AU2003235006B2 - Surface-active alkylurethanes of fructans - Google Patents

Description

14/01/03 17:33 CHRYSILIOU LAW 4 NO.989 P006 WO 9964549 C .CIEP99M3931 SURFEAC-ACTIVE ALKYILURETHANES OF FRUCTANS Field of the invention This invention relates to the use of alkylurethanes of fruns as surfactants, to compositions comprising alkylurethanes of fructans as surfactants, to novel alkylurethanes of fructans and to a process for their manufacture.

Bac ~rund and grior art Surface-active agents are widely used in compositions for household and industrial applications in which they act as detergents, foaming agents, foam stabiliers, wetting agents, emulsifiers and/or emulsion stafilises. The oldest type of surface-active agents, mainly used as detergents, are the alkali soaps of fatty adds. Later an these soaps have been replaced to a large extent by much stronger synthetic surfactants. The elder generation of synthetic surfactants consisted mainly of alkylbenzeesulfonates (ABS). However, ABS caused considerable water pollution due to their poor biodegradability.

At present, ABS have been largely replaced by linear alkylsulfonates (LAS) having ten or more carbon atoms in the alkyl chain, which present improved biodegradability compared to ABS surfactants.

To day, the search for altemrnative, more efficient and better biodegradable surfactants is still going on.

According to one approach, sugars such as glucose and sucrese (saccharose) have been used as starting material for the synthesis of non-ionic derivatives with surface-active properties.

V. Maunier et aL (Carbohydrate Research, 2 49-57, (1997)) disclosed tenslo-active properties of several 6-amrninocarbonyl derivatives of methyl a- D-glucopyranoside and D-glucose and compared them with the ones of the urethane named methyl 6-O-(N-heptylcarbamoyl)- a-D-glucopyranoside.

T. Lesiak et al. prakt. Chem, 322 877-883, (1980)) disclosed the use of 1-methyl-24-bis(isocyanato)benzene (commonly named tolylene-2,4dilsocyanate; in short 2,4-TDI) for the synthesis of urethanes of glucose and sucrose. First 2,4-TDI was reacted with various aliphatic long chain alcohols or terpene alcohols in a molar ratio 1 1 The reaction essentially occurred with the isocyanate group at position 4 and the urethane-mono-isocyanates obtained were then reacted with glucose, respectively sucrose, to yield the corresponding di-urethanes which presented moderate tensio-activity.

COMS ID No: SMBI-00378064 Received by IP Australia: Time 17:35 Date 2003-08-14 14/08/03 17:33 CHRYSILIOU LAW NO.989 P007 WO 99/64549 PCT/EP 31 2 The synthesis of several sucrose N-n-alkylurehanes and their tensioactive properties have been disclosed inter alia by l Bertsch et al prakt.

Chem., 1 108 (1960)) and by W. Gerhardt (Abh. Dtsch. Akad. Wiss. Berlin, Chem., Geol. BioL, Vol 1966 24-32, (1967)). These derivatives present moderate to good tensio-active properties but only at rather high concentration. The urethanes have been prepared by reaction of sucrose with the selected n-alkylisocyanate Bertsdch et aL and by transformation of sucrose with potassium cyanate and an n-alkylhalogenide in dimethyl formamide Gerhardt, .c Howevr, sucrose nalkylurethanes with longer alkyl chains, suffer from a moderate to poor solubility in water.

To improve the solubility in water of sugar n-alkylurethanes, corresponding -akylurethanes have been prepared from ethoxylated or propoxyTlateh syenthesis and tenso-active properties of n-alkylur t der ived from ethoxylated and propoxylated sucrose, rpcti mra vbet ql osed by W. Gerhardt and German Patent DE 1 518 696). Furthermore, l-n-alkyloxy)-ethyluthanes of sucrose have been synthesised and their tenso-active properties determined by T. Lesiak et al. prakt. Chm., M2 727-731, (1977)).

Moreover, the preparation Of miscellaneous urethanes derived from various carbohydrates have been disclosed.

European patent application EP 0 801077 discloses n-alkyl C-Cs18 urethanes of polysaccharides and ethoxylated polysaccharides, in prticular of cellulose, and their use as thermoplastic material. Similarly, Germnnan patent application DE 43 38 152 Al discloses n-alkylurethanes of starch and starch derivatives, such as acetylated starch, and their use as thermoplastic material.

European patent application EP 0 157 365 discloses various urethane derivatives of polysaccharides, inter alia inulin tri(phenylcarbarnate), and discloses their use in the optical resolution of racemic mixtures.

I. Wolff et al. Anm. Chem. Soc., M6 757 (1954)) disclosed to have prepared urethanes of starch, but later studies by E. Asveld et al (Carbohydrate Polymers, L 103-110, (1984)) revealed that in the aqueous reaction conditions used by L Wolff et al. no urethanes but only mixtures of the carbohydrate and the urea compounds have been obtained.

In view of the steadily increasing demand for surface-active agents for use in various applications, industry is continuously confronted with the COMS ID No: SMBI-00378064 Received by IP Australia: Time 17:35 Date 2003-08-14 14/OB/03 33 CHRYSILIOU LAlW 4 NO.989 P009 WO 9O4549 mam mS 3 need for alternative surface-active agents, which preferably present improved tensio-active properties and/or biodegradability.

ObQject of the.invention it is the object of the present invention to provide a solution to one or more S of the above mentioned problems by the provision of altemrnative surfaceactive products which are readily soluble at low concentration in water at room temperature and which present good tensio-active properties and good biodegradability.

pDescrition.of the invention In their search for alternative and/or improved surfactants, the inventors have found that certain urethanes of fructans provide a solution to one or more of said problems.

In accordance with these findings, the present invention provides the use of certilokylurethanes of fructans as surfactants, certain novel alkylurethanesof fruetans suitable for use as surfactants, methods for preparing twcomwnponds, and compositions ompxiztg one or more of said alkyhrethanes as surfactants and/or stabilisers.

By surface-active agent, surfactant or tensio-active agent are rmeant herein compound that reduce the surface tension when dissolved in water or in an aqueous medium, or which reduce Interfacial tension between two liquids, between a liquid and a solid or between a liquid and a gas. These terms are used herein interchangeably. The same applies to the terms designating said properties.

By the term alkylurethanes are commonly indicated a class of S 25 compounds resulting from the reaction of an alkylisocyanate with an alcoholic hydroxyl oup bearing substrate, whereas the individual reaction products are named as N-alkyrcarBanates, as esters of N-alkylcarbamlc acid. However, the terms are often, also in this descdpon, interchanged Fructans are well known naturally occurring polysaccharides embracing,the carbohydrates levan and inulin.

Levans are D-fructans generally consisting of chains of polyfructose of which the fructose units are connected to each other'mostly or exclusively by 8(2-6) fructosyl-fuctose linkages. Levans occur in nature in certain plant species (in this case they are also called phleins) and also originate from the activity of certain bacteria. Levans can be produced, according to conventional techniques, by extraction from certain plants, by fermentation techniques and by enzymatic in vitro synthesis. Levans usualljr occur as a COMS ID No: SMBI-00378064 Received by IP Australia: Time (Hm) 17:35 Date 2003-08-14 14/08/03 17:33 CHRYSILIOU LAId NO.989 P0B9 WO 99164549 PCT/EP99/331 4 polydispee mixture of said polyfructose chains. The chains may be linear, but mostly they are branched.

Inulins are D-fructans too, generally consisting of chains of polyfructose but of which the fructose units are connected to each other mostly or exclusively by 8(2-1) linkages. Inulin occurs in nature, in genial, as a polydisperse mixture of polyfructose chains most of which are ending in one glucosyl unit Inulin can be from bacterial origin, from vegetal origin or can be made in vitro by enzymatic synthesis starting from sucrose. Inulin produced by bacteria is more branched than inulin from plant orgin and has commonly a higher molecular weight (ranging from about 2,000 up to about 20,000,000), whereas inulin from plant origin is generally composed of linear or slightly branched polyfructose chains or mixtures thereof with a molecular weight commonly ranging from about 600 to about 20,000.

Inulin can be represented, depending from the terminal carbohydrate unit, by the general formulae GFn or Fn, whermi G represents a glucosyl unit, F a fructosyl unit, and n is an integer representing the number of fructosyl units linked to each other in the carbohydrate chain The number of saccharide units (fructose and glucose units) in one inulin molecule, i.e.

the values n+l and n in the respective formulaeabove, are referred to as the degree of polymerisation, represented by Often, the parameter (number) average degree of polymerisation, represented by is used too, which is the value corresponding to the total number of saccharide units (G and F units) in a given inulin composition divided by the total number of inulin molecules present in said inulin composition, without taking into account the possibly present monosaccharides glucose and fructose and the disaccharide sucrose The average degree of polymerisation (DP) can be determined, for example, by the methoddescribed by L De Leenheer (Sarch, 6 193-196, (1994), and Carbohydrates as Organic Raw Materials, Vol. III, p. 67-92, (1996)).

At industrial scale, inulin is commonly prepared from plant sources, mainly from roots of Chicory (Ckhorium intybus) and from tubers of Jerusalem artichoke (Helianthus tuberosus), in which inulin can be present in concentrations of about 10 to 20 w/w on fresh plant material Inulin from plant origin is, in general, a polydisperse mixture of linear and slightly branched polysaccharide chains with a degree of polymerisation

(DP)

ranging from 2 to about 100. In accordance with known techniques, inulin can be readily extracted from said plant parts, purified and optionally COMS ID No: SMBI-00378064 Received by IP Australia: Time 17:35 Date 2003-08-14 14/09/03 17:34 CHRYSILIOU LAJ 4 NO.999 wo 9 as49 PCrAEP9943931 fractionated to remove impurities, mono- and disaccharides and undesired oligosaccharides, in order to provide various grades of inulin, as eg.

described in European patent applications EP 0 769 026 and EP 0 670 850.

Inulin is commercially available, typically with a ranging from about 6 to about 40. Inulin from chicory is for example availale as RAFTLINIE from ORAFTI, (Tienen, Belgium) in various grades. Typical RAFIL;INE@ grades include RAFTILINE@ ST (with a of about 10 and containing in total up to about 8 by weight glucose, fructose atd sucrose), RAFILLINE® LS (with a D) of about 10 but containing in total' less than 1 by weight glucose, fructose and sucrose), and RAFIIUNE® HP (with a of at least 23, commonly with a (DP) of about 25, and virtually free of glucose, fructose and sucrose).

Inulins with a lower degree of polymerisation, usually defined as a (DP) 10, are commonly named inulo-oligosaccharides, fructo-oligosaccharides or oligofructose. Oligofructose can be conventionally obtained by partial (preferably enzymatic) hydrolysis of inulin and can also be obtained by enzymatic in vitro synthesis from sucrose according to techniques which are well-known in the art. Several grades of oligofructose are cormerdcially available, for example as RAFTILOSE® from ORAEI, (Tienen, Belgium), e.g. RAFTILOSE® P95 with a mean content of about 95% by weight of oligofructose with a degree of polymerisation (DP) ranging from 2 to 7 and containing about 5 by weight in total of glucose, fructose and sucrose.

In one aspect, the present invention relates to the use as surface-active agent of a fructan alkylurethane also named fructan N-alkylcarbamate 25 which is composed of saccharide units of general formula (I) A (O-CO-NH-R), (II) wherein A represents a fructosyl unit or a terminal glucosyl unit of said fructan, being a levan or an inulin, with a degree of polymerisation (DP) of minimum 3, (0 CO NH R) represents an N-alkylaminocarbonyloxy group, also called an alkykarbamte group, replacing a hydroxyl group of the saccharlde wit A, wherein R represents a linear or branched, saturated or unsaturated alkyl group containing from 3 to 22 carbon atoms and any mixture thereof, and a represents the number of alkylcarbamate groups per saccharide unit which is expressed as degree of substitution (commonly abbreviated as DS), COMS ID No: SMBI-00378064 Received by IP Australia: Time 17:35 Date 2003-08-14 14/0e/033 1?:38 CHRYSILIOU LAW 4 NO.990 P001 WO flM49 PC4EP99iO/39 6 i.e. the average number of substituents per saccharide .unit of said fructan, and which DS has a value ranging from about 0.10 to about 20 The number of hydroxyl groups per saccharide unit of the fructan molecules which can be substituted by a carbamate group is for a nonterminal, non-branched sacchaide unit maximal 3, whereas said number for a terminal saccharide unit and for a non-terminal branched unit is, respectively, 4 and 2 Furthermore, since the DS represents an average number of substituents per saceharide unit, it is obvious that in a fructan N-alkylcarbamate molecule there may be saccharde units prsent which are not substituted by an alkylcarbamate group at all.

In another aspect, the present invention relates to a composition comprisins as surface-active agent one or more fructan alkylurethanes (1) defined above.

In a further aspect, the present invention relates to novel fructan alkylurethanes defined above.

In still a further aspect, the present invention relates to a process for the manufacture of fructan alkylurethanes defined above.

In still another aspect, the present invention relates to a process for the manufacture of compositions comprising as surface active asent one or more fructan alkylurethanes defined above.

In a preferred embodiment of the present invention, the fructan alkylcarbamate is made from a levan. In an other preferred embodiment, the fructan alkylcarbanmate is made from an inulin. Levans and inulins which are suitable according to the present invention include, respectively, S 25 polydisperse levanus and inulins composed of essentially linear polysaccharide chains, of essentially branched polysaccharide chains, as well as of respective mixtures thereof.

In view of its better biodegradability, the inulin is preferably a polydisperse linear nulin or a polydisperse slightly branched inulin or a mixture thereof When the inulin is a slightly branched one, it is preferably an inulin of which maximally about 3 of the fructose units of the inulin chains present 3 fructosyl-fructose bonds. The degree of branching can be determined by known methods, for example by permethylation techniques in combination with gas chromatography analysis, e.g. as described by L De Leenheer et at in Starch, 193196 (1994).

In a more preferred embodiment, said polydisperse inulin consists of polysaccharide chains with a degree of polymerisation (DP) ranging from 3 COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17,39 CHRYSILIW LAJ NO.990 P002 W 9964549 PCTEP9903931 7 to 100, typically from about 5 to about 75. Even more preferably said polydisperse inulin has an average degree of polymerisation between 6 and 40, most preferably a (LW) ranging from about 10 to about The alkyl group of the alkylurethanes of the prdsent invention, i.e.

the R group in formula is preferably a saturated alkyl group, more preferably a saturated C3 C 18 alkyl group, and most preferably a saturated linear or slightly branched C6 S alkyl group or a mixture hereof.

Typically alkyl groups include propyl, butyl, hexyl, octyl, decyl, dodecyl, teradecyl, hexadecyl and octadecyl, and any mixtures thereof. In another preferred embodiment, the alkyl group is a monounsaturated C3- Cj8 alkyl group, more preferably a mono-unsaturated C- Cis alkyl group, even more preferably a mono-unsaturated C6-C 16 alkyl group. Typically suitable mono-unsaturated alky groups, i.e. alkenyl groups, include hexenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, and any mixtures thereof.

In a further embodiment, the alkyl group R can represent a mixture of one or more saturated alkyl groups with one or more unsaturated, preferably mono-unsaturated, alkyl groups.

The alkylurethanes in accordance with the present invention, particularly the ones derived from inulin, have a degree of substitution preferably ranging from about 0.15 to about 1.5, more preferably from about 0-20 to about 1.2, even more preferably from about 0.4 to about 0.8, and most preferably from about 0.50 to about 0.60.

The positions on the saccharide units of the fructan alkyhlurethanes (I) where the said alkylcarbamate substituent or substituants are located, are not critical with respect to the present invention.

The fnuctan alkylurethanes can be prepared in analogy with conventional methods for the preparation of urethanes of mono- and disaccharides, and of urethanes of polysaccharides such as starch. The products can be prepared, for example, by reacting the substrate carbohydrate (levan or inulin) with the selected alkylisocyanate, in solution in a solvent which is inert with respect to the polysaccharide, the isocyanate and the reaction product. Suitable solvents include, for example, rather polar solvents or solvent mixtures, free of reactive hydroxyl and amine groups, such as dimethyl formamide and dimethyl sulfoxide.

Saturated alkylisocyanates can be prepared conventionally. e.g. by reacing a primary or secondary alcyl-amine with phosgene. Unsaturated COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:39 CHRYSILIOU LAW NO.990 P003 WO 99/64549 PCT/EPO9 31 8 alkylisocyanates can be prepared similarly from alkenyl-amines. Alpha-beta unsaturated alkylisocyanates of formula R 2

R

3 C CH NCO (II) wherein R2 represents hydrogen or an alkyi group and R3 represents an alkyl or vinyl group, can be prepared by condensation of the aldehyde

R

2

R

3 CH CHO with Me3 C NH2, followed by reaction of the resultant Schiff base (in equilibrium with its enamine form) with phosgene, and thermal elimination of Me C Cl, as disclosed by K. Koenig et al. (Angew. Chem., 21(4), 334335 (1979)).

Furthermore, various unsaturated alkylisocyanates are disclos, inter alia in US 3,890383 and US 3,803062 of Dow Chemical Co.

The reaction between the fructan and the alkyisocyanate can be carried out, preferably in the absence of humidity, over a wide temperature range, typically from room temperature till the reflux temperature of the reaction mixture, preferably at a temperature from about 60 0 C to about 80"C. The fructan is dissolved in a suitable solvent, where necessary under heating, and the isocyanate (optionally dissolved in the same or in another inert solvent which is preferably miscible with the former solvent) is then added to the dissolved fructan slowly and under stirring. The desired degee of substitution of the fructan alkylurethanes can be obtained by controlling the ratio of the reactants. Since the reaction of an alkylisocyanate with an alcoholic hydroxyl group to form an urethane is virtually quantitative, the degree of substitution of the compounds can be controlled by selection of the proper mole ratio of the alkylisocyanate per saccharide unit of the fructan substrate. Usually the reaction mixture is heated during a certain 25 time with stirring in order to complete the reaction between the reagents.

The reaction mixture can be worked up, for example, by precipitating the formed fructan alkylurethane by pouring the eaction mixture in a precipitant solvent, i.e. a solvent which is miscible with the solvent or solvents used to dissolve the reagents but in which the fructan alkyluethane is virtually not or poorly soluble.

A convenient method to synthesise a desired, scrose alkylurethane which is also suitable for the synthesis of huctan alkylurethanes (1) according to the present invention, has been described by W. Gerhardt, Abh. Dtsch. Akad. Wiss. Berlin, KL Chem. Geol. Biol, Vol 1966(6), 24-36, (1967) (CA, 68, 14323). It involves the transformation, in a one pot reaction, of sucrose with potassium cyanate and an alkyl halogenide, preferably an alkyl bromide, in dimethyl formamide.

COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:39 CHRYSILIOU LAW 4- NO.990 P004 WO 9916449 PCTEP99M391 9 Furthermore, the inventors have developed an alternative, very suitable method for the manufacture of fructan alkylurethanes which enables to use as substrate, a fructan which may contain mono- and disaccharides to an extent of up to about 10 by weight.-According to this process, the starting fructan, for example inulin containing about 8 monoand disaccharides (such as e.g. RAPFTILNE ST from ORAFI®, Belgium) or oligofructose containing about 5 mono- and disaccharides (such as e.g.

RAFTILOSE® P95 from ORAFTI®, Belgium), are reacted in an inert solvent or solvent mixture (termed herein first solvent) with the alkyliWcyanate which is optionally dissolved in the same or in another inert first solvent After the reaction is completed, usually by heating under stirring for some time, the reaction mixture is treated, preferably after concentration by evaporation of a part of the first solvent under reduced pressure, with a solvent or solvent mixture (termed herein precipitant solvent) wherein the first solvent of the reaction as well as the alkylrethanes of the mono- and disaccharides remain in solution, but wherein the fructan alkylurethanes

(I)

are virtually not soluble.

Accordingly, the formed fructan alkylurethanes precipitate in the precipitant solvent from which they can be isolated easily by a conventional physical separation technique such as decantation and/or filtration, or centrifugation. To complete the removal of remaining first solvent and possibly present small amounts of alkylurethanes of mono- and disaccharides, the isolated reaction product can be washed and/or triturated with the precipitant solvent or with another suitable precipitant solvent, or S 25 other conventional techniques can be used such as eg. redissolving and reprecipitation of the reaction product, followed by its isolation and drying.

Suitable first solvents include, for example, dimethyl formamide and dimethyl sulfoxide; suitable precipitant solvents include, for example, ethers, ketones, alcohols and esters.

The fructan alkylurethanes are readily soluble at low concentration in water at room temperature and they present good to excellent tensioactive properties, even at very low concentration. Accordingly, they are very useful as surface-active agents because they significantly reduce interfadal tension between an aqueous liquid and a non-aqueous liquid, between an aqueous liquid and a solid, and between an aqueous liquid and a gas.

Preferably the fructan alkylurethanes are used as surface-active agent in an aqueous medium, more preferably in water, at a concentration ranging COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:39 CHRYSILIOU LAWl NO.990 P005 WO 915s PCTEP993931 from about 0.0005 to about preferably from about 0.001 to about 3%, more preferably from about 0.005 to about 2 even more preferably from about 0.01 to about 1 (concentration in weight/volume As a non-limiting illustration of the present invention, the preparation and tensio-active properties of some fructan alkylurethanes are shown in the Examples and Tables below.

General aocedure used for the manufacture o fructan ankvytrethans M.

The reaction is preferably carried out in the absence of humidity with anhydrous reagents and solvents. The fructan, preferably conventionally dried, eg. under vacuum over P20s or by azeotropically distilling off of the water by means of a suitable solvent, is dissolved, with stirring under heating, in a minimum amount of solvent, e.g. dimethyl formamide (DMF).

To avoid thermal degradation, the temperature has to'be kept below about 110IC Preferably the mixture is kept between about 60'C to about 80°C until all fructan has dissolved. Then, at a temperature between about 60DC to about 80 0 C, a pre-defined amount (determined in mole equivalents on fructose units in the fructan; for the calculation, the amount of fructan starting material is taken as composed of 100 fructose iits) of a selected alkylisocyanate, optionally diluted with a suitable solvent, e.g. DMF, is added slowly, preferably dropwise, under vigorous stirring to the fructan solution and the obtained mixture is stirred at said temperature for a certain time to complete the reaction. After a few hours, the mixture may already turn cloudy by precipitation of formed fructan alkyhuethae but usually stirring is continued for about 24 hours in total after addition of the alkylisocyanate Accordingly, the mixture is cooled to room,temperature, optionally part of the solvent is removed by evaporation under reduced pressure, and a precipitant solvent, e.g. diethyl ether, is added under stirring.

The formed fructan alkylurethane precipitates, usually as a more or less sticky mass. After removal of the supernatant solvent, the sticky mass is repeatedly treated under stirring with solvent mixtures with decreasing polarity until the fructan alkylurethane is obtained in powder or granulate form, which is then isolated and dried.

Alternatively, in order to avoid the formation of said sticky mass, the farmed fructan alkylurethanes can advantageously be isolated after completion of the reaction by slow, preferably dropwise, addition under vigorous stirring of the cooled and optionally concentrated reaction mixture to an excess of precipitant solvent, e.g. ether. Typically the formed fructan COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/09/03 17:40 CHRYSILIOU LAW 4 ND.990 P06 WO 99A/6459 PCT/Pe9asl 11 alkylurethianes precipitate in a granular or powder fonrm and can be easily isolated. After their separation from the solvent mixture, e.g. by filtration, the fructan alkylurethanes can be further purified by washing, trituration with a non-solvent, e.g. ether, or they may be redissolved and reprecipitated to remove possibly included solvent and impurities. The formation of the fructan alkylurethanes has been confirmed by IR- spectroacopy (presence of -NH-CO- band at 1705 c 1 (arnide I band) and 1543 an- (ame II band) and by 13C NMR spectroscopy (where following resonance peaks were fomnd for inulin N-n-octylaibamate: a (pm; 68MHz :13.87; 22l.05; 26.23; 28.64; 29.33; 30.74; 31.21; 35.77; 6145; 73.99; 7656; 81.59; 103.19 and 156.08).

As to the synthesis of inulin alkycarbamates the yields commonly obtained are good. For the synthesis made at a 0.2 mole scale, typical yields of inulin octylcarbamates (D 5:032 059) obtained are as follows: with RAPTLNE@ HP (inulin with (DP) of about 25): yield about 70-95 with RAFILINEC ST (inulin with (DP) of about 10): yield about 55-75 with RAFTILOSE® P95 (95% w/w oligofructose with (DP) from 2 to 7): yield about 50-65 The above general procedure is further illustrated by the following examples. The tensio-active properties of the fructan alkylurethanes were determined by measuring the surface tension at 20 C of an aqueous solution of the compounds with a tertsiometer following the Wilhelmy or the Du Nouy Ring method.

ExamIple 1 inulin N-ntlda bamateg (1) In a 100 ml flask, 5.0 g inulin (RAFTILINE® HP with a (DP) of about 25; 27.7 millimole fnuctose equivalents) were dissolved under stining at about 70 0

C

in 8 ml dry DMF. To the yellowish solution 29 ml n-octylisocyanate (16.7 millimole; 0.6 mole equivalents determined on fructose units) were added dropwise with stirring at 7 9 C. Stirring was continued for 24 hours at Then, after cooling, most of the DMF was evaporated under reduced pressure (t 6.7 Pa: 0.05 mm Hg). To the residue at room temperature, 10 mi of dry diethyl ether was added under stirring and the mixture was stirred for 1 hour. The white precipitate formed was isolated by filtration, washed with ml dry ether and the residual solvents (DMF and ether) were removed under reduced pressure (t 6.7 Pa; 0.05 mm HS), yielding inulin' N-n-octyl- COMS ID No: SMBI-00378070 Received by IP Austraria: Time 17:50 Date 2003-08-14 14/0B/03 17:40 CHRYSILIOU LAW NO.990 P007 WO 9964549 PCTIEP99M931 12 carbamate with a degree of substitution of 056 (detenined by 1-.

NMR 270 MHz). Compound was obtained as a white powder in a yield of 92 The efficiency calculated as [DS (molar ratio octylsocyanate/ fructose equivalent)] was 93%. The surface tension of product in a 0.01% w/v solution in water was 32.4 mN/m.

Example 2: inulin .N-n-ocylrarhamate (2) In a 500 ml flask, 333 g inulin (RAFTILINE® HP with a (DP) of about 0.185 mole fructose equivalents) was dissolved at 60'C in 60 mldry DMP. To the yellowish solution kept at 60*C, 19.56 ml n-octylisocyanate (0.111 mole; 0.6 equivalents determined on fructose units) was added dropwise under stirring. Then the mixture was heated to 70C and stirred for 24 hous,. After cooling to room teerature, 150 ml diethyl ether waS added slowly under vigorous si Aftostopping the stirring, the reaction product quickly settled and mh of-te sorent was removed b decantation. Under stirring 100 mn dry ,tjir was added to the residue, which became gummy-like. After addition ofaiother50an ether the residue started to gtanulate and after 1 hour stirring a white suspension was formed. The precipitated solid was filtered off, washed with dry ether and dried under reduced pressure 6.7 Pa; 0.05 mm.Hg), yielding inulin N-n-octylcarbamate with a degree of substitution (D5) of 0.58 -(determined by 1 H-NMR 270MHz) in a yield of about 95% and with an efficiency of 96 The surface tension of product (2) in a 0.01% w/v solution in water was 34 mN/ma Several other nulin alkylurethanes have been prepared by reacting various grades of inulin with various n-alkylisocyanates in accordance with the general procedure desacribed above, and their ensio-acte properties were determined. These products and data, including also Examples 1 and 2 above, are listed in Table 1 below.

COMS 0ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/OB/03 17:41 14/0/03 7241 C-RYSILIDU LPJ O90P8 NO.990 POOB WO A99V4 Product ixauln alkyl degree Surfre tension No gxade group subst atO001% wlvin (DP) water OzzN/mW 1 25 n-octyl 0.56 n24 2 25 n-octy 0O5 34 3 25 ni-propyl 0.13 61.6 4 25 n-propyl 0.18 65-2 25 nf-propyl 0.35 59.2 6 25 n-propyl 0.72 46 7 25 n-propyl 1.2 41.2 8 25 n'hexyl 0.37 4 9. 25 n-hexyl 0.46 36 25 n-octl 0.21 11 25 n-octyl 0.37 45.6 12 25 n-octy 0355 13 25 n-Octyl 0.56 32.4 14. 25 n-octyl 0.78 36 1525 n-octy 0.86 36.8 *16- 25 n-dodecyl 0.21 .42 17 25 n-dodecyl 0.29 31.6 158 25 n-octyl 0.56 35-2 19 25 n-octyl 0.59 35-6 10 n-octyl 053 34.6 21 95% DP2-7 aoyl0.51 31.7 22 25 n-octyl 0.56 23 25 n-dodecyl 0.34 56 24 25 n-caer 0.0500 63.5 *The inulin grades used were:- (DP 25 RAFFIINE®0HP (DfP: 10 =RAFlLNB®QDSr and (95 DP2-7)u=RAFflLQSODV?95.

*The isocyanates were corrnercially available technia grade products.

DS: measurd by 1 H-NlhAR 270 Wiz 0' not measured by NMR; value estimted based on 0.05 mnole equivalent C08 aflkyl Isocyanate put into reaction.

The value of the surface tension of pure water measured under the same ,conditions ranges between about 72 to 74 mN/rn.

COMB IE)No: SMSI-00378070 Received by IF' Australia: Time (ktm) 17:50 Date 2003-08-14 14/08/03 17:41 i4~00/0317241 Q-RYS IL IOU LAW 4NO90P9 NO.990 P009 WO 9W$49 14 Furthermore, for some of the inulin N-n-octylcarbamnates the citical nidele oncenfration (CMC) has been determined which are shown in Fig1,PFig 2and Fig 3.

Fig. 1: prestmts the surface tension in function of the concetnrtiont Of inulin (DI 25) N-n-octylcarbamate (1DS: 0.56) (18) measued at room temperature in water and the resulting critical miucelle concentration (CMC=12.8 i0r 3 Fig I: presents the surface tension in function of the concentration of inulin (TP 10) N-n-ocicarbamnate 0,53) (20) mneasured at roomteprue lo in water and the result citical wicelle concentration (CMC-16.0 10- g/l); Fig 3: presents the surface tension in function of the concentation of inulin DP. 2-7) N-n-octykarbamare (DS: 0.5) (21) measured at room teniperature in water and the resulting citical micelletconcenttation (CMC= 23.9 10-3 g/l).

The experimental data shown in Table 1 and in Figures 1 to 3 dlearly indi~cate ftht the alhietaes present useful to excellent tenso-aclive properties at low concentration e.g. a concentration of 0.01 w/v in water and even at aconcentration ofo.001 w/v in water, and from saiddata it can be concluded th-at the alcylurethanes have gret potential as surf actants.

E Diapdakl4 The alkylurethanes, are well biodegradable. To illustrate said characteristic, the Biological Oxygen Demand (DOID) and Chemica Oxygen Demand (COD) for some Inulin N-.n-octylalklcarbarnates, measured by the Sapromat method, are given below:- Carbainate DOD (Ing 02/S) COD (Mg 02/g) HOD COD PrdtasNo~. is 620 1064 05%3 21 943 1108 0.851 Esaml bmn Mtd The alylcarbaxnats (II) are good foaming agents and present good fom stabillixtg effects. To illustate these properties, results of measurements by means of a gas injecton method are presented in Table 2 below.

COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:42 CHRYSILIOU LAW N0.990 P010 WO 99/49 PCTFEP99/03931 The gas injection method used was as follows. Foam was made in a reproducible manner by blowing a defined volume of nitrogen gas at a constant flow rate through a sintered glass disc at the bottom of a cylindrical glass tube containing a known volume of the solution to be foamed. After providing a defined amount of gas (exactly 100 m 3 the evolution of the liquid phase and the foam phase were determined as a function of time. All glass material used was placed in chromic acd overnight and thoroughly rinsed with milli-Q water before use. The experimental conditions were as follows: room temperature; gas flow: 100 cm 3 (51/i for exactly.2 seconds); disc porosity diameter 16-24 micrometer; column size: 0.4 m x 0.030 m (inner diameter); sample volume: 20 ml; duration of the analysis: minutes with measurement of the foam height every minute,and samples of the carbamates were dissolved at 0.1 (1000 ppmn in milli-Q water. The foam height as a function of time was measured and expressed in MD values, Le. the foam volume /liquid volume. The results are summarised in Table 2.

Table 2: rFamfn proerties of inulin N-n-octcarbfamtes Product inulin Degree MD MD MD MD MD No grade* substit* initial 3 min 7 nin 15 min 20 min 19 (DP: 25) 059 53.6 14.1 11.0 9.6 9.1 (DP:10) 0.53 36.0 10.8 9.4 7.9 7.4 21 95%DP2-7 0.51 36.9 11.7 9A 7.9 7.

The inulin grades used were (DP :25 RAINE HP; (DP 10 RA LINE ST and (95 DP 2-7) RAFI L OSE& DS measured by 1 H-NMR 270 MHz The data of Table 2 dearly indicate the potential of inulin N-n-alkylcarbamates as foaming agents and as foam stabilisers.

Exame 5: Interfacial tension.

The Interfacial tension has been measured by means of the Du Nouy ring method at 20 "C for water/oil systems in which inulin N-nalkylcarbamates were used as surface-active agent The results are presented in Table 3. The products (Product No) are described in Table 1.

COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:43 CHRYSILIOU LAlW NO.990 PO11 WO 99644549 PCTUPgAKMI31 Table nlrfeadial teUsion of inalin N-n-alkyl arbamats a) Surfactant (I) Cone. in wyv Product in sufactant No (water) solution I Typeofoil I Interaial Tension at 2rc (mNim) 4 1 0.1 0.01 0 0.1 0.01 0 0.1 0.01 0# 0.1 0.01 00 0.01 0.01 paraffinic oil' paraffinic oil'* paraffinic oil' aromatic oil" aromatic oil"* aromatic oil*" silicon oil** silicon oil"* silicon oil" vegetable oil"" vegetable oil""** vegetable oil"" paraffinic oil* paraffinic oil* 7 44 2.7 5.4 29 5.6 13.4 295 3 48 12.6 27 comparative test I: soparaffinic hydrocarbon "Isopar M" (Exxon) naphthalenic oil "Solvesso 200" (Exxon) Ssilicon oil "Cydomethicon E344" (Dow) soybean oil (Sainor) rawPlet &Emnsifying ;rp ertisI of aall-rithnes (1) The alkyluretbanes present very good emulsifyng properties, in particular with respect to oil/water systems. Typical oils include, for example, vegetable oils, hydrocarbon oils and mineral oils, and any mixture thereof. The emulsons may find wide applications, depending of the nature of the oil, in various fields, such as, for example, in household products, in person cae applications, in agrochemicals, in pesticides and in industrially used emulsions.

COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:43 CHRYSILIOU LAJ 4> N0.990 P012 WO 64149 PCTiSPPiW931 17 The oil content in the emulsions can, for example, ange from about 5 wt to about 75 wt The total concentration of the suractant, akylcarbamate (I) or a mixture of two or more alkylcarbamates in the surfactant solution used to build the water phase can, for example, range from about 03 wt to about 3 wt typically from about 0.5 wt to about 2 wt The emulsifying properties of the alkyurethanes are illustrated by the example below in which various oil/water emulsions, containing one or more alkylcarbamates as surfactant, were prepared and evaluated according to standard procedures.

Prerato o M the emulsions.

To 25 ml surfcctant solution, composed of a given concentration of one or more alkylcarbamates in demineralised water, were added dropwise 25 ml oil, while the mixture was stirred by means of an Ultra- Turrax (CAT X620) (trade name). The oil was added during the first step of a four step mixing process, in which the mixing speed was stepwise increased as indicated in table 4 below, yielding the emulsion. However, the mixing procedure is not critical since also other procedures than. the one given yield about the same results.

Table 4: Miing procedure 1Step _2 3 4 Stirring speed (rpm) 9,500 13,500 20,5O 24,000 Strring time (sec) 120 60 45 Evluation of the emulsions The evolution in time of the emulsions kept at room temperature was followed both microscopically (evolution of the droplet size) and macroscopically (visual check for oil/water separation). The results are shown in Table 5 below.

COMS ID No: SMBI-00378070 Received by IP Australia: Time (H:mr) 17:50 Date 2003-08-14 14/06/03 17:44 CHRYS ILI I U LAWd 4 NO.990 P013 WO 99164549 Lke Evaluation of oil /water emulsion. containing alkvarbamates a) Total wt of Alkylcarbamate Oil Stabiity of surfactants Product No emulsion in the (days) (2) surfactant solution water phase) 22 o il(1) 2 22 oil 1 22 s an 1 24 apfic 1 23 Rfn oil) 1 22+23 isopaMffin oi(1) 1 22+24 oil) 1 23+24 ic oil 1 22+23+24 isoparaffinicoi :In the mixture of alkylcarbamates the products were used at the same weight i.e. respectively in the weight ratio 1:1 and 1:1:1.

The prodct corresponding to the product number is descibed in Table 1.

isoparaffinic hydrocarbon "Isopar M" (trade name of Exxon) the emulsion was stable (no oil/water separation observed) for at least the indicated time.

Example 7: Emultossai taininga alkVICS Mane ID and inalin The stability of oil/water emulsions containing one or more alkylcarbamates as surfactant can be further improved by increasing the viscosity of the aqueous phase by the addition of inulin to It.

In typical test runs, respectively 0.5 g 1 g; 2 g and 2.5 g inuin (RA rILINE@ ST or RAFTLNE® HP) (all of about 96 wt dry matter) were slowly added to 25 mi surfactant solution composed of 1 wt respectively 0.5 wt%, alkylcarbanate No 22 in demineralised water under stirring (Ultra-Turrax at A800D rpmn for 15 to 60 sec). With the so obtained surfactant solution, COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/08/03 17:44 CHRYSILIOU LPFJ 4 NO.990 P014 WO 99/44549 W9649 19 PCTIEP9910331 emulsions with isoparaffinic hydrocarbon oil ("Isopar M trade name of Exxon) were prepared according to the procedure described in Example 6.

All the emulsions obtained were still stable (visual inspection) after storage for 20 days at room temperature.

Example Use ofalklurethanes as dispersant Dispersions were made from surfactant solutions containing one or more alkylcarbaates described above by adding a product in powder form to said surfactant solution under stirring by means of'an Ultra-Titrax (CAT X 620) trade name). The powder was added during the first step of a four step mixing process (1st step: 9,500 rpm; 90 sec.; 2nd step: 13500 rpm; 60 sec.; 3rd step: 20,500 rpm; 30 sec.; 4th step: 24,000 rpm; 15 sec.).

However, the mixing procedure is not critical since also other procedures than the one given above yield about the same results. The dispersions obtained were inspected visually and microscopically (100 x) in function of the time.

Test nms, for example a dispersion of 05 g carbon black (Eftex 575 variant, Cabot Corporation) in 25 ml surfactant solution of 0.5 wt alkylcarbamate No 22, showed that with alkylcarbamates as surfactants, dispersions with a very good stability were obtained in which the particle size of the dispersed product was smaller than in a corresponding dispersion similarly made from water (without any surfactant) and the powder product.

The above indicates that alkylarbamates have great potential as dispersants, particularly for hydrophobic products, since they enable to prepare dispersions with good stability.

The above indicated properties of the alkylcrarbmates and the combination thereof in the individual alkylcarbamates, make that the fructan alkylurethanes are highly valuable for use as surface-active agents in various compositions and in premixes for the preparation of said compositions These compositions and premixes can be prepared according to conventional techniques, for example, by simple mixing, preferably under low speed stirring, of all ingredients of the composition in the required amounts, including the selected one or more alkylurethanes or by addition of a desired amount of the one or more selected alkylurethanes (I) to a pre-mix of all other ingredients, or by adding a premix containing all COMS 10 No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/0803 17:45 CHQRYSILIOU LAJ NO.990 P015 WO 9W6452 PCTA49/03931 required ingredients, including the selected one or more alkylurethanes to a medium such as water or an aqueous or non-aqueous liquid, for example an oil, or a pasty composition.

The surface-active agents of the present invention are suitable for use as detergents, emulsfiers, emulsion stabilisers, liposome stabiisers, foaming agents, foam stabilisers and/or wetting agents in various household and industrial applications, such as for example in detergents for laundry washing& detergents for dish washing, industrial detergents, emulsifiers in cosmetics, emulsifiers and stabilisers in iks, in'patintigs and in coating compositions, and foaming agents and/or foant stabilisers in shampoo's.

Furthermore, the alkylurethanes present good thermal and chemical stability in combination with good biodegradability and they are free of phosphor/phosphates. Furthermore, the main raw drateals for the manufacture of the alkylcarbamates i.e. the fructans levan and inulin, are commonly agro-demnicals, i.e. carbohydrates from vegetal origin which in fact constitute renewable resources. The combination of said features makes that the fructn N-alkylcarbamates are environmentally well acceptable.

Besides, said carbohydrates, particularly inulin, are available at industial scale in suitable quality and at acceptable raw mateial prices which is an economically very important feature, maldking the use of alkylurethanes I as surfactants at industrial scale possible and attractive.

COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14

Claims (12)

1. Use as surface-active agent of a fructan N-alkylurethane (1) which is composed of saccharide units of general formula (U) A (O-CO-NH-R)s (II) wherein A represents a fructosyl unit or a terminal glucosyl unit of said fructan, being a levan or an inulin, with a degree of polymeriation (DP) of minimum 3, (0 CO NH R) represents an N-alkylaminocarbonyloxy roup replacing a hydrocyl group of the saccharide unit A, wherein R represents a linear or branched, saturated or unsaturated alkyl group containing from 3 to 22 carbon atoms and any mixture thereof, and s represents the number of N-alkylminoarbonylaxy groups per saccharide unit which is expressed as degree of substitution and said DS has a value ranging fromrn 0.10 to 2.0

2. Use according to claim 1 of an alkylrwethane wherein the alkyl group R is a saturated C-C22 alkyl group or a mixture of said alkyl groups.

3. Use according to claim 1 of an alkylurethane wherein the alkyl group R is a mono-unsaturated C3-C22 alkyl group or a mixture of said unsaturated alkyl groups.

4. Use according to any one of claims 1 to 3 of an alkylurethane (I) wherein the alkyl group R is a linear or branched C-C18 al&yl group or a. mixture thereof. Use according to any one of claims 1 to 4 of an alkylurethane wherein the degree of substitution has a value ranging from 015 to

6. Use according to any one of cdaims 1 to 5 of an alkylurethane (I) wherein the frctn is an inulin.

7. Use according to claim 6 of an alkylurethane wherein the fructan is a polydisperse linear or slightly branched inulin or a mixture thereof with a degree of polymerisation (DP) ranging from 3 to 100.

8. Use according to any one of claims 6 or 7 wherein the inulinhas an average degree of polymerisation (IDP) ranging fromn 6 to

9. Use according to claim 6, wherein the inulin is an oligofructose with a DP Use as a detergent, emulsifier, emulsion stabiliser, foaming agent, foam stabiliser, liposome stabiliser, dispersant and/or wetting agent of a fretan N-atkylurethane as defined in any one of claims 1 to 9.

11. Fructan N-alkylurethane as defined in any one of claimns 1 to 9. COMS ID No: SMBI-00378070 Received by IP Australia: Time 17:50 Date 2003-08-14 14/0e/03 1?:4G i4/0/~3 7:46 CHRYSILIOU LAW 4NO90P? NO.990 P017 WO PCFJKPfl/6931 22

12.. Frtan N-alkylurttafl according to claimn 11, which is selected frm the group consisting of inulin N- n-octylcarbat#, inulin N4HndeCYlCS bake and inulin N-n-octadecylcarbinltt

13- Composition coznprisrn as surface-active agent one or mor~e fructan N-alkyluretnes as defined ink any one of laiMs 1 to 9 and 12. 14t Composition according to claim 13 wherein the one or more fruclan M-alkyluirtthint$ are present mn a total oneatOf 0.001% to w/4) Composition accrding to claimn 13 or dm 14 whkih is a pro-mitx coImston suitable for the wlanufacture, by dilution with water or an aqueous rmdnw, of a composition as deffined in any one of claims 13 or 14.

16. Process for the manufacture of a fructan N-alkyiuretbam as defined in any one of clin:1 to 9 and claim 12, cohprising reacting a frua&Wai-t aflit solvent with such an amount of alkylisocyanate is that anN#~efj isyeded having'i depee of substitadion rangig fig,*O tDtO, tbk fiSt solvent being inert with respect to the fructan, tj socyan e and to alkylurethan fczlowed by precipitation of the formed, alkylurethane optionally after pata removal of the first solvnt by evaporation under reduced pressure, either by additio under staring of a precipitantt solvent to the reaction mixture or by slowly pouring =nder sfirring thie reaction xnittr into a precipitant solvent, followed by isolation of the precipitated alkylurethane M-) COMS ID No: SMBl-00378070 Received by II' Australia: Time (I-tm) 17:50 Date 2003-08-14