Patent Publication Number: US-2023159664-A1

Title: Mechanical treatment of polysaccharide with hydrophobic alcohol

Description:
The present invention relates to a process for the preparation of an alkyl polyglycoside comprising the step of mechanically treating a polysaccharide in the presence of an acid and a hydrophobic alcohol, wherein the mechanical treatment is effected by grinding, extruding or kneading. The invention further relates to an alkyl polyglycoside obtainable by said process. 
     Alkyl polyglycoside (also called APG) are important industrial non-ionic surfactants. They are usually biodegradable and based on biological raw materials, such as monoaccharides and fat. 
     There are two typical methods of making AGP. Either these are in a direct synthesis from glucose and e.g. via Fischer acetalization from monosaccharides like glucose or highly degraded glucose syrup and fatty alcohols. This happens at temperatures of 120° C. and a pressure of 2,000 Pa. D 
     Alternatively, APG can also be prepared in two stages via a transacetylation. First, the reaction takes place with a short-chain alcohol, e.g. butanol at about 115° C. and normal pressure for glucose and 140° C. and 400,000 Pa for starch instead of raw material. In a second reaction, the short chain alkyl glucoside with a fatty alcohol, e.g. dodecanol, at temperatures of 120° C. and a pressure of 2,000 Pa to a long-chain alkyl glucoside. 
     Object was to develop a process for the preparation of an alkyl polyglycoside, which offers advantages over the prior art: no excess of hydrophobic alcohol required, allows the suppression of insoluble polydextrose, APG can be made with hydrophobic alcohols having higher than C 14  alkyl chains, non-edible sources of carbohydrates can be used, the APG have a high water solubility, the APG have a higher degree of polymerization, the APG have a high HLB value, and the APG have a high emulsification efficiency. 
     The object was solved by a process for the preparation of an alkyl polyglycoside comprising the step of mechanically treating a polysaccharide in the presence of an acid and a hydrophobic alcohol. The object was also solved by an alkyl polyglycoside obtainable by said process. 
     The hydrophobic alcohol may be linear or branched, saturated or unsaturated C 1 -C 22  (preferably C 1 -C 18  in particular C 10 -C 16 ) aliphatic alcohol, or mixtures thereof. The hydrophobic alcohol can be a linear or branched C 1 -C 22  alkanol, preferably a C 1 -C 18  alkanol, or in particular a C 10 -C 16  alkanol or mixtures thereof. In another form t the hydrophobic alcohol can be a linear or branched C 6 -C 22  alkanol, preferably a C 8 -C 18  alkanol. In another form the hydrophobic alcohol is a fatty alcohol, or mixtures thereof. Suitable hydrophobic alcohols are the primary alcohols of methanol, ethanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol or mixtures thereof. 
     The molar ratio of the hydrophobic alcohol to the monomeric units of the polysaccharide is usually from 1:10 to 10:1, preferably from 1:10 to 1:1. 
     Usually, 0.01 to 20 mmol, preferably 0.1 mmol to 6.2 mmol, of the hydrophobic alcohol are present per g polysaccharide. 
     The mechanical treatment can be effected by grinding, extruding or kneading, preferably by grinding. Grinding can by made by mills, such as swing mills, stirred mills, stirred-media mills, vibration mills, agitator mills, agitator ball mills, hammer mills or ball mills, where ball mills are preferred. In ball mills a speed of 400 to 1200, preferably 800 to 1000 rpm is suitable. For vibration mills a frequency of 1 to 50 Hz is suitable. 
     The mechanical treatment can be made for up to 48, 24, 18, 14, 12, 10, 8, 6, 4, 3, 2, 1, or 0.5 hours. Usually, the mechanical treatment be made for 1 min to 12 hours, preferably from 30 min to 6 hours. 
     The mechanical treatment is often made at a reaction temperature of below 300, 250, 200, 150, 130, 120, 110, 100, 90, 80, 70, 60, or 50° C., for example in a range of 0 to 300° C., preferably 0 to 150° C. 
     The polysaccharide may be present in form of a purified polysaccharide or a polysaccharide-containing material (e.g. natural products like wood (e.g. from spruce, pine, birch, beech, poplare), grass, hay, sprucewood, sugarcane bagasse, cotton, bast fibers). 
     Suitable polysaccharides are homopolysaccharides (e.g. amylose, cellulose, dextran, pectin) and heteropolysaccharides (e.g. guar, xanthan, chitosan, chitin), such as starch, cellulose, hemicellulose or guar, preferably starch or cellulose. In a preferred form the polysaccharide is alpha-cellulose. 
     The polysaccharide is preferably derived from cellulose, which may be present in form of a purified cellulose or a cellulose-containing material (e.g. natural products like wood, grass, hay, cotton). 
     The polysaccharide may have a degree of polymerization of at least 50, 100, 200, 300, 400, 500, 1000, 2000 or 5000. The polysaccharide may have a degree of polymerization of up to 10 000, 8000, 6000, 4000, 2000 or 1000. The polysaccharide may have a degree of polymerization of 100 to 2000, or 300 to 1200, or 500 to 800. The degree of polymerization may be determined by known methods, such as gel permetion chromatography, viscosimetry or carbonyl number. 
     The polysaccharide has usually a solubility in water at 25° C. of up to 1, 0.5, 0.3, or 0.1 g/l. 
     The polysaccharide is usually a solid at 20° C. The polysaccharide may have a residual moisture (e.g. from water) content of less than 20, 15, 10, 8, 6, 4, 2, or 1 wt %. The polysaccharide may have a solids content of at least 50, 70, 80, 85, 90, 92, or 95 wt. 
     The acid may be inorganic or organic acid, preferably an inorganic acid, such as mineral acids. 
     The acid may have a pK a  of of below 2, preferably below −2. Preferably, the acid is an inorganic acid which has a pK a  of below 2, preferably below −2. 
     Suitable acids are sulfuric acid, hydrochloric acid, sulphur dioxide, sulphur trioxide, phosphoric acid, phosphotungstic acid, halo-alkanecarboxylic acid (e.g. trifluoroacetic acid), benzenesulfonic acids and derivatives thereof, methanesulfonic acid, oxalic acid and nitric acid. 
     Preferred acids are sulfuric acid, hydrochlorid acid, and methane sulfonic acid. 
     The acid may be present in liquid or gaseous form (e.g. as gaseous HCl). 
     The acid can be used in catalytic amounts. Typically, the acid is present in an amount of 0.0001 to 10 mmol per g, or 0.001 to 1 mmol per g, or 0.01 to 1 mmol per g of polysaccharide. 
     The process comprises the step of mechanically treating the polysaccharide in the presence of the acid and the hydrophobic alcohol. 
     The the polysaccharide, the acid and the hydrophobic alcohol can be mixed in any order. They may be mixed before or during the mechanical treatment. 
     In one form the hydrophobic alcohol and the acid are premixed, and this premix mixed with the polysaccharide before or during the mechanical treatment. 
     In a preferred form the acid is contacted with the polysaccharide before the mechanical treatment to prepare an acid impregnated polysaccharide. 
     The acid impregnated polysaccharide may be obtainable by treating the polysaccharide with the acid in an organic solvent. Suitable organic solvents are water, C 1 -C 22  alkanols (e.g. methanol, ethanol, or the hydrophobic alcohol), alkyl ether (e.g. dimethylether, diethylether, methylethylether, tert-butylmethylether), C 4-18  alkanes (e.g. pentane, hexane, heptane), supercritical carbon dioxide, dichloromethane, tetryhydrofurane, ethyl acetate, methyl acetate or acetone. Preferably, the organic solvent is methanol or the hydrophobic alcohol (e.g. C 6 -C 22  alkanol, preferably a C 8 -C 14  alkanol). In a preferred form the organic solvent is methanol or ethanol. In another preferred form the organic solvent is the same as the hydrophobic alcohol. 
     The organic solvent can be removed (e.g. by filtration or evaporation) in part or completely before or during the mechanical treatment of the acid impregnated polysaccharide in the presence of the hydrophobic alcohol. In one form the organic solvent is identical to the hydrophobic alcohol, and this form the organic solvent is not removed. 
     In another form the acid impregnated polysaccharide may be obtainable by treating the polysaccharide with the acid in the absence of the organic solvent. In this form the acid may be present in gaseous form, preferably as gaseous HCl or gaseous SO 3 . 
     The acid impregnated polysaccharide can be prepared by treating of the polysaccharide with the acid from 1 min to 72 h, or from 10 min to 24 h, or from 30 min to 5 h. The treating of the polysaccharide with the acid may be made at a temperature from 0 to 150° C., or 5 to 100° C., or 5 to 40° C. 
     The acid impregnated polysaccharide is usually a solid at 20° C. The acid impregnated polysaccharide may have a residual moisture (e.g. from the organic solvent or water) content of less than 20, 15, 10, 8, 6, 4, 2, or 1 wt %. The acid impregnated polysaccharide may have a solids content of at least 50, 70, 80, 85, 90, 92, or 95 wt. 
     Typically, an alkyl polyglycoside is obtainable by the process according to the invention. The alkyl polyglycoside may have a degree of polymerization in the range of 1 to 50, or 1 to 30, or 1.1 to 30 or 1.2 to 20. The alkyl polyglycoside may have a degree of polymerization of above 1, 1.1 or 1.2. The alkyl polyglycoside may have a degree of polymerization of up to 20, 15, 10, 5, 4, 3, 2, 1.9, 1.8, 1.7, 1.6 or 1.5. 
     The alkyl polyglycoside may have a solubility in water at 25° C. of at least 0.5, 1, 2, 3, 5, 10 or 50 g/l. 
     The alkyl polyglycoside can be used as surfactant in any applications where alkyl polyglycosides according to the state of the art are already used, such as in home care, cosmetics, personal care, pharmaceuticals, detergents, cleansers, or in industrial applications, e.g. in emulsion polymerization. 
    
    
     EXAMPLES 
     Example 1—Impregnated α-cellulose 
     Impregnation: 
     In a one liter one-neck flask 3.1 g sulfuric acid (96%) was dissolved in 300 g methanol. After adding 33 g α-cellulose (solid content: 93.3%, degree of polymerization about 500 to 700, commercially available from Sigma-Aldrich GmbH, Germany) to the acidic methanol solution, the suspension was stirred at room temperature for an hour. The solvent was evaporated at 50° C. and 10 mbar using a rotary evaporator. The residue was homogenized by mortar and pistil. 
     A) Mechanical Treatment with Cool Down 
     4 g of the acid impregnated cellulose and 0.5 g 1-octanol were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled together with a 15 mm diameter WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 30 min. The residue was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS, which confirmed the octylization of the cellulose. 
     B) Mechanical Treatment without Cool Down 
     4 g of the acid impregnated cellulose and 0.5 g 1-octanol were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled without interruption together with a 15 mm diameter WC-ball at 30 Hz for overall 4.5 h by Retsch MM400. The residue (Sample B) was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS, which confirmed the octylization of the cellulose. 
     MALDI(+)-MS Analysis 
     The MALDI(+)-MS analysis of the reaction products of was made on a Bruker UltrafleXtreme TOF/TOF, Reflectron-Mode. Sample preparation: 6 μL of the aqueous sample solution were mixed with a spatula tip of 2,5-Dihydroxybenzoic acid (DHB) and 1 μL aq. NaCl solution using mortar and pistil. Peaks for the following structures (FIG. 3) were detected: Octylpolyglycoside, methylpolyglycoside and polyglycoside. Tables 1 and 2 summarize the peaks detected for the respective species for Example 1 A and 1 B. 
     
       
         
         
             
             
         
       
     
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Detected MS-signals of Example 1 A 
               
            
           
           
               
               
               
               
            
               
                   
                 m/z 
                 m/z 
                 m/z 
               
               
                   
                 (Octylpolygycoside + 
                 (Methylpolyglycoside + 
                 (Polyglycoside + 
               
               
                 n 
                 Na + ) 
                 Na + ) 
                 Na + ) 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 315 
                 217 
                 203 
               
               
                 2 
                 477 
                 379 
                 365 
               
               
                 3 
                 639 
                 541 
                 527 
               
               
                 4 
                 801 
                 703 
                 689 
               
               
                 5 
                 963 
                 865 
                 851 
               
               
                 6 
                 1125 
                 1027 
                 1013 
               
               
                 7 
                 1287 
                 1189 
                 1175 
               
               
                 8 
                 1450 
                 1351 
                 1337 
               
               
                 9 
                 1612 
                 1513 
                 1499 
               
               
                 10 
                 1774 
                 1676 
                 1661 
               
               
                 11 
                 1936 
                 1838 
                 1824 
               
               
                 12 
                 2098 
                 2000 
                 1986 
               
               
                 13 
                 2260 
                 2162 
                 2148 
               
               
                 14 
                 — 
                 2324 
                 — 
               
               
                 15 
                 — 
                 2486 
                 — 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Detected MS-signals of Example 1 B 
               
            
           
           
               
               
               
               
            
               
                   
                 m/z 
                 m/z 
                 m/z 
               
               
                   
                 (Octylpolygycoside + 
                 (Methylpolyglycoside + 
                 (Polyglycoside + 
               
               
                 n 
                 Na + ) 
                 Na + ) 
                 Na + ) 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 315 
                 217 
                 203 
               
               
                 2 
                 477 
                 379 
                 365 
               
               
                 3 
                 639 
                 541 
                 527 
               
               
                 4 
                 801 
                 703 
                 689 
               
               
                 5 
                 963 
                 865 
                 851 
               
               
                 6 
                 1125 
                 1027 
                 1013 
               
               
                 7 
                 1287 
                 1189 
                 1175 
               
               
                 8 
                 1450 
                 1351 
                 1337 
               
               
                 9 
                 1612 
                 1513 
                 1499 
               
               
                 10 
                 1774 
                 1676 
                 1661 
               
               
                 11 
                 1936 
                 1838 
                 1824 
               
               
                 12 
                 2098 
                 2000 
                 1986 
               
               
                 13 
                 2260 
                 — 
                 2148 
               
               
                 14 
                 — 
                 2324 
                 2310 
               
               
                 15 
                 — 
                 — 
                 — 
               
               
                 16 
                 — 
                 2648 
                 — 
               
               
                   
               
            
           
         
       
     
     Interfacial Properties 
     The surface tensions of solutions of the Examples 1A and 1B in distilled water were determined using the Wilhelmy plate method. The crude products of the examples were purified from unreacted alcohols by washing with chloroform. After drying the residue, the surface tension was measured. The results are summarized in Table 3. The results showed that the reaction products of Example 1 A and 1 B display surface activities. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                 Compound 
                 Concentration 
                 T 
                 Surface Tension 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Distilled Water 
                 — 
                 25° C. 
                 72 
                 mN/m 
               
               
                 Example 1 A 
                 1 g/L 
                 25° C. 
                 40.0 
                 mN/m 
               
               
                 Example 1 B 
                 1 g/L 
                 25° C. 
                 42.3 
                 mN/m 
               
               
                   
               
            
           
         
       
     
     Example 2—Impregnated Straw 
     Impregnation 
     In an 800 ml beaker 6.8 g sulfuric acid (96%) was dissolved in 280 g methanol. After adding 19.6 g cutted straw (from Germany) to the acidic methanol solution, the mixture was stirred at room temperature for an hour. The suspension was filtered off and the wet residue was dried at 50° C. and 50 mbar for 3 h. The residue was homogenized by mortar and pistil. 
     Mechanical Treatment 
     2 g of acid impregnated straw were filled in a 25 ml tungsten carbide (WC) grinding beaker and was milled with a 15 mm WC-ball at 30 Hz for 10 min by Retsch MM400. Additional 2 g of acid impregnated straw were filled and was milled for further 60 min at 30 Hz. To the milled straw 1 g of 1-octanol/H 2 SO 4 -mixture (95/5, w/w) were filled and the mixture was milled for 60 min. The paste-like residue was suspended in chloroform for an hour and was filtered off. After drying at 50° C. and 50 mbar for 2 h, the residue was analyzed by  1 H-NMR (in D 2 O/NaOD) and MALDI-MS, which confirmed the octylization of the straw. 
     The surface tension of solution in distilled water was determined using the Wilhelmy plate method. The result of σ (1 g/L, 25° C.)=45 mN/m showed that the reaction product displays surface activity. 
     Example 3—Impregnated α-Cellulose 
     Impregnation 
     In an 800 ml beaker 6.6 g sulfuric acid (96%) was dissolved in 300 g methanol. After adding 33 g α-cellulose (as described in Example 1) to the acidic methanol solution, the mixture was suspended at room temperature for an hour. The suspension was filtered off and the wet residue was dried at 50° C. and 30 mbar for 3 h. The residue was homogenized by mortar and pistil. 
     A) Mechanical Treatment (No Additional Alcohol) 
     4 g of the acid impregnated cellulose were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm diameter WC-ball at 30 Hz for 90 min by Retsch MM400. The residue was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected (cf. Table 4): Methylpolyglycoside and polyglycoside. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Detected MS-signals 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Methylpolyglycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 217 
                 203 
               
               
                 2 
                 379 
                 365 
               
               
                 3 
                 541 
                 527 
               
               
                 4 
                 703 
                 689 
               
               
                 5 
                 865 
                 851 
               
               
                 6 
                 1027 
                 1013 
               
               
                 7 
                 1189 
                 1175 
               
               
                 8 
                 1351 
                 1337 
               
               
                 9 
                 1513 
                 1499 
               
               
                 10 
                 1676 
                 1661 
               
               
                 11 
                 1838 
                 1824 
               
               
                 12 
                 — 
                 1986 
               
               
                 13 
                 2162 
                 2148 
               
               
                 14 
                 2324 
                 2310 
               
               
                 15 
                 2486 
                 — 
               
               
                 17 
                 2810 
                 — 
               
               
                   
               
            
           
         
       
     
     B) Mechanical Treatment with Additional Octanol 
     4 g of milled cellulose from Example 3 A and 1 g of 1-octanol/H 2 SO 4 -mixture (90/10, w/w) were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm diameter WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 30 min. The crude product was purified from unreacted alcohols by washing with chloroform. After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected: Octylpolyglycosid, methylpolyglycoside and polyglycoside. 
     Table 5: Detected MS-signals 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Detected MS-signals 
               
            
           
           
               
               
               
               
            
               
                   
                 m/z 
                 m/z 
                 m/z 
               
               
                   
                 (Octylpolygycoside + 
                 (Methylpolyglycoside + 
                 (Polyglycoside + 
               
               
                 n 
                 Na + ) 
                 Na + ) 
                 Na + ) 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 315 
                 217 
                 203 
               
               
                 2 
                 477 
                 379 
                 365 
               
               
                 3 
                 639 
                 541 
                 527 
               
               
                 4 
                 801 
                 703 
                 689 
               
               
                 5 
                 963 
                 865 
                 851 
               
               
                 6 
                 1125 
                 1027 
                 1013 
               
               
                 7 
                 1287 
                 1189 
                 1175 
               
               
                 8 
                 1450 
                 1351 
                 1337 
               
               
                 9 
                 1612 
                 1513 
                 1499 
               
               
                 10 
                 1774 
                 1676 
                 1661 
               
               
                 11 
                 1936 
                 1838 
                 1824 
               
               
                 12 
                 — 
                 2000 
                 1986 
               
               
                 13 
                 — 
                 2162 
                 2148 
               
               
                 14 
                 — 
                 — 
                 2310 
               
               
                   
               
            
           
         
       
     
     C) Mechanical Treatment without Impregnation 
     4 g of α-cellulose (solid content: 93.3%) and 1 g of 1-octanol/H 2 SO 4 -mixture (80/20, w/w) were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm diameter WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 30 min. The crude product was purified from unreacted alcohol by washing with chloroform. After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected: Octylpolyglycoside and polyglycoside. 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Detected MS-signals 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Octylpolygycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 315 
                 203 
               
               
                 2 
                 477 
                 365 
               
               
                 3 
                 639 
                 527 
               
               
                 4 
                 801 
                 689 
               
               
                 5 
                 963 
                 851 
               
               
                 6 
                 1125 
                 1013 
               
               
                 7 
                 1287 
                 1175 
               
               
                 8 
                 1450 
                 1337 
               
               
                 9 
                 1612 
                 1499 
               
               
                 10 
                 1774 
                 1661 
               
               
                 11 
                 1936 
                 1824 
               
               
                 12 
                 — 
                 1986 
               
               
                 13 
                 — 
                 2148 
               
               
                 14 
                 — 
                 2310 
               
               
                 15 
                 — 
                 2472 
               
               
                 16 
                 — 
                 2634 
               
               
                   
               
            
           
         
       
     
     Interfacial Properties 
     The surface tensions of solutions of the examples 3 A, B and C in distilled water were determined using the Wilhelmy plate method. The results are summarized in Table 7. The results showed that the reaction products display surface activites. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 7 
               
               
                   
               
               
                 Compound 
                 Concentration 
                 T 
                 Surface Tension 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Distilled Water 
                 — 
                 25° C. 
                 72 
                 mN/m 
               
               
                 Example 3 A 
                 1 g/L 
                 25° C. 
                 71.8 
                 mN/m 
               
               
                 Example 3 B 
                 1 g/L 
                 25° C. 
                 45.8 
                 mN/m 
               
               
                 Example 3 C 
                 1 g/L 
                 25° C. 
                 47.6 
                 mN/m 
               
               
                   
               
            
           
         
       
     
     Example 4—Without Impregnation 
     The α-cellulose was the same as in Example 1. The maize starch was commercially available from Roquette GmbH, Germany with a solid content of 86.5 wt %. Before milling, the polysaccharide as listed in was dried at 100° C. and 50 mbar for 3 h. After drying, the polysaccharide and acidic dodecanol solution were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 15-30 min. The crude product was purified from unreacted alcohols by washing with chloroform. 
     After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected: Dodecylpolyglycoside and polyglycoside. The recipes are listed in Table 8. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 8 
               
               
                   
               
               
                   
                   
                 amount 
                   
                   
               
               
                   
                 polysac- 
                 polysac- 
                   
                 amount acid- 
               
               
                 Compound 
                 charide 
                 charide 
                 Acidic dodecanol 
                 solution 
               
               
                   
               
             
            
               
                 Example 4 A 
                 α-cellulose 
                 4 g 
                 H 2 SO 4 /H 2 O 
                 0.24 g 
               
               
                   
                   
                   
                 (20/80, w/w) 
               
               
                 Example 4 B 
                 maize starch 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.53 g 
               
               
                   
                   
                   
                 (20/80, w/w) 
               
               
                 Example 4 C 
                 α-cellulose 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.52 g 
               
               
                   
                   
                   
                 (20/80, w/w) 
               
               
                 Example 4 D 
                 α-cellulose 
                 4 g 
                 MeSO 3 H/Dodecanol 
                 0.50 
               
               
                   
                   
                   
                 (30/70, w/w) 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Detected MS-signals of Ex. 4 A 
               
            
           
           
               
               
               
            
               
                   
                 n 
                 m/z (Polyglycoside + Na + ) 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 1 
                 203 
               
               
                   
                 2 
                 365 
               
               
                   
                 3 
                 527 
               
               
                   
                 4 
                 689 
               
               
                   
                 5 
                 851 
               
               
                   
                 6 
                 1013 
               
               
                   
                 7 
                 1175 
               
               
                   
                 8 
                 1337 
               
               
                   
                 9 
                 1499 
               
               
                   
                 10 
                 1661 
               
               
                   
                 11 
                 1824 
               
               
                   
                 12 
                 1986 
               
               
                   
                 13 
                 2148 
               
               
                   
                 14 
                 2310 
               
               
                   
                 15 
                 2472 
               
               
                   
                 16 
                 2634 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Detected MS-signals of Ex. 4 B 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Dodecylpolygycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 371 
                 203 
               
               
                 2 
                 533 
                 365 
               
               
                 3 
                 695 
                 527 
               
               
                 4 
                 857 
                 689 
               
               
                 5 
                 1019 
                 851 
               
               
                 6 
                 1182 
                 1013 
               
               
                 7 
                 1344 
                 1175 
               
               
                 8 
                 1506 
                 1337 
               
               
                 9 
                 1668 
                 1499 
               
               
                 10 
                 1830 
                 1661 
               
               
                 11 
                 1992 
                 1824 
               
               
                 12 
                 2154 
                 1986 
               
               
                 13 
                 2316 
                 2148 
               
               
                 14 
                 2478 
                 2310 
               
               
                 15 
                 2640 
                 2472 
               
               
                 16 
                 — 
                 2634 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Detected MS-signals of Ex. 4 C 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Dodecylpolygycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 371 
                 203 
               
               
                 2 
                 533 
                 365 
               
               
                 3 
                 695 
                 527 
               
               
                 4 
                 857 
                 689 
               
               
                 5 
                 1019 
                 851 
               
               
                 6 
                 1182 
                 1013 
               
               
                 7 
                 1344 
                 1175 
               
               
                 8 
                 1506 
                 1337 
               
               
                 9 
                 1668 
                 1499 
               
               
                 10 
                 1830 
                 1661 
               
               
                 11 
                 1992 
                 1824 
               
               
                 12 
                 2154 
                 1986 
               
               
                 13 
                 2316 
                 2148 
               
               
                 14 
                 2478 
                 2310 
               
               
                 15 
                 — 
                 2472 
               
               
                 16 
                 — 
                 2634 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 12 
               
             
            
               
                   
               
               
                 Detected MS-signals of Ex. 4 D 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Dodecylpolygycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 371 
                 203 
               
               
                 2 
                 533 
                 365 
               
               
                 3 
                 695 
                 527 
               
               
                 4 
                 857 
                 689 
               
               
                 5 
                 1019 
                 851 
               
               
                 6 
                 1182 
                 1013 
               
               
                 7 
                 1344 
                 1175 
               
               
                 8 
                 1506 
                 1337 
               
               
                 9 
                 1668 
                 1499 
               
               
                 10 
                 1830 
                 1661 
               
               
                 11 
                 1992 
                 1824 
               
               
                 12 
                 2154 
                 1986 
               
               
                 13 
                 2316 
                 2148 
               
               
                 14 
                 2478 
                 2310 
               
               
                 15 
                 — 
                 2472 
               
               
                 16 
                 — 
                 2634 
               
               
                 17 
                 — 
                 2796 
               
               
                   
               
            
           
         
       
     
     The surface tensions of solutions of the examples 4 A to D in distilled water were determined using the Wilhelmy plate method. The results are summarized in Table 13. The results showed that the reaction products of Example 4 display surface activities. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 13 
               
               
                   
               
               
                 Compound 
                 Concentration 
                 T 
                 Surface Tension 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Distilled Water 
                 — 
                 25° C. 
                 72 
                 mN/m 
               
               
                 Example 4 A 
                 1 g/L 
                 25° C. 
                 70.3 
                 mN/m 
               
               
                 Example 4 B 
                 1 g/L 
                 25° C. 
                 29.7 
                 mN/m 
               
               
                 Example 4 C 
                 1 g/L 
                 25° C. 
                 26.4 
                 mN/m 
               
               
                 Example 4 D 
                 1 g/L 
                 25° C. 
                 25.5 
                 mN/m 
               
               
                   
               
            
           
         
       
     
     Example 5—Polysaccharide from Straw or Wood 
     Following raw materials were used: 
     Straw: Native straw from Germany was cut in small pieces and 1.5-2 g were filled in a 25 ml stainless steel grinding beaker. The straw was milled with a 15 mm stainless steel ball at 30 Hz for 3 min by Retsch MM400. After repeating this procedure several times, the pre-milled straw was dried at 100° C. and 50 mbar for 3 h. The solid content was 88.5%. 
     Straw meal: Commercially available from Agri-Stro B.V., Netherlands as Hackselstroh dust-free. 2-2.5 g were filled in a 25 ml stainless steel grinding beaker. The straw meal was milled with a 15 mm stainless steel ball at 30 Hz for 5 min by Retsch MM400. After repeating this procedure several times, the pre-milled straw meal was dried at 100° C. and 50 mbar for 3 h. The solid content was 89.2%. 
     Birch, Pine or Beech (all from Germany): The stored wood was sawed, and the wood shavings were collected. The shavings were dried at 100° C. and 50 mbar for 3 h. The solid content of the appropriate wood was 82.9% for birch, 85.7% for pine and 87.0% for beech. 
     Straw (A), straw meal (B), wood shavings from birch (C), pine (D) and beech (E) were used. The dried residue and the acidic dodecanol solution were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 15-30 min. The crude product was purified from unreacted alcohols by washing with chloroform. After drying the residue, the soluble part of the product was analyzed by  1 H-NMR (in D 2 O). The recipes are listed in table 6. The surface tensions of solutions in distilled water were determined using the Wilhelmy plate method. The results are summarized in Table 14 and 15. The results showed that the reaction products display surface activities. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 14 
               
               
                   
               
               
                   
                   
                 amount 
                   
                   
               
               
                   
                 polysac- 
                 polysac- 
                   
                 amount acid- 
               
               
                 Compound 
                 charide 
                 charide 
                 Acidic dodecanol 
                 solution 
               
               
                   
               
             
            
               
                 Example 5 A 
                 straw 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.50 g 
               
               
                   
                   
                   
                 (20/80, w/w) 
               
               
                 Example 5 B 
                 straw meal 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.50 g 
               
               
                   
                   
                   
                 (30/70, w/w) 
               
               
                 Example 5 C 
                 birch 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.53 g 
               
               
                   
                   
                   
                 (30/70, w/w) 
               
               
                 Example 5 D 
                 pine 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.53 g 
               
               
                   
                   
                   
                 (30/70, w/w) 
               
               
                 Example 5 E 
                 beech 
                 4 g 
                 H 2 SO 4 /Dodecanol 
                 0.52 g 
               
               
                   
                   
                   
                 (30/70, w/w) 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
             
               
                 TABLE 15 
               
               
                   
               
               
                 Compound 
                 Concentration 
                 T 
                 Surface Tension 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Distilled Water 
                 — 
                 25° C. 
                 72 
                 mN/m 
               
               
                 Example 5 A 
                 1 g/L 
                 25° C. 
                 44 
                 mN/m 
               
               
                 Example 5 B 
                 1 g/L 
                 25° C. 
                 49.6 
                 mN/m 
               
               
                 Example 5 C 
                 1 g/L 
                 25° C. 
                 41.1 
                 mN/m 
               
               
                 Example 5 D 
                 1 g/L 
                 25° C. 
                 40.4 
                 mN/m 
               
               
                 Example 5 E 
                 1 g/L 
                 25° C. 
                 40.7 
                 mN/m 
               
               
                   
               
            
           
         
       
     
     Example 6: Polysaccharide from Pulp 
     Washed pulp from industrial paper production based on spruce from Sweden (pulp obtained after the refiner (8 bar, 170° C. in 12 inch disc refiner) and washing step) was dried at 100° C. and 50 mbar for 4 h. The solid content was 27.2%. 2 g of dried pulp was filled in a 25 ml tungsten carbide (WC) grinding beaker and was milled with a 15 mm WC-ball at 30 Hz for 5 min by Retsch MM400. Additional 2 g of dried pulp was filled and was milled for further 5 min at 30 Hz. To the milled pulp 0.52 g of H 2 SO 4 -/1-dodecanol mixture (30/70, w/w) were filled and the mixture was milled analog for overall 4 h. After every hour, the mixture was allowed to cool down for 15 min. The crude product was purified from unreacted alcohols by washing with chloroform. After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O). 
     The surface tension of solution of in distilled water were determined using the Wilhelmy plate method. The result of 6 (1 g/L, 25° C.)=44.3 mN/m showed that the reaction product displays surface activity. 
     Example 7: Hexadecyl- and Octadecylpolyglycosid 
     Before milling, α-cellulose as used in Example 1 was dried at 100° C. and 50 mbar for 3 h to a solid content of 93%. 4 g of the dried cellulose and 0.70 g of C16/C18-alcohol/H 2 SO 4 -mixture (70/30, w/w) (Hydroxyl value for C16/C18-alcohol: 217.4 mg KOH/g) were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm WC-ball at 30 Hz for overall 5 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 30 min. The crude product was purified from unreacted alcohols by washing with chloroform. After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected, see also Table 16: Polyglycoside, hexadecylpolyglycoside and octadecylpolyglycoside. 
     The surface tension of solution in distilled water was determined using the Wilhelmy plate method. The result of 6 (1 g/L, 25° C.)=43.8 mN/m showed that the reaction product displays surface activity. 
     
       
         
           
               
             
               
                 TABLE 16 
               
             
            
               
                   
               
               
                 Detected MS-signals 
               
            
           
           
               
               
               
               
            
               
                   
                 m/z 
                 m/z 
                   
               
               
                   
                 (Octadec- 
                 (Hexa- 
                 m/z 
               
               
                   
                 ylpolygycoside + 
                 decylpolygycoside + 
                 (Polyglycoside + 
               
               
                 n 
                 Na + ) 
                 Na + ) 
                 Na + ) 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 455 
                 427 
                 203 
               
               
                 2 
                 617 
                 589 
                 365 
               
               
                 3 
                 779 
                 751 
                 527 
               
               
                 4 
                 941 
                 913 
                 689 
               
               
                 5 
                 1104 
                 1076 
                 851 
               
               
                 6 
                 1266 
                 1238 
                 1013 
               
               
                 7 
                 1428 
                 1400 
                 1175 
               
               
                 8 
                 1590 
                 1562 
                 1337 
               
               
                 9 
                 1752 
                 1724 
                 1499 
               
               
                 10 
                 1914 
                 1886 
                 1661 
               
               
                 11 
                 2076 
                 — 
                 1824 
               
               
                 12 
                 2238 
                 — 
                 1986 
               
               
                 13 
                 — 
                 — 
                 2148 
               
               
                 14 
                 — 
                 — 
                 2310 
               
               
                   
               
            
           
         
       
     
     Example 8: Behenylpolyglycoside 
     Before milling, α-cellulose as in Example 1 was dried at 100° C. and 50 mbar for 3 h. 4054 mg of the dried cellulose, 411 mg of behenyl alcohol (1-docosanol) and 156 mg MeSO 3 H were filled in a 25 ml tungsten carbide (WC) grinding beaker. The mixture was milled with a 15 mm diameter WC-ball at 30 Hz for overall 4 h by Retsch MM400. After every hour, the mixture was allowed to cool down for 30 min. The crude product was purified from unreacted alcohol by washing with chloroform. After drying the residue, the product was analyzed by  1 H-NMR (in D 2 O) and MALDI-MS. Peaks for the following structures were detected: Polyglycoside, behenylpolyglycoside. The surface tension of the solution in distilled water was determined using the Wilhelmy plate method. The result of 6 (1 g/L, 25° C.)=67.9 mN/in showed that the reaction product displays surface activity. 
     
       
         
           
               
             
               
                 TABLE 17 
               
             
            
               
                   
               
               
                 Detected MS-signals 
               
            
           
           
               
               
               
            
               
                   
                 m/z 
                 m/z 
               
               
                 n 
                 (Octadecylpolygycoside + Na + ) 
                 (Polyglycoside + Na + ) 
               
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 511 
                 203 
               
               
                 2 
                 673 
                 365 
               
               
                 3 
                 835 
                 527 
               
               
                 4 
                 997 
                 689 
               
               
                 5 
                 1160 
                 851 
               
               
                 6 
                 1322 
                 1013 
               
               
                 7 
                 1484 
                 1175 
               
               
                 8 
                 1646 
                 1337 
               
               
                 9 
                 1808 
                 1499 
               
               
                 10 
                 1970 
                 1661 
               
               
                 11 
                 2132 
                 1824 
               
               
                 12 
                 2294 
                 1986 
               
               
                 13 
                   
                 2148 
               
               
                 14 
                   
                 2310