Europaisches Patentamt 0 338 151 European Patent Office v\) Publication number: A1 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 88303525.5 © int. Ci.4: C07H 15/04 @ Date of filing: 19.04.88 © Date of publication of application: © Applicant: HENKEL CORPORATION 25.10.89 Bulletin 89/43 300 Brookside Avenue Ambler Pennsylvania 19002(US) © Designated Contracting States: AT BE CH DE ES FR GB GR IT LI LU NL SE @ Inventor: McDaniel, Robert S., Jr. 968 Montgomery Court Oecatur Illinois 62526(US) Inventor: McCurry, Patrick M. 3146 Lake Bluff Drive Decatur Illinois 62521 (US) Inventor: Short, Rolland W.P. 2657 Gregory Court Decatur Illinois 62526(US) Inventor: Glor, Paul R. 448 Ewing Avenue Decatur Illinois 62522(US) ©" Representative: Harle, Horst, Dr. et al c/o Henkel KGaA TFP/Patentabteilung Postfach 1100 Henkelstrasse 67 D-4000 Dusseldorf(DE) © Decolorization of glycosides. © Hydrogenation of a glycoside composition is ef- fected to reduce the color of the composition. < in CO Xerox Copy Centre EP0 338 151 A1 Decolonization of glycosides This patent deals with the decolorization of the average polysaccharide chain length exceeds glycosides which are useful as surfactants and for about 20. United States Patent 4,393,203 to Leslie other purposes. issued July 12, 1983 describes the treatment of Glycosides are known to have several uses glycosides with a wipe film evaporator to assist in including their incorporation into detergent products 5 color reduction. Rau in United States Patent as nonionic surfactants. Lower glycosides, that is 4,465,828 issued August 14, 1984 suggests using those materials having a short hydrophobic moiety hydroxy carboxylic acids to minimize color forma- attached to the saccharide backbone as later de- tion when preparing glycosides. scribed, are useful as intermediates for manufactur- A general method of preparing glycosides is ing higher glycosides. The lower glycosides are 70 found in Untied States Patent 3,219,656 to Boettner also useful for such purposes as mold release issued November 23, 1965. Descriptions of produc- agents, for polymers which require a hydroxyl func- ing alkyl glycosides are also found in United States tionality, and as a formaldehyde scavenger in var- Patent 3,547,828 to Mansfield issued December ious products which utilize formaldehyde as a reac- 15, 1970 and United States Patent 3,598,865 to tant. 75 Lew issued August 10, 1971. Roth also describes Glycosides are typically formed from a lower the preparation of glycosides in United States Pat- saccharide which may be either monomeric or ent 4,223,129 issued September 16, 1980. polymeric with regard to the saccharide unit. For It is also known that glycosides may be decol- reasons which are not fully understood the orized by using a bleaching material. Suitable glycosides obtained from most processes are dark 20 bleaches include materials such as hydrogen per- colored. The color ranges from dark yellow to cof- oxide for bleaching. It has been observed, however, fee black depending upon the conditions under that upon exposure to high temperature, a which the glycoside is produced. The color is not bleached glycoside product can revert to a darker inherent to the glycoside per se but rather to the color product upon standing. presence of humins which are co-produced with 25 • Hydrogenation of saccharides to form polyols ' the glycoside. ■ has been known as evidenced by Kool in United It has been suggested that the color bodies States Patent 2,609,399 issued September 2, 1952. (humins) in the glycoside composition may be re- It is not the intent of the present invention to form moved by adsorption with resinous components. polyols by hydrogenation as this destroys the ke- This process requires that the entire glycoside 30 tone and aldehyde functionality desired for composition be mixed with a resin in sufficient glycoside formation. volume to substantially remove the color forming It has now been discovered that hydrogenation, materials. preferably catalytic hydrogenation, of a glycoside It has also been suggested that the color bod- composition can substantialy reduce the color. The ies present in a glycoside composition may be 35 hydrogenation of the glycoside composition ac- eliminated by treatment with various reducing ac- cording to the present invention allows for consid- ids. The acid reduction has its limitations in that the erably greater stability after color removal than acidic material must be neutralized or removed does bleaching. That is, the hydrogenation of the from the end products. This is the case with laun- color forming bodies in the glycoside composition dry detergents. Typically laundry detergent pro- 40 leads to a more stable product than does bleaching ducts are formulated in the alkaline pH range to which gives products capable of reversible reac- facilitate removal of body soil. Thus while there is tions. some market for glycosides in the acid pH range it Throughout the specification and claims per- is desired not to incorporate any more acid than is centages and ratios are by weight, temperatures necessary. For a description of the use of reducing 45 are degrees Celsius and pressures are in KPascals acids to produce glycosides see European Patent unless otherwise indicated. To the extent that any Application No. 82305286.5 to Arnaudis published of the references mentioned in this application are as 0 077 167 on April 20, 1983. applicable to the present invention they are herein Further discussion of treating a glycoside com- incorporated by reference. position to reduce color is found in European Pat- so In one aspect, the present invention provides a ent Application No. 83200572.2 to Mao published process for reducing the color of a glycoside com- as 0 092 875 on November 2, 1983. In Mao the position containing colored humins having conju- acid catalyst employed is stated to be destroyed gated unsaturation, characterized in that said pro- after at least 90% of the short chain alkyl monosac- cess comprises subjecting said composition to hy- charide (glycoside) has been destroyed and before drogenating conditions whereby to decrease the EP 0 338 151 A1 color of components of said composition, conve- ably from about 2 to about 18 carbon atoms. Spe- niently by contacting said composition with hy- cific alcohols which may be utilized herein include drogen or a hydrogen source under humin hy- methyl, ethyl, propyl, isopropyl, butyl, pentyl, drogenating conditions preferably in the presence hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, of a hydrogenation catalyst, and, if appropriate, by 5 tridecyl, tetradecyl, pentadecyl, hexadecyl, hep- subsequently recovering the glycoside composition tadecyl, and octadecyl. herein of reduced color, e.g. after separating any hy- Further alcohols which may be utilized drogenation catalyst from the composition. In the include benzyl alcohol, phenol, and the sterol al- cholesterol, sitosterol, stig- process of the invention, the step of subjecting the cohols including glycoside composition to hydrogenating conditions, io masterol, and the like. Also valuable herein are both aromatic and aliphatic e.g. a step of contacting the composition with hy- alcohols containing an drogen or a hydrogen source and, preferably, a structure such as nonylphenol. Similarly, alkoxylat- hydrogenation catalyst under hydrogenation con- ed alcohols may be utilized which include materials ditions is effected for sufficient time to effect a such as the ethylene and propylene oxide adducts decrease in the color of the composition but prefer- 75 of any of the aforementioned alcohols or the poly- ably is not effected for so long or under such merized forms of the aforementioned oxides, e.g. conditions as to cause substantial polyol formation. polyethylene glycol or polypropylene glycol. Typically, hydrogenation times where a catalyst is The glycosides which are suggested for use in selected from used will range from 5 minutes to 16 hours, prefer- the present invention include those ably 10 minutes to 12 hours, especially 15 minutes 20 the group consisting of fructoside, glucoside, man- to 9 hours and more particularly 30 minutes to 6 noside, galactoside, taloside, aldoside, altroside, hours. idoside, arabinoside, xyloside, lyxoside and In a further aspect, the invention provides a riboside and mixtures thereof. Preferably the glycoside composition containing hydrogenated glycoside is a fructoside and most preferably a humins. 25 glucoside. All of the aforementioned glycosides with The glycoside may be obtained through, for may be obtained from sugars (saccharides) example, the methods of the Mansfield, Lew, Boett- the preferential fructose and glucose starting ma- ner or Roth patents previously incorporated by terials being obtained from corn syrup. Complex reference. A glycoside is a material containing a glycosides, those containing one or more different saccharide structure which may be represented by 30 saccharide units, may also be used as starting the formula materials. ,; R(OG)X The glycoside has the ability to utilize the where R is a hydrophobic moiety, 0 an oxygen monomeric saccharide unit to promote chain atom and (G) is the saccharide structure growth of the glycoside. Thus x in the above for- (backbone) of the glycoside. The value x is the 35 mula may vary between 1 and 10, preferably from number of monosaccharide units in the glycoside. about 1.2 to about 5, and most preferably from The value also be The oxygen atom shown in the formula above about 1.3 to about 3.5. x, may is typically derived from an alcohol with R being referred to as the degree of polymerization (DP.) the hydrophobic moiety of the alcohol. The oxygen of the glycoside. This number is an average de- atom is attached to the saccharide in an ether 40 gree of polymerization. In obtaining a glycoside, linkage. Where the aldehyde or ketone structure of polymerization of the monosaccharide units occurs the saccharide is involved in the glycoside forma- to some extent usually through a 1,6 linkage.