WO2000075155A1 - An improved process for the preparation of alkyl polyglycosides - Google Patents
An improved process for the preparation of alkyl polyglycosides Download PDFInfo
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- WO2000075155A1 WO2000075155A1 PCT/US2000/015099 US0015099W WO0075155A1 WO 2000075155 A1 WO2000075155 A1 WO 2000075155A1 US 0015099 W US0015099 W US 0015099W WO 0075155 A1 WO0075155 A1 WO 0075155A1
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- Prior art keywords
- fatty alcohol
- mixture
- saccharide
- dispersion
- alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
Definitions
- Alkyl polyglycosides have been known for at least sixty years. They are nonionic surfactants with low toxicity and gentleness to the skin. They can be made from renewable resources and are rapidly degraded in the environment.
- alkyl polyglycosides Early processes for the preparation of alkyl polyglycosides were two-step processes.
- the first step comprised the reaction of a lower alcohol having 1 to 6 carbon atoms with a source of saccharide in the presence of an acid catalyst to form the alkyl polyglycoside.
- These alkyl polyglycosides do not have useful surfactant properties. Since water is miscible with, or highly soluble in, the alcohols, the reaction mixture can contain substantial quantities of water (see U.S. 4,721 ,780).
- the higher alkyl polyglycosides in which the aliphatic group contains from 7 to 22 carbon atoms were prepared by transacetalization of the lower glycosides with higher fatty alcohols under substantially anhydrous conditions.
- alkyl polyglycosides having alkyl groups with from 7 to about 22 carbon atoms have been prepared by a "direct process".
- a long chain fatty alcohol is reacted with a source of saccharide in the presence of an acid catalyst under conditions in which the water formed in the reaction is removed as quickly as it is formed to maintain the water content of the reaction mixture at as low a level as is reasonably possible.
- the water formed in the reaction is only slightly soluble in the fatty alcohol and any undissolved water results in the rapid formation of unwanted byproducts.
- the parameters of the "direct process” were set out in U.S. 3,839,318, which is incorporated herein by reference.
- Other patents such as U.S. 4,939,245, U.S. 4,950,743 and U.S. 5,003,057 also describe the "direct process” and are incorporated herein by reference.
- an anhydrous source of saccharide or a hydrous saccharide source mixed with an alcohol, present in stoichiometric excess is heated under reduced pressure to remove the water.
- An acid catalyst is added to the mixture of saccharide source and fatty alcohol and after the water has been substantially eliminated, the mixture is heated under reduced pressure to form the alkyl polyglycoside.
- a slurry of anhydrous saccharide and alcohol can be formed. The slurry is then added to a heated second portion of alcohol. It is preferred to use a hydrous saccharide source since hydrous saccharide sources are much less expensive than the anhydrous material.
- Sources such as 70% high dextrose syrup being liquids are easier to handle, easier to pump and significantly less expensive then the anhydrous sources presently being used, but have not been used because of the inherent problems caused by the water present. Water in the reaction is only slightly soluble in the fatty alcohol and any undissolved water results in the rapid formation of unwanted byproducts. Also high dextrose syrup is less pure then other forms of dextrose presently being used. It is therefore desirable to find a method of producing alkyl polyglycoside which can use a hydrated saccharide, such as high dextrose syrup, as a source of dextrose as a raw material in the process.
- a hydrated saccharide such as high dextrose syrup
- One aspect of the invention pertains to a process for preparing a substantially dry mixture of a saccharide in a solvent such as an alcohol.
- the first step of the process comprises mixing a dextrose syrup with an amount of
- step a second portion of a second C j _22 fatty alcohol is added to the mixture
- the third step involves allowing the dispersion to stand for a period of time sufficient to form solid particles.
- the dispersion forms as a semi solid mass which is broken into smaller particles.
- the next step comprises reducing the water content of the dispersion subsequent to the solid particles being formed by reducing the pressure to from about 100 to about 1 mm Hg and a temperature wherein the lower temperature limit is selected such that the solvent is maintained in a liquid phase.
- Another aspect of the invention pertains to a process for producing alkyl polyglycosides which utilizes the substantially dry saccharide-solvent mixture described above. This process is comprised of all of the above steps
- the present invention permits the manufacture of an alkyl polyglycoside using a relatively inexpensive liquid, high dextrose carbohydrate syrup as a raw material and the simultaneous process advantages of using an anhydrous dextrose.
- the anhydrous dextrose is formed with minimal energy requirements compared to known dehydration methods.
- fatty alcohol refers to aliphatic alcohols having from about 7 to about 22 carbon atoms.
- the alcohol may also be an alkoxylated alcohol represented by the formula:
- RO(CR 1 H-CH 2 0) y H wherein R is the residue of a fatty alcohol containing form about 7 to 22 carbon atoms, R1 is H, CH3, or-CH2-CH3 and Y is a number form 0 to 5.
- the alcohols can be saturated or unsaturated, natural or synthetic, straight chain or branched chain.
- the fatty alcohol used in the process of the invention can be a single alcohol or a mixture of alcohols.
- the fatty alcohols are aliphatic alcohols having from 8 to about 18 carbon atoms. Alcohols having aromatic or other cyclic moieties in their structure can also be reacted but the glycosides formed are generally not as biodegradable as the glycosides formed from aliphatic alcohols.
- A measured absorbence at 470 nm
- C concentration in grams per cm3
- L path length in centimeters
- a “hydrous saccharide source” refers to a reducing sugar or an oligomer or polymer comprising moieties of a reducing sugar which under the acid conditions of the process forms a reducing saccharide required to react with the alcohol.
- examples of some saccharides that can be used are any 6 carbon or 5 carbon sugars such as dextrose, mannose, xylose or arabinose.
- the term “hydrous” refers to a solid or liquid saccharide source which contains water. Materials such as dextrose monohydrate, solidified high dextrose corn syrup, liquid high dextrose corn syrup and the like have been found useful to prepare the alkyl polyglycosides by the improved process of the invention.
- alkyl polyglycoside is used to denote a composition of the formula:
- R is the residue of a fatty alcohol having from about 7 to about 22 carbon atoms; R 1 is H, CH 3 or CH 2 CH 3 , G is the residue of a reducing saccharide; y is an average number of from 0 to about 5; and x is an average number of from 1 to about 5. Preferably x is a number of from 1 to about 2.5. G is the residue of a reducing saccharide.
- the residue of a reducing saccharide can be the residue of a monosaccharide such as glucose, fructose, lactose, mannose, xylose and the like or the residue or fragments of a polysaccharide or oligosaccharide such as isomaltose, maltose, cellobiose, mellobiose, maltotriose and the like.
- the oligosaccharides can undergo transgiycosidation under the acid conditions and elevated temperature of the process to produce the reducing saccharide moieties which react with the alcohol and/or a hydroxyl of a mono or polyglycoside.
- the source of saccharides useful in the practice of the present invention are hydrous materials; that is, they contain water.
- the water may be in the form of water of crystallization or merely water which has been adsorbed on the surface of the saccharide source or the source of saccharide may be in a liquid syrup form.
- Materials such as dextrose monohydrate which contain one molecule of water for each saccharide unit and solidified high dextrose corn syrup are useful in the practice of the invention.
- the process consists of two processing steps involving a hydrous saccharide source, particularly high dextrose corn syrup (HDCS) in preparing it for an alkyl polyglycoside synthesis.
- a hydrous saccharide source particularly high dextrose corn syrup (HDCS)
- HDCS high dextrose corn syrup
- Step 1 A heated (all-liquid) hydrous saccharide such as HDCS (70-71% dissolved solids) is combined with a solvent, preferably a long chain fatty alcohol, allowed to cool and solidify as small particles in the solvent.
- Step 2 The solidified saccharide is dehydrated at low pressure and low temperature, ultimately, to the anhydrous solid state, where upon, a catalyst is added (optionally, more fatty alcohol can be added) as needed for the alkyl polyglycoside surfactant synthesis to be carried to completion.
- a catalyst is added (optionally, more fatty alcohol can be added) as needed for the alkyl polyglycoside surfactant synthesis to be carried to completion.
- solidify it is meant that the particles formed in the mixture are a combination of crystalline and amorphous particles.
- the beta-form of the dextrose molecule is the preferential form to solidify.
- 60 to 95% of the dextrose is in the beta form.
- the rate of reaction is controlled by the rate of dissolution and since the beta form is faster to dissolve than the alpha form, the beta form has a higher rate of reaction. This makes a mixture enriched in the beta form of dextrose, a preferential form for the raw material used in the reaction to form alkyl polyglycoside.
- the process according to the invention comprises the steps of: a) mixing a hydrous saccharide with a suitable first portion of a suitable solvent to form a mixture; b) combining a suitable second portion of a second suitable solvent, wherein the second solvent is an alcohol, with the mixture of step a) to form a dispersion; c) allowing the dispersion to stand for a suitable period of time sufficient to form solid particles (crystal slurry); d) reducing the size of the solid particles; e) reducing the water content of the dispersion subsequent to the solid particles being formed (dehydrated crystal slurry); f) contacting the reduced water content dispersion containing solid particles with an effective amount of acid catalyst; and g) reacting the solvent of step b) with the saccharide at a temperature of from about 80°C to about 140°C under a reduced pressure to form a reaction mixture containing the alkyl glycoside.
- a "suitable first portion" of solvent refers to the quantity of solvent with which the hydrated saccharide source is combined.
- the first portion of the solvent i.e., fatty alcohol
- the first portion of the solvent generally is less than half of the total amount of solvent present during crystallization/solidification and subsequent dehydration (steps a-e) of the hydrous saccharide.
- the first portion of the solvent comprises from about 5% to about 45% and more preferably about
- Alcohol can be added to the dehydrated crystal slurry before the addition of the catalyst
- a "suitable second portion" of solvent refers to the quantity of solvent in which the hydrated saccharide source is dispersed.
- the second portion of the solvent i.e., fatty alcohol
- the second portion of the solvent generally is more than half of the total amount of solvent present during crystallization/solidification and subsequent dehydration (steps a-e) of the hydrous saccharide.
- the second portion of the solvent comprises from about 55% to about 95% and more preferably about 80% to about 90% of the amount of the total solvent present in the crystal slurry.
- first suitable solvent and the second suitable solvent can be the same solvent.
- a pressure of about 100 mm Hg or less can be used to remove the water from the saccharide slurry, preferably at a pressure below about 50 mm Hg, if the solvent is an alcohol containing at least 10 carbon atoms.
- the pressure at which the water removal is accomplished is dependent upon the solvent used in the process and is preferably in the range at which the reaction between the alcohol and saccharide source is to be carried out.
- the pressure is preferably in the range of from about 1 mm Hg to about 100 mm Hg, more preferably in the range of from about 5 mm Hg to about 70 mm of Hg.
- the reaction between the alcohol and saccharide source is carried out in the same pressure range.
- the reduced pressure is useful in reducing the amount of water in the mixture to a level at which the likelihood of unwanted side reactions is low and the process is directed to formation of the alkyl polyglycoside.
- the lower limit of the temperature is selected such that the solvent remains liquid.
- the temperature is maintained below 30 degrees C for the initial water removal and then can be increased in the later stages to from about 80 degrees C to about 140 degrees C.
- the lowest temperature must be above the freezing point of the alcohol mixture at the working pressure.
- a mixture of saccharide source and fatty alcohol containing an amount of water which approaches the equilibrium moisture content under the conditions of temperature and pressure is considered as substantially anhydrous.
- the preferred compositions generally contain less than 1% by weight water, preferably less than 0.5% by weight water. The amount of water present in the mixture depends upon the alcohol present and the temperature and pressure under which the mixture is maintained.
- the fatty alcohol present in the reacting mixture ranges from more than 1 mole of fatty alcohol per mole of the reducing saccharide residue to a practical limit of about 15 moles of fatty alcohol per mole of reducing saccharide residue.
- the amount of fatty alcohol in the reacting mixture ranges from about 1.5 moles to about 8 moles and most preferably from about 2 to about 7 moles and more preferably from about 2.5 to about 5 moles of fatty alcohol per mole of reducing saccharide residue.
- the fatty alcohol is always present in stoichiometric excess during the reaction.
- the ratio of fatty alcohol to reducing saccharide residue during the alkyl polyglycoside reaction is generally maintained at a point at which the reacting mixture has sufficient fluidity so that it can be adequately heated, pumped and stirred to keep the undissolved source of saccharide in suspension and to permit the water formed in the reaction to be rapidly removed from the reacting mixture.
- the ratio of moles of fatty alcohol to moles of reacted reducing saccharide residue in the reacting mixture also impacts the degree of polymerization (DP) or the value of x in the alkyl polyglycoside product.
- the mixture is heated to a temperature in the range of the reaction temperatures.
- the reaction between a fatty alcohol and a source of reducing saccharide is generally carried out in the range of from about 80°C to about 140°C, and preferably in the range of from about 95°C to about 125°C and most preferably from about 100°C to about 120°C.
- the reduced pressure which can be maintained on a C 7 alcohol is higher than one which can be maintained when a C 22 fatty alcohol is utilized as the reactant.
- the pressure must be as low as possible without boiling a substantial amount of the fatty alcohol from the reaction mixture.
- the mixture of the anhydrous saccharide in the fatty alcohol produced by the crystallization and subsequent dehydration of the hydrous saccharide source is heated until the alkylpolyglycoside reaction temperature range is attained.
- the water has been reduced to a level at which undissolved water is minimal in the reaction mixture and most preferably to a level as low as is commercially practical.
- Water content can be further lowered by the use of an inert gas sweep over the crystallized mixture during the water removal step.
- inert gases that can be used for the sweep include but are not limited to nitrogen, helium, carbon dioxide and hydrogen. All of the water cannot be removed from the mixture under any reasonable conditions and therefore a small amount of water is always present in the reacting mixture.
- an acid catalyst is introduced into the mixture.
- the acid catalysts useful in the practice of the present invention are well known materials.
- examples of inorganic acids useful as the acid catalyst in the practice of the present invention include, but are not limited to, sulfuric acid, phosphoric acid, hydrochloric acid, and the like, and mixtures thereof.
- organic acids useful as the acid catalyst in the practice of the present invention include, but are not limited to trifluoroacetic acid, paratoluene sulfonic acid, sulfosuccinic acid, cumene sulfonic acid, sulfonated fatty acids and sulfonated fatty acid esters, acid forms of surfactants such as mono- or di-alkyl benzene sulfonic acids, fatty alcohol sulfates, alkoxylated fatty alcohol sulfates, alkylsulfonates, alkyl esters of sulfosuccinic acid, mono- or di-alkyl naphthalene sulfonates wherein the alkyl group or groups contain more than a total of about 8 carbon atoms, and preferably in the range of 16 to about 32 carbon atoms, acid forms of resins and other known acid catalysts for the acetalization of reducing saccharides by fatty alcohols, and mixtures thereof
- the reacting mixture is well agitated and maintained at the reaction temperature in the range of from about 80°C to about 140°C under a reduced pressure to remove the water formed in the reaction substantially immediately as it is formed.
- the mixture of fatty alcohol and saccharide source is in the required temperature range, as soon as the acid catalyst is introduced into the mixture, the fatty alcohol begins reacting with the saccharide source to form water and the alkyl polyglycoside.
- a temperature lower than reaction temperature is selected for catalyst addition. After catalyst addition, the temperature is raised to promote the desired reaction rate.
- the reaction is carried out for a sufficient length of time to react the source of saccharide present in the reaction mixture with the fatty alcohol to form the alkyl polyglycoside.
- degree of polymerization the number of glycoside residues which are polymerized and attached to an aliphatic group
- reaction time, temperature and pressure is determined by: 1. structure and the excess of the fatty alcohol; 2. the amount and type of catalyst utilized; and 3. reaction time, temperature and pressure. The effect of these variables is known in the art and will not be discussed here.
- the mixture of the saccharide source and the fatty alcohol is reacted for from about 1 to about 15 hours after the acid catalyst has been introduced into the mixture.
- the reaction is carried out until the amount of unreacted saccharide source in the mixture has reached a predetermined level.
- the amount of unreacted saccharide source in the reaction mixture is less than about 5% by weight of the alkyl polyglycoside formed and preferably less than about 2% by weight of the alkyl polyglycoside formed and most preferably less than 0.25% by weight of the alkyl polyglycoside formed.
- the reaction mixture can be cooled. After the reaction mixture has been cooled to a predetermined temperature, the reaction mixture can be transferred to the product recovery portion of the process for further treatment.
- the reaction can be run as a batch or continuous process.
- a neutralizing material such as an alkali metal hydroxide, alkali earth metal oxide, alkali earth metal hydroxide or a mixture thereof can be added to neutralize the acid catalyst.
- the neutralized mixture is then passed to a means for separating the unreacted fatty alcohol to recover the alkyl polyglycoside and the alkyl polyglycoside can be mixed with water and/or further treated to reduce the color, stabilize the color and dilute the material to the concentration at which it is to be sold.
- the alkyl polyglycosides are sold as aqueous mixtures containing from about 30% to about 80% by weight of the active surfactant material.
- the important parameters of the process are the formation of a slurry of a hydrous source of reducing saccharide in a first portion of fatty alcohol, introducing the slurry of the hydrous saccharide source in the first portion of the fatty alcohol into a second portion of fatty alcohol, agitating, allowing sufficient time for the saccharide to solidify, and breaking any semi solid mass formed into smaller particles. Water is removed from the fatty alcohol containing the now solidified hydrous saccharide under a reduced pressure and at a low temperature for the initial stages of water removal and then at an elevated temperature for later stages of water removal.
- the temperature is generally maintained at a level such that water can be removed from the mixture but the hydrous saccharide does not liquefy.
- the mixture of fatty alcohol and saccharide is contacted with an effective amount of an acid catalyst and the temperature is raised to, or maintained in, the range for reaction between the alcohol and saccharide.
- the mixture is reacted at an elevated temperature and reduced pressure to form the alkyl polyglycoside.
- the alkyl polyglycoside containing mixture is generally further treated to neutralize the acid catalyst, separate the excess or unreacted fatty alcohol from the alkyl polyglycoside product, mix with water, reduce the level of color of the product, stabilize the color and adjust the concentration of the alkyl polyglycoside to the concentration and pH level at which it is sold.
- the acid can be neutralized with alkali metal hydroxides, alkaline earth metal oxides or hydroxides, aluminum hydroxide or oxide or mixtures thereof.
- the unreacted fatty alcohol can be separated from the alkyl polyglycoside product by solvent extraction, low pressure evaporation such as in a thin film evaporator, wiped film evaporator and the like, such as by the method described in U.S. patents 5,304,639 and 5,480,978, the contents of each of which is incorporated herein by reference.
- the product can be treated to reduce and stabilize the color before or after separation of the fatty alcohol from the neutralized reaction mixture, such as by the method described in U.S.
- the fatty alcohol is removed from the product before the product is treated to reduce and stabilize the color.
- the color level can be reduced by known oxidation means such as hypochlorite bleaching, peroxide bleaching, ozone treatment, alkali metal borohydride addition and the like.
- a 5 liter, 4 neck flask was equipped with a mechanical stirrer, thermometer, nitrogen purge capillary, vapor takeoff assembly train including a cold H 2 O condenser, and graduated receiver. Vacuum was provided by recycle aspirator, heat by an electric mantle, as required. An addition funnel was provided for catalyst addition and a rubber septum for hypodermic sampling.
- the carbohydrate was a high dextrose corn syrup (HDCS) with a nominal dextrose equivalent value of 95 and nominally 71 wt% dissolved solids. To be in an all liquid state HDCS, all of the dextrose must be melted. This temperature can be readily determined by one skilled in the art. At lower temperatures HDCS solidifies.
- HDCS high dextrose corn syrup
- EXAMPLE 3 Crystallization with a C8-C10 Alcohol.
- the dehydration of the resulting crystal slurry from example 3 has a Temperature Profile and a Water Removal Profile comparable to Example 2 which are shown in Table 2.
- LOROL® 1214A is a fatty alcohol nominally comprising 67% C12, 27% C14, 6%
- Alcohol is liquid.
- Alcohol is liquid.
- example 1 The procedure of example 1 was used. Three moles of HDCS was crystallized in LOROL® 1214A while trying to maintain a temperature of 25°C to 27°C. After 9 hours the temperature decreased to 24°C. A liquid-crystal slush resulted. This was stirred and dehydrated.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001502436A JP2003501438A (en) | 1999-06-08 | 2000-06-01 | Improved method for preparing alkyl polyglycosides |
AU54564/00A AU5456400A (en) | 1999-06-08 | 2000-06-01 | An improved process for the preparation of alkyl polyglycosides |
EP00939484A EP1183264B1 (en) | 1999-06-08 | 2000-06-01 | An improved process for the preparation of alkyl polyglycosides |
BR0011389-1A BR0011389A (en) | 1999-06-08 | 2000-06-01 | Process for the production of polyglycoside alkyl, method for producing a substantially dry mixture of a suitable saccharide and solvent, and process for producing polyglycoside alkyl |
DE60044900T DE60044900D1 (en) | 1999-06-08 | 2000-06-01 | AN IMPROVED METHOD FOR THE PRODUCTION OF ALKYLPOLYGLYCOSIDES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/327,932 | 1999-06-08 | ||
US09/327,932 US6204369B1 (en) | 1999-06-08 | 1999-06-08 | Process for the preparation of alykl polyglycosides |
Publications (1)
Publication Number | Publication Date |
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WO2000075155A1 true WO2000075155A1 (en) | 2000-12-14 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2000/015099 WO2000075155A1 (en) | 1999-06-08 | 2000-06-01 | An improved process for the preparation of alkyl polyglycosides |
Country Status (8)
Country | Link |
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US (1) | US6204369B1 (en) |
EP (1) | EP1183264B1 (en) |
JP (1) | JP2003501438A (en) |
AU (1) | AU5456400A (en) |
BR (1) | BR0011389A (en) |
DE (1) | DE60044900D1 (en) |
ES (1) | ES2351954T3 (en) |
WO (1) | WO2000075155A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0814093B1 (en) * | 1996-06-19 | 2003-05-07 | Canon Kabushiki Kaisha | Polymeric compound comprising glycopolymer and a method for decomposing the same |
US20060122355A1 (en) * | 2004-10-15 | 2006-06-08 | O'connor James | Derivatized highly branched polysaccharide and a mix for production of polyurethane thereof |
US7465757B2 (en) * | 2004-10-15 | 2008-12-16 | Danisco A/S | Foamed isocyanate-based polymer, a mix and process for production thereof |
CA2584201C (en) * | 2004-10-15 | 2014-12-23 | Danisco A/S | A foamed isocyanate-based polymer, a mix and process for production thereof |
NZ584758A (en) * | 2007-10-16 | 2013-03-28 | Tyco Fire Products Lp | Fire extinguishing composition comprising fluoroalkenyl poly[1,6]glycosides |
US8735460B2 (en) | 2009-01-09 | 2014-05-27 | DuPont Nutrition BioScience ApS | Foamed isocyanate-based polymer, a mix and process for production thereof |
RU2488588C1 (en) * | 2012-05-24 | 2013-07-27 | Общество с ограниченной ответственностью Научно-производственное объединение "НИИПАВ" | Method of producing modified alkyl polyglucoside |
WO2021158932A1 (en) * | 2020-02-06 | 2021-08-12 | Cargill, Incorporated | Glucose in solid form and process for manufacturing glucose in solid form |
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1999
- 1999-06-08 US US09/327,932 patent/US6204369B1/en not_active Expired - Lifetime
-
2000
- 2000-06-01 BR BR0011389-1A patent/BR0011389A/en not_active IP Right Cessation
- 2000-06-01 JP JP2001502436A patent/JP2003501438A/en active Pending
- 2000-06-01 WO PCT/US2000/015099 patent/WO2000075155A1/en active Application Filing
- 2000-06-01 AU AU54564/00A patent/AU5456400A/en not_active Abandoned
- 2000-06-01 ES ES00939484T patent/ES2351954T3/en not_active Expired - Lifetime
- 2000-06-01 EP EP00939484A patent/EP1183264B1/en not_active Expired - Lifetime
- 2000-06-01 DE DE60044900T patent/DE60044900D1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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AU5456400A (en) | 2000-12-28 |
EP1183264B1 (en) | 2010-09-01 |
JP2003501438A (en) | 2003-01-14 |
BR0011389A (en) | 2002-03-05 |
EP1183264A1 (en) | 2002-03-06 |
ES2351954T3 (en) | 2011-02-14 |
US6204369B1 (en) | 2001-03-20 |
DE60044900D1 (en) | 2010-10-14 |
EP1183264A4 (en) | 2002-09-18 |
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