AU2001255110A1 - Improved synthesis of anhydroglycitol esters of improved colour - Google Patents
Improved synthesis of anhydroglycitol esters of improved colourInfo
- Publication number
- AU2001255110A1 AU2001255110A1 AU2001255110A AU2001255110A AU2001255110A1 AU 2001255110 A1 AU2001255110 A1 AU 2001255110A1 AU 2001255110 A AU2001255110 A AU 2001255110A AU 2001255110 A AU2001255110 A AU 2001255110A AU 2001255110 A1 AU2001255110 A1 AU 2001255110A1
- Authority
- AU
- Australia
- Prior art keywords
- process according
- reaction
- acid
- isosorbide
- sorbitan
- 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.)
- Granted
Links
Description
Improved synthesis of anhydroglycitol esters of improved colour
The invention relates to an improved synthesis of al yl and aryl esters of anhydroglycitol derivatives. These compounds are commercially interesting derivatives of the raw material sorbitol and other glycitols. The potential applications of these compounds are highly diverse. Esters of monoanhydrosorbitol (sorbitan) are widely used as emulsifiers (Span, Tween) ' . In addition, esters of dianhydrosorbitol (isosorbide) have many potential applications: as preservatives " , lubricants , polymer stabiliser , emulsifier in cosmetics 89, dispersing agents for pigments 10 or as plasticisers for vinyl resins π" 5.
The dehydration of sorbitol, as an example of that of the glycitols, is shown in the diagram below:
D-sorbitol lydrosorbitc >l (sorbitan) dianhydrosorbitol (isosorbide)
The current synthesis methods are usually based on acid-catalysed direct esterifications, sulphuric acid or ?-toluenesulphonic acid being used as catalyst ' . Base- catalysed reactions are also known; however, the reactions concerned here are usually
1 - ι o transesterification reactions at high temperature (above 200°C) " . Furthermore, the use of acid ion exchange resins of the gel type as catalyst is also reported ' ; in this context yields of 61 and 63% for isosorbide dibutyrate and isosorbide dipropionate, respectively, are reported, starting from isosorbide.
In the case of the direct esterification the reaction equilibrium is shifted by removal of the water of reaction. This can be achieved by azeotropic distillation with toluene or xylene 13, '20, or by the use of a vacuum 21. Yields in excess of 70% diester, starting from isosorbide, are not achieved with any of the above-mentioned methods.
The esterification of isosorbide is shown in the following equation:
+ (n-l) RCOOH + H20 0
The invention relates to the synthesis of esters of dianhydrosorbitol and other dianhydroglycitols with high conversion (98 - 100%) and a substantially improved colour, as a result of which distillation of the product can be dispensed with. According to the invention use is made of a macroporous acid ion exchange resin as catalyst. In addition, an inert gas, such as nitrogen gas, is preferably dispersed through the reaction mixture in order to accelerate the removal of the water of reaction. A further improvement is obtained by increasing the turbulence of the reaction mixture, so that the removal of the water of reaction is further promoted. A reduced pressure of, for example, 10 - 50 mbar is also advantageous. The colour of the reaction mixture is substantially improved because the reaction temperature can be kept below 150°C. Furthermore, addition of activated charcoal to the reaction mixture leads to a further reduction in the colour.
In addition to dianhydrosorbitol (isosorbide) as starting material it has also proved possible to use anhydrosorbitol (sorbitan) and even sorbitol as starting material. If the reaction temperature in the initial stage of the reaction is kept low (120 - 125°C), selective dehydration takes place, followed by esterification after raising the reaction temperature to
22
140 - 150°C. Giacometti et al. ' merely reported the possibility of in situ formation of anhydrosorbitol derivatives during the esterification of sorbitol with j3-toluenesulphonic acid, without specifying experimental details for this. Although ion exchange resins have been used as catalyst in the reaction for the dehydration 19,21'24 0f sorbitol, the conversions were too low (39 - 57%) and the reaction times usually too long (2 - 24 hours). Feldmann et al. (DE 3 041 673) reported the dehydration of sorbitol with the aid of a macroporous ion exchange resin, the water of reaction being removed with the aid of a stream of nitrogen. Despite the high yield of isosorbide (93%), the reaction mixture was severely discoloured and the reaction time was long (5 h).
21
Matyschok et al. also reported the synthesis of isosorbide esters with the aid of an acid ion exchange resin of the gel type (Wofatit KPS), in which context it must be mentioned that the alkanoic acids used by them have a short chain and thus high intrinsic acidity (acetic acid, propionic acid, butyric acid). The reported yields are, however, too low to be of industrial relevance (60 - 70%).
The process according to the invention preferably relates to the synthesis of diesters in accordance with the following equation:
Surprisingly it has been found that a substantially improved method of preparation for dianhydrosorbitol diesters has been developed by a combination of techniques known per se. In view of the increasing industrial relevance of dianhydrosorbitol diesters, this meets an important need.
The process according to the invention can be used for the esterification of glycitols and the monoanhydro and dianhydro derivatives thereof. A glycitol is understood to be a sugar alcohol having at least 6 carbon atoms. These include, first of all, sorbitol, mannitol, iditol and other hexitols, but also higher analogues such as heptitols and glycitols derived from the di- and oligo-saccharides, such as lactitol, maltitol, and the like. The process according to the invention can also be used for glycitols (sugar alcohols) that cannot be converted to dianhydro analogues, such as pentitols (xylitol, etc.), in which case diesters and higher esters of the monoanhydro analogues (xylitan, etc.) are then formed.
The esterification can take place with any carboxylic acid, such as alkanoic acids, alkenoic acids, alkadienoic acids, cycloalkanecarboxylic acids and arenecarboxylic acids. The carboxylic acids can be either straight-chain or branched. Examples are propionic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, stearic acid, cyclohexanecarboxylic acid, optionally substituted benzoic acids, phenylacetic acid, naphthalenecarboxylic acid, etc. The diesters of C3 - C2Q carboxylic acids are particularly advantageous. Mixtures of acids, in particular fatty acids of varying chain length, can also be used.
The esters of shorter chain carboxylic acids, such as C3 - C6, can be used in the main as solvents, those of medium chain length alkanoic acids, in particular of C6 - C12 carboxylic acids, are outstandingly suitable as plasticisers and the longer chain length, for example C12 - C18, carboxylic acids are mainly usable as lubricants. If desired, monoesters of dianhydroglycitols can also be obtained by using smaller amounts of fatty acids, for example 1 to 2 mol per mol (anhydro)glycitol. What is concerned in this case is then mainly the preparation of emulsifiers, such as the monoesters of C12 - C20 alkanoic acids or alkenoic acids and monoaryl and monoaralkyl esters.
The choice of the catalyst resin is important. This is an acid catalyst resin of the macroporous or macroreticular type. In contrast to resins of the gel type, these are resins with a relatively high degree of crosslinking and consequently a high porosity. A description of suitable resins is to be found in standard works on catalyst resins, such as "Ion Exchangers" by Konrad Dδrfher, published by De Gruyter, Berlin, 1991, in particular pages 22 - 23 thereof. Examples of suitable resins are the commercially available resins, such as Amberlyst-15-wet, Amberlyst-15-dry, Amberlyst-16-wet and Amberlyst-36-dry from Rohm and Haas, and comparable resins from other suppliers.
Examples General procedure
The reaction was carried out in a 2.0 1 four-necked, round-bottomed flask equipped with a gas inlet tube (with glass frit), a Pt-100 temperature sensor, a Dean-Starck condenser and a mechanical stirrer. The mechanical stirrer was equipped with a stainless steel centrifugal stirrer (60 mm diameter). Stirring was carried out at a speed of 900 revolutions per minute. Heating of the reactor was achieved using an Isopad 2.0 1 electrical heating jacket, equipped with a temperature control unit. During the reaction nitrogen gas was
dispersed through the reaction mixture via a gas inlet tube at a flow rate of 400 ml per minute. The progress of the reaction was followed both by measuring the quantity of water formed over time and by GLC determination of the reaction mixture. After complete conversion had been achieved, the reaction mixture was cooled to approximately 60 - 80°C, after which the catalyst was removed by means of a sieve. The reaction mixture was then stirred for some time (0.5 - 1.5 hours) with active charcoal at 80 - 100°C. Filtration of this mixture through a glass filter with Filteraid yielded a pale yellow viscous mixture of isosorbide diester and alkanoic acid. The excess alkanoic acid was then removed by means of vacuum distillation. GLC and C NMR analysis (of both the product and the hydrolysed product) of the product thus obtained showed only the presence of the desired isosorbide diester. Average isolated yields were between 95 and 99%.
Example 1: Synthesis of isosorbide 2,5-di-n-octanoate using isosorbide as the starting material A mixture of isosorbide (292.3 g, 2.00 mol), n-octanoic acid (865.3 g, 6.00 mol, 3 eq) and 40g Amberlyst 15 (dry) resin was stirred at a constant temperature (see Table 1). After complete conversion had been achieved, the yellow transparent reaction mixture was decolourised with active charcoal. The excess n-octanoic acid was then distilled off under vacuum. The product was a pale yellow transparent viscous liquid (95 - 98%).
Table 1: Esterification of isosorbide with n-octanoic acid: reaction times at complete conversion
isosorbide acid T reaction time colour (mol) (eq) (°C) (hours)
1 5 145 6 pale yellow
2 3 120 11 yellow
2 3 145 7 yellow
Example 2: Synthesis of isosorbide 2,5-di-2-ethylhexanoate using isosorbide as the starting material
A mixture of isosorbide (292.3 g, 2.00 mol), 2-ethylhexanoic acid (865.3 g, 6.00 mol, 3 eq) and 40g Amberlyst 15 (dry) resin was stirred at a constant temperature (see Table 2). After complete conversion had been achieved, the yellow transparent reaction mixture was
decolourised with active charcoal. The excess 2-ethylhexanoic acid was then distilled off under vacuum. The product was a pale yellow transparent viscous liquid (95 - 98%).
Table 2: Esterification of isosorbide with 2-ethylhexanoic acid: reaction times at complete conversion isosorbide acid T time colour
(mol) (eq) (°C) (hours)
1 5 145 13 yellow
2 3 145 12 pale yellow
2 3 160 6 yellow
Example 3: Synthesis of isosorbide 2,5 di-n-octanoate using 1,4-sorbitan as the starting material
A mixture of 1,4-sorbitan, (164.5 g, 1.00 mol), n-octanoic acid (432.7 g, 3.00 mol, 3 eq) and 20 g Amberlyst 15 (dry) resin was stirred at 145°C. Complete conversion was achieved after 8 hours. After removal of the catalyst, the yellow transparent reaction mixture was decolourised with active charcoal. C NMR analysis of the hydrolysed product of the reaction mixture indicated only the formation of isosorbide dioctanoate. Distilling off the excess n-octanoic acid, followed by a second decolourisation, gave a pale yellow product in a yield of 80%.
Example 4: Synthesis of isosorbide 2,5 di-n-octanoate using sorbitol as the starting material
A mixture of sorbitol, (364.34 g, 2.00 mol), n-octanoic acid (865.3 g, 6.00 mol, 3 eq) and 40 g Amberlyst 15 (dry) resin was stirred at 125°C. After approximately 4 mol water had been collected (indicative of quantitative dehydration), the temperature was raised to 145°C. Complete conversion was achieved after 8 hours. After removal of the catalyst, the yellow-brown transparent reaction mixture was decolourised with active charcoal.
1
C NMR analysis of the hydrolysed product of the reaction mixture indicated only the presence of isosorbide dioctanoate.
Example 5: Synthesis of isosorbide 2,5 di-n-octanoate using isosorbide and active charcoal as the starting materials
A mixture of isosorbide (292.3 g, 2.00 mol), n-octanoic acid (865.3 g, 6.00 mol, 3 eq), 40 g Amberlyst 15 (dry) resin and 20g active charcoal was stirred at 145°C. After complete conversion had been achieved, the reaction mixture was filtered. The excess n-octanoic acid was then removed from the resulting pale yellow reaction mixture by means of distillation. After adding n-hexane and further active charcoal (10 g) the product was stirred for a further 1 hour at 80°C. Removal of the charcoal by filtration, followed by removal of the n-hexane (under reduced pressure), yielded a virtually "water-white" product.
Literature references
1) Kobayashi T.; Mori, N.; Nishida, M.; Isobe, K.; Iwasaki, R. Surface active agent composition; Lion Corp.: Japanese Patent Application JP-A-8-173787, 1996.
2) Kobayashi T.; Mori, N.; Iwasaki R. Draining agent and draining method; Lion Corp.: Japanese Patent Application JP-A-8-281003, 1996.
3) Amano, H.; Yoshida, C; Nakamura, A. Chem. Abstr.1980, 93, 69076.
4) Knightly, W.H. Preparation of baked goods; Atlas Chemical Industries: US Patent 3,394,009, 1968.
5) Rusch, D.T. Chem. Abstr. 1971, 75, 117364 6) Hughes, F.A. Preventing blocking of aluminium sheets; Atlas Chemical Industries: US Patent 3,468,701, 1969.
7) Stephen, J.F.; Smith, J.H.; Meshreki, M.H. Hindered phenolic compounds derived from hexides as stabilizers; ICI Americas Inc: US Patent 4,613,638, 1986.
8) Ochiai, ML; Ozawa, T. Chem. Abstr. 1979, 90, 209946. 9) Kazuhisa, F. Cosmetics containing isosorbide fatty acid diesters; Nihon Surfactants Co.: Japanese Patent Application JP-59-125408, 1984.
10) anonymous Res. Disci. 1977, 158, 45-47.
11) Braun, D.; Bergmann, M. Angew. Macromol. Chem. 1992, 199, 191-205.
12) Le Maistre, J.W.; Ford, E.C. Epoxidized diesters of polyoxyethylene isosorbide; Atlas Chemical Corporation: US Patent 3,225,067, 1965.
13) MacKay Bremner, J.G.; Beaumont, S. Improvements in and relating to the production of heterocyclic compounds; ICI, British Patent 613,444, 1946.
14) Hayashi Kogyo Kagaku zasshi 1953, 56, 623-625.
15) Luitjes, L.; Jansen, J. Bicyclooctane derivatives as plasticisers; ATO-DLO: International Patent Application WO 99/45060 (PCT/NL99/00115).
16) Prossel, G.; Papenfuhs, B. Verfahren zur Herstellung von Mischungen aus Sorbitmonoestem, Sorbitdiestem und Partialglyceriden (Process for the preparation of mixtures of sorbitol monoesters, sorbitol diesters and partial glycerides); Clariant GmbH: European Patent Application EP 0 889 023 Al, 1999.
17) Stuehler, H.; Kremp, E.; Oberhauser, A. Anhydrohexitol carboxylic acid esters; Hoechst AG, German Patent Application DE 3119 553, 1982.
18) Stockburger, G.J. Process for preparing sorbitan esters; ICI Americas Inc: US Patent 4,297,290, 1981.
19) Goodwin, J.C.; Hodge, J.E.; Weisleder, D. Carbohydrate Res. 1980, 79, 133-141.
20) Matyschok, H.; Ropuszynski, S. Pr. Nauk. L st. Technol. Org. Tworzyw. Sztucznych Polytech. Wroclaw, 1973, 13, 377-387.
21) Fleche, G.; Huchette, M. Starch 1986, 26-30. 22) Giacometti, J.; Wolf, N.; Gomzi, Z.; Milin, C. React. Kinet. Catal. Lett. 1996, 59,. 235- 240.
23) Giacometti, J.; Milin, C; Wolf, N.; Giacometti, F. J. Agric. Food Chem. 1996, 44, 3950-3954.
24) Bock, K.; Pedersen, C; Thogersen, H. Acta Chem. Scand. 1981, B 35, 441-449.
Claims (12)
1. A process for the preparation of esters of (dianhydroglycitols by esterification of dianhydroglycitols, anhydroglycitols and/or glycitols with alkylcarboxylic or arylcarboxylic acids in the presence of an acid catalyst, characterised in that the acid catalyst is a macroporous acid ion exchange resin.
2. A process according to Claim 1, wherein the molar ratio of carboxylic acid to ((di)anhydro)glycitol is selected between 2 and 5, and in particular between 2 and 3.
3. A process according to Claim 1 or 2, wherein the water of reaction is removed by passing a stream of inert gas through the reaction mixture.
4. A process according to one of Claims 1 - 3, wherein the reaction temperature is between 120°C and 180°C, in particular between 120°C and 150°C.
5. A process according to one of Claims 1 - 4, wherein a sulphonic acid ion exchange resin of the styrene-divinylbenzene copolymer type is used.
6. A process according to Claim 5, wherein a macroporous ion exchange resin of the Amberlyst type is used.
7. A process according to one of Claims 1 - 6, wherein the carboxylic acids contain 3 to 18, in particular 5 to 14 carbon atoms.
8. A process according to one of Claims 1 - 7, wherein the dianhydroglycitol is isosorbide.
9. A process according to one of Claims 1 - 8, wherein the anhydroglycitol is 1,4-sorbitan, 2,5-sorbitan or 3,6-sorbitan, or a mixture of sorbitan isomers.
10. A process according to one of Claims 1 - 9, wherein sorbitol is esterified.
11. A process according to one of Claims 1 - 10, wherein a glycitol or monoanhydro- glycitol is esterified and the reaction temperature is kept between 120°C and 130°C during the dehydration reaction of the glycitol (first step) and the reaction temperature is raised to 130°C to 160°C after the dehydration reaction.
12. A process according to one of Claims 1 - 11, wherein the reaction is carried out with active charcoal in the reaction mixture.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1015119A NL1015119C2 (en) | 2000-05-04 | 2000-05-04 | Improved synthesis of anhydroglycitol esters with improved color. |
NL1015119 | 2000-05-04 | ||
PCT/NL2001/000342 WO2001083488A1 (en) | 2000-05-04 | 2001-05-04 | Improved synthesis of anhydroglycitol esters of improved colour |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2001255110A1 true AU2001255110A1 (en) | 2002-01-31 |
AU2001255110B2 AU2001255110B2 (en) | 2006-05-04 |
Family
ID=19771327
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU5511001A Pending AU5511001A (en) | 2000-05-04 | 2001-05-04 | Improved synthesis of anhydroglycitol esters of improved colour |
AU2001255110A Ceased AU2001255110B2 (en) | 2000-05-04 | 2001-05-04 | Improved synthesis of anhydroglycitol esters of improved colour |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU5511001A Pending AU5511001A (en) | 2000-05-04 | 2001-05-04 | Improved synthesis of anhydroglycitol esters of improved colour |
Country Status (13)
Country | Link |
---|---|
US (1) | US6693209B2 (en) |
EP (1) | EP1278752B1 (en) |
JP (1) | JP5099952B2 (en) |
KR (1) | KR20030004382A (en) |
AT (1) | ATE278696T1 (en) |
AU (2) | AU5511001A (en) |
CA (1) | CA2430090C (en) |
DE (1) | DE60106227T2 (en) |
DK (1) | DK1278752T3 (en) |
ES (1) | ES2228854T3 (en) |
NL (1) | NL1015119C2 (en) |
PT (1) | PT1278752E (en) |
WO (1) | WO2001083488A1 (en) |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112005001607T5 (en) * | 2004-07-08 | 2007-05-24 | Archer-Daniels-Midland Co., Decatur | Epoxidized esters of vegetable oil fatty acids as reactive diluents |
FR2879611B1 (en) * | 2004-12-22 | 2007-06-22 | Roquette Freres | PREPARATION AND PROCESSING OF COMPOSITIONS BASED ON BITUMEN, HYDROCARBON AND / OR RESIN |
US20060210697A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Infant formula composition |
US7776365B2 (en) * | 2005-03-18 | 2010-08-17 | Sakura Properties, Llc | Article with skin protecting and moisturizing compound |
US7666448B2 (en) * | 2005-03-18 | 2010-02-23 | Sakura Properties, Llc | Skin cleansing article |
US20060210496A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Compositions for skin protection from ultraviolet damage |
US7749545B2 (en) * | 2005-03-18 | 2010-07-06 | Sakura Properties, Llc | Fucoidan compositions and methods for dietary and nutritional supplements |
US20060210688A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Dehydrated sports drink powder |
US20060210514A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Skin protection and moisturizing compositions and method of making the same |
US20070020358A1 (en) * | 2005-03-18 | 2007-01-25 | Mower Thomas E | Sports drink concentrate |
US20060210515A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Hair growth formula |
US20060210692A1 (en) * | 2005-03-18 | 2006-09-21 | Mower Thomas E | Baby food composition |
FR2883877B1 (en) | 2005-04-01 | 2008-10-10 | Roquette Freres | PROCESS FOR THE PREPARATION OF DIANHYDROHEXITOL DIESTER (S) COMPOSITIONS |
US7772412B2 (en) * | 2006-01-26 | 2010-08-10 | Battelle Memorial Institute | Methods for dehydration of sugars and sugar alcohols |
US7728156B2 (en) * | 2006-01-26 | 2010-06-01 | Battelle Memorial Institute | Method of performing sugar dehydration and catalyst treatment |
US7649099B2 (en) * | 2006-01-26 | 2010-01-19 | Battelle Memorial Institute | Method of forming a dianhydrosugar alcohol |
US7615652B2 (en) * | 2006-01-26 | 2009-11-10 | Battelle Memorial Institute | Two-stage dehydration of sugars |
BE1017157A3 (en) | 2006-06-02 | 2008-03-04 | Flooring Ind Ltd | FLOOR COVERING, FLOOR ELEMENT AND METHOD FOR MANUFACTURING FLOOR ELEMENTS. |
DE102007006442A1 (en) * | 2007-02-05 | 2008-08-07 | Evonik Oxeno Gmbh | Mixture of diesters of Dianhydrohexitolderivaten with carboxylic acids of the empirical formula C8H17COOH, process for preparing these diesters and use of these mixtures |
DE102007028702A1 (en) | 2007-06-21 | 2008-12-24 | Evonik Oxeno Gmbh | Process for the preparation of dianhydrohexitol diesters |
EP2174641A1 (en) * | 2008-10-09 | 2010-04-14 | Cognis IP Management GmbH | Oil body mixtures containing derivatives of the isosorbid |
KR101616593B1 (en) | 2008-12-19 | 2016-05-12 | 플로어링 인더스트리즈 리미티드 에스에이알엘 | Coated panel comprising foam or polyvinyl chloride and method for manufacturing |
BE1018680A5 (en) | 2008-12-19 | 2011-06-07 | Flooring Ind Ltd Sarl | METHODS FOR MANUFACTURING PANELS AND PANEL OBTAINED HEREBY |
EP2239315A1 (en) | 2009-04-09 | 2010-10-13 | Cognis IP Management GmbH | Isosorbide monoesters and their use in household applications |
US8496917B2 (en) * | 2009-11-13 | 2013-07-30 | Sytheon Ltd | Compositions and methods for improving skin appearance |
HUE044231T2 (en) | 2009-12-22 | 2019-10-28 | Flooring Ind Ltd Sarl | Method for producing covering panels |
BE1019501A5 (en) | 2010-05-10 | 2012-08-07 | Flooring Ind Ltd Sarl | FLOOR PANEL AND METHOD FOR MANUFACTURING FLOOR PANELS. |
BE1019331A5 (en) | 2010-05-10 | 2012-06-05 | Flooring Ind Ltd Sarl | FLOOR PANEL AND METHODS FOR MANUFACTURING FLOOR PANELS. |
US8925275B2 (en) | 2010-05-10 | 2015-01-06 | Flooring Industries Limited, Sarl | Floor panel |
DE102011077857A1 (en) * | 2011-06-21 | 2012-12-27 | Evonik Oxeno Gmbh | Dianhydrohexitol diester of 2-ethylheptanoic acid |
CN103747776B (en) * | 2011-08-04 | 2017-06-09 | 克拉里安特国际有限公司 | Cosmetic, dermatology or pharmaceutical compositions comprising isobide diester and ultraviolet filtering agent |
EP2758404B1 (en) * | 2011-09-19 | 2019-01-09 | Basf Se | Use of isosorbide alkyl monoesters as foam improvers in aqueous cosmetic preparations |
WO2013040662A1 (en) * | 2011-09-20 | 2013-03-28 | Dhaymers Industria E Comercie De Produtos Quimicos Ltda. | Mixture of biodegradable esters of plant origin for use as plasticiser of polymeric materials |
DE102011089495A1 (en) * | 2011-12-21 | 2013-06-27 | Evonik Industries Ag | Dianhydrohexitol diester mixture GC |
DE102011089493A1 (en) | 2011-12-21 | 2013-06-27 | Evonik Industries Ag | Dianhydrohexitol diester mixture NMR |
JP6042909B2 (en) * | 2012-01-17 | 2016-12-14 | クローダ,インコーポレイティド | Seal swelling additive |
FR2998569B1 (en) * | 2012-11-26 | 2015-01-09 | Roquette Freres | PROCESS FOR PRODUCING 1,4: 3,6-DIANHYDROHEXITOL DIESTER COMPOSITIONS |
US20170008902A1 (en) * | 2013-12-19 | 2017-01-12 | Archer Daniels Midland Company | Improved glycol acylation process with water-tolerant metal triflates |
EP2990024B1 (en) * | 2014-08-26 | 2019-09-25 | Oleon N.V. | Pigment concentrate |
KR101688859B1 (en) * | 2014-12-19 | 2016-12-23 | 주식회사 삼양사 | Anhydrosugar alcohol ester with improved color and method for preparing the same |
US10597402B2 (en) | 2015-03-27 | 2020-03-24 | Sytheon Limited | Compositions and methods for restoring epidermal integrity and function and treating dermatological diseases |
ES2826825T3 (en) | 2015-03-27 | 2021-05-19 | Symbionyx Pharmaceuticals Inc | Compositions and methods for the treatment of psoriasis |
ES2770111T3 (en) | 2015-04-24 | 2020-06-30 | Basf Se | Isosorbide diesters as pearlescent and opacifying agents |
US10517809B2 (en) | 2015-05-27 | 2019-12-31 | Basf Se | Combination of isosorbide diesters with non-ionic surfactants for use as pearlizing agent |
EP3287462A1 (en) | 2016-08-25 | 2018-02-28 | Nitto Denko Corporation | Isosorbide derivatives to treat bacterial biofilms |
BE1025875B1 (en) | 2018-01-04 | 2019-08-06 | Unilin Bvba | Methods for manufacturing panels |
CN112745328B (en) * | 2019-10-29 | 2022-05-06 | 中国科学院大连化学物理研究所 | Method for synthesizing isohexide ester |
CN113072743B (en) * | 2021-04-06 | 2022-08-30 | 杭州安誉科技有限公司 | Porous module high temperature resistant hot plate for auxiliary control device |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB613444A (en) * | 1946-01-17 | 1948-11-29 | John George Mackay Bremner | Improvements in and relating to the production of heterocyclic compounds |
DE3041673C2 (en) * | 1980-11-05 | 1983-12-08 | Maizena Gmbh, 2000 Hamburg | Process for the preparation of 1,4-anhydrotetrites, 1,4-anhydropentites or 1,4; 3,6-dianhydrohexites |
DE3119553A1 (en) * | 1981-05-16 | 1982-12-02 | Hoechst Ag, 6000 Frankfurt | "METHOD FOR PRODUCING CARBONIC ACID ESTERS OF ANHYDROHEXITES" |
JPH06116256A (en) * | 1992-10-06 | 1994-04-26 | Nikken Kasei Kk | Production of erythritan |
DK1058711T3 (en) * | 1998-03-04 | 2003-07-21 | Ato Bv | Bicyclooctane derivatives as plasticizers |
-
2000
- 2000-05-04 NL NL1015119A patent/NL1015119C2/en not_active IP Right Cessation
-
2001
- 2001-05-04 AU AU5511001A patent/AU5511001A/en active Pending
- 2001-05-04 KR KR1020027014662A patent/KR20030004382A/en not_active Application Discontinuation
- 2001-05-04 DE DE60106227T patent/DE60106227T2/en not_active Expired - Lifetime
- 2001-05-04 JP JP2001580915A patent/JP5099952B2/en not_active Expired - Fee Related
- 2001-05-04 CA CA002430090A patent/CA2430090C/en not_active Expired - Fee Related
- 2001-05-04 US US10/258,968 patent/US6693209B2/en not_active Expired - Fee Related
- 2001-05-04 WO PCT/NL2001/000342 patent/WO2001083488A1/en active IP Right Grant
- 2001-05-04 DK DK01928252T patent/DK1278752T3/en active
- 2001-05-04 EP EP01928252A patent/EP1278752B1/en not_active Expired - Lifetime
- 2001-05-04 ES ES01928252T patent/ES2228854T3/en not_active Expired - Lifetime
- 2001-05-04 AU AU2001255110A patent/AU2001255110B2/en not_active Ceased
- 2001-05-04 PT PT01928252T patent/PT1278752E/en unknown
- 2001-05-04 AT AT01928252T patent/ATE278696T1/en active
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1278752B1 (en) | Improved synthesis of anhydroglycitol esters of improved colour | |
AU2001255110A1 (en) | Improved synthesis of anhydroglycitol esters of improved colour | |
EP1999134B1 (en) | Process for the production of anhydrosugar alcohols | |
CN101896474B (en) | Prepare the method for ketal and acetal | |
US10633359B2 (en) | Preparation of macrocyclic lactones | |
EP2609070B1 (en) | Process for making acylated citrate esters | |
EA012568B1 (en) | Method of preparing monoesters of polyhydroxyl alcohols | |
CA1178288A (en) | Process for preparing anhydro polyol containing polyol mixtures | |
FR2617846A1 (en) | PROCESS FOR PREPARING ANHYDRIDES OF HEXITOLS, HEXONOLACTONES AND HEXOSIDES | |
US2759922A (en) | Direct esterification of glycosides with fatty acids | |
US6617304B1 (en) | Method for producing macrocyclic lactone | |
KR101688859B1 (en) | Anhydrosugar alcohol ester with improved color and method for preparing the same | |
US2835696A (en) | Esters of carbocyclic 1, 2-dicarboxylic acids and method of making the same | |
CA2578182C (en) | Improved synhesis of alkoxylated sucrose esters | |
KR20170114269A (en) | Esters of anhydrosugar alcohol with improved color and method for preparing the same | |
AU677918B2 (en) | Process for the production of 2-vinyl-1, 3- dioxolane | |
JPH04266884A (en) | Preparation of mixture of cyclic acrolainglycerineacetal | |
KR20180127342A (en) | Process for producing dianhydrohexitol by distillation on a thin film evaporator | |
EP0984916B1 (en) | Oligomers of fatty acids | |
US3890306A (en) | Novel acetals and methods for their preparation | |
JP2002308826A (en) | Method for producing benzyl hydroxybenzoate | |
JP2001302653A (en) | Method for producing lactone | |
JPS6328118B2 (en) | ||
JP2000229964A (en) | Pentacyclotetradecane derivative and its production | |
JPH07157451A (en) | Production of unsymmetrical diester |