less than 900 g.
  • Example 2 is repeated, except that sodium borohydride is added to the initial mixture in an amount 25 % over the stoichiometric amount required to reduce all the "Reducing Sugars" in the sorbitol used.
  • the product has a lighter color than that of the product from Experiment 2, but other results are essentially the same.
  • This example illustrates the preparation of a sorbitan ester from sorbitol by first esterifying under basic catalysis, then neutralizing, then cyclizing.
  • the equipment used is the same as for Example 1.
  • a nitrogen atmosphere is established in the flask, and 669 g of 70 % sorbitol (from Roquette as above), 541 g of iauric acid (Grade E - 626 from Emery as above), 3.0 g of 50 % aqueous H 3 PO 2 , and 3.0 g of 50 % aqueous NaOH are charged to the flask at room temperature in the order given above, with stirring.
  • Heating is then begun, with stirring continuing, and the flask contents temperature reaches 126o C after about one hour and 215o C after another 130 min.
  • the temperature is then maintained in the range from 215 - 220o C for another SO min, after which time the Acid No. of the contents has fallen to 6.2.
  • Example 4 This is the same as Example 4, except that the neutralization with H 3 PO 4 is not performed at the point indicated in Example 4, but instead is performed after all other described process steps.
  • the color of the product is much darker than in Example 4.
  • Example 2 This is the same as Example 2, except that (1) 820 g of oleic acid is used instead of the stearic acid of Examp le 2, (2) the temperature before addition of the potassium hydroxide is not allowed to rise above 165o C, with a slight vacuum to produce a vapor temperature of about 95o C being maintained for the last 200 sinutes before addition of the potassium hydroxide; (3) the temperature after addition of the potassium hydroxide is kept at or below 200o C, with vacuum after the first two hours of reaction to reduce the vapor temperature into the range of 60 - 80o C; and (4) the final product is 1087 g of sorbitan monooleate with a Gardner color of 2+, an Acid No. of 6.69, a Saponification No. of 150.63, and a Hydroxyl No. of 205.5.
  • 820 g of oleic acid is used instead of the stearic acid of Examp le 2
  • the temperature before addition of the potassium hydroxide is not allowed to rise above 165o C, with a

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le fait de procéder à des estérifications de polyols d'oxyhydrocarbures et de leurs éthers en présence d'un agent de réduction, ou de prétraiter ces matières à l'aide d'un agent de réduction permet la synthèse de produits d'esters légèrement colorés sans décoloration. Ce procédé est particulièrement utile conjointement avec la préparation d'esters d'acides gras de sorbitan à partir de sorbitol lorsque la cyclization du sorbitol précède l'estérification, et l'on peut améliorer le rendement du procédé précité par estérification à une pression atmosphérique. Le procédé est également très utile dans la synthèse d'esters d'acides gras de glucosides d'alkyle, et on peut améliorer les résultats de ce procédé par transestérification à l'aide d'esters d'acide gras d'alcools inférieurs catalysés à des températures égales ou inférieures à 180 °C par des ions hypophosphite.
PCT/US1991/004877 1990-07-09 1991-07-09 Esterification amelioree de polyols d'oxyhydrocarbures ainsi que de leurs ethers, et produits obtenus WO1992000947A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54983490A 1990-07-09 1990-07-09
US549,834 1990-07-09

Publications (1)

Publication Number Publication Date
WO1992000947A1 true WO1992000947A1 (fr) 1992-01-23

Family

ID=24194542

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/004877 WO1992000947A1 (fr) 1990-07-09 1991-07-09 Esterification amelioree de polyols d'oxyhydrocarbures ainsi que de leurs ethers, et produits obtenus

Country Status (1)

Country Link
WO (1) WO1992000947A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5360900A (en) * 1993-08-12 1994-11-01 Oxid, Inc. Aromatic polyester polyol
EP0647652A3 (fr) * 1993-10-05 1995-08-09 Gen Foods Inc Procédé de préparation de polyesters de saccharides par transestérification.
US5518754A (en) * 1994-08-19 1996-05-21 Kraft Foods, Inc. Chocolate products with sucrose fatty acid polyester fat substitutes
US5532019A (en) * 1995-06-05 1996-07-02 Kraft Foods, Inc. Process for making stable emulsified dressings with polyol fatty acid polyesters
US5596085A (en) * 1995-04-11 1997-01-21 Kraft Foods, Inc. Method for preparing polyol fatty acid polyesters by transesterification
US5681948A (en) * 1995-03-06 1997-10-28 Kraft Foods, Inc. Two-stage method for preparing polyol fatty acid polyesters
WO1998004540A1 (fr) * 1996-07-31 1998-02-05 Imperial Chemical Industries Plc Fabrication d'esters d'acide gras de sorbitanne comme tensio-actifs
US6515734B1 (en) 1999-12-06 2003-02-04 Olympus Optical Co., Ltd. Exposure apparatus
WO2009007326A2 (fr) 2007-07-06 2009-01-15 Basf Se Procédé de préparation d'une solution de glucose aqueuse
US7511014B2 (en) 1989-02-20 2009-03-31 Novartis Ag Cyclosporin galenic forms
WO2011083000A1 (fr) 2009-12-16 2011-07-14 Basf Se Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
WO2020068582A1 (fr) * 2018-09-27 2020-04-02 Arkema Inc. Compositions contenant un éther cyclique et un hydroxyle, utiles pour produire des polymères d'alkyde secs rapides et procédés de fabrication de telles compositions contenant un éther cyclique et un hydroxyle

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297290A (en) * 1980-07-17 1981-10-27 Ici Americas Inc. Process for preparing sorbitan esters
EP0132941A1 (fr) * 1983-06-23 1985-02-13 The Procter & Gamble Company Synthèse de polyesters de polyols supérieurs et d'acides gras utilisant un carbonate comme catalyseur
US4562007A (en) * 1982-11-05 1985-12-31 Hoechst Aktiengesellschaft Process for preparing carboxylic acid esters of hexitols
DE3729335A1 (de) * 1986-09-17 1988-03-31 Kao Corp Verfahren zur herstellung eines sorbitanesters
US4788009A (en) * 1986-11-14 1988-11-29 Union Camp Corporation Method of preparing rosin esters of improved thermal stability with inorganic salt of phosphorous or hypophosphorous acid
US4861513A (en) * 1987-02-04 1989-08-29 Huels Aktiengesellschaft Preparation of specifically adjusted polyalcohol mixtures based on sorbitol
EP0349221A2 (fr) * 1988-06-30 1990-01-03 The Procter & Gamble Company Fabrication de polyesters polyols avec contenu teneur réduite en couleur
US4897474A (en) * 1986-07-11 1990-01-30 Huels Aktiengesellschaft Carbohydrate fatty acid esters and a process for preparing them

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297290A (en) * 1980-07-17 1981-10-27 Ici Americas Inc. Process for preparing sorbitan esters
US4562007A (en) * 1982-11-05 1985-12-31 Hoechst Aktiengesellschaft Process for preparing carboxylic acid esters of hexitols
EP0132941A1 (fr) * 1983-06-23 1985-02-13 The Procter & Gamble Company Synthèse de polyesters de polyols supérieurs et d'acides gras utilisant un carbonate comme catalyseur
US4897474A (en) * 1986-07-11 1990-01-30 Huels Aktiengesellschaft Carbohydrate fatty acid esters and a process for preparing them
DE3729335A1 (de) * 1986-09-17 1988-03-31 Kao Corp Verfahren zur herstellung eines sorbitanesters
US4788009A (en) * 1986-11-14 1988-11-29 Union Camp Corporation Method of preparing rosin esters of improved thermal stability with inorganic salt of phosphorous or hypophosphorous acid
US4861513A (en) * 1987-02-04 1989-08-29 Huels Aktiengesellschaft Preparation of specifically adjusted polyalcohol mixtures based on sorbitol
EP0349221A2 (fr) * 1988-06-30 1990-01-03 The Procter & Gamble Company Fabrication de polyesters polyols avec contenu teneur réduite en couleur

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Dialog Information Services, File 351, World Patent Index 81-91, Dialog Accession no. 004576470, (DETE-) INTR DETERGENT TIMI), "Sorbitol ester of fatty acid prepd. by alcoholysis of sorbitol with fatty acid ester of prim. alcohol using acid or basic catalyst", RO 87381, A, 850830, 8612 (Basic) *
Patent Abstracts of Japan, Vol 12, No 301, C521, abstract of JP 63- 72697, publ 1988-04-02 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7511014B2 (en) 1989-02-20 2009-03-31 Novartis Ag Cyclosporin galenic forms
US5360900A (en) * 1993-08-12 1994-11-01 Oxid, Inc. Aromatic polyester polyol
EP0647652A3 (fr) * 1993-10-05 1995-08-09 Gen Foods Inc Procédé de préparation de polyesters de saccharides par transestérification.
US5518754A (en) * 1994-08-19 1996-05-21 Kraft Foods, Inc. Chocolate products with sucrose fatty acid polyester fat substitutes
US5681948A (en) * 1995-03-06 1997-10-28 Kraft Foods, Inc. Two-stage method for preparing polyol fatty acid polyesters
US5596085A (en) * 1995-04-11 1997-01-21 Kraft Foods, Inc. Method for preparing polyol fatty acid polyesters by transesterification
US5532019A (en) * 1995-06-05 1996-07-02 Kraft Foods, Inc. Process for making stable emulsified dressings with polyol fatty acid polyesters
WO1998004540A1 (fr) * 1996-07-31 1998-02-05 Imperial Chemical Industries Plc Fabrication d'esters d'acide gras de sorbitanne comme tensio-actifs
AU739483B2 (en) * 1996-07-31 2001-10-11 Imperial Chemical Industries Plc Manufacture of fatty acid esters of sorbitan as surfactants
US6362353B1 (en) 1996-07-31 2002-03-26 Imperial Chemical Industries Plc Manufacture of fatty acid esters of sorbitan as surfactants
RU2189375C2 (ru) * 1996-07-31 2002-09-20 Империал Кемикал Индастриз ПЛС Получение сложных эфиров сорбитана и жирных кислот в качестве поверхностно-активных веществ
CN1131857C (zh) * 1996-07-31 2003-12-24 帝国化学工业公司 作为表面活性剂的脱水山梨醇脂肪酸酯的生产方法
US6515734B1 (en) 1999-12-06 2003-02-04 Olympus Optical Co., Ltd. Exposure apparatus
WO2009007326A2 (fr) 2007-07-06 2009-01-15 Basf Se Procédé de préparation d'une solution de glucose aqueuse
EP2474235A2 (fr) 2007-07-06 2012-07-11 Basf Se Procédé de production de gluten de maïs
WO2011083000A1 (fr) 2009-12-16 2011-07-14 Basf Se Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
WO2020068582A1 (fr) * 2018-09-27 2020-04-02 Arkema Inc. Compositions contenant un éther cyclique et un hydroxyle, utiles pour produire des polymères d'alkyde secs rapides et procédés de fabrication de telles compositions contenant un éther cyclique et un hydroxyle
CN112771050A (zh) * 2018-09-27 2021-05-07 阿科玛股份有限公司 用于生产快干醇酸聚合物的含环醚和羟基的组合物及制备此类含环醚和羟基的组合物的方法
CN112771050B (zh) * 2018-09-27 2024-01-19 阿科玛股份有限公司 用于生产快干醇酸聚合物的含环醚和羟基的组合物及制备此类含环醚和羟基的组合物的方法
US11912820B2 (en) 2018-09-27 2024-02-27 Arkema Inc. Cyclic ether- and hydroxyl-containing compositions useful for producing fast dry alkyd polymers and methods for making such cyclic ether- and hydroxyl-containing compositions

Similar Documents

Publication Publication Date Title
WO1992000947A1 (fr) Esterification amelioree de polyols d'oxyhydrocarbures ainsi que de leurs ethers, et produits obtenus
US4830771A (en) Process for the preparation of trialkanolamine di(fatty acid) esters, and the use thereof for softening fabrics
US4806632A (en) Process for the post-hydrogenation of sucrose polyesters
US6620904B2 (en) Processes for preparing linear polyglycerols and polyglycerol esters
CA1331015C (fr) Preparation de glycerine propoxylee esterifiee par transesterification
EP0915862B1 (fr) Fabrication d'esters d'acide gras de sorbitanne comme tensio-actifs
US4861513A (en) Preparation of specifically adjusted polyalcohol mixtures based on sorbitol
US6310227B1 (en) Reduced calorie cooking and frying oils having improved hydrolytic stability, and process for preparing
DE3636086A1 (de) Fettsaeureester von polyglycerinpolyglykolethern, ihre herstellung und ihre verwendung
EP0785815A4 (fr) Composition antimousse et son procede d'utilisation
KR100242176B1 (ko) 알킬폴리글리코시드의 연속 표백방법
US4803299A (en) Preparation of polytetramethylene ether glycol diesters having a low color number
US3071604A (en) Preparation of light colored fatty acid esters
JP5120682B2 (ja) アルケニル基含有ポリオキシアルキレン誘導体及びその製造方法
KR0176964B1 (ko) 고순도 테트라히드로푸란 중합체의 제조방법
JP4106831B2 (ja) ポリグリセリン脂肪酸エステル及びその製造方法
JPH09509426A (ja) アルキルポリグリコシドの連続的漂白方法
AU683513B2 (en) Improvement in the production of alkylpolyglycosides
US4521595A (en) Process for the purification of esters
US6130191A (en) Process for the preparation of trimethylolpropane caprylate/caprate
Moody et al. Effect of traces of acids on reaction of sucrose in dimethyl sulfoxide
JP2001139679A (ja) ポリグリセリンモノ脂肪酸エステル及びその製造方法
KR20030093012A (ko) 솔비탄 지방산에스테르의 제조방법
CA2157546A1 (fr) Methode de preparation de polyglycosides alkyles
JP4128267B2 (ja) ポリオール部分エステルの製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载