FI106207B - Process for preparing an amide-modified carboxyl- containing polysaccharide, and a fatty amide-modified polysaccharide which is obtained by means of the process, and its use - Google Patents

Description

106207

The present invention relates to a process for the amidation of a polysaccharide material containing at least one carboxyl group and to a process for the amidation of a polysaccharide material containing at least one carboxyl group. The invention also relates to hydrophobic modified polysaccharides containing carboxyl groups thus obtained.

A method for amidating at least one carboxyl group-containing polysaccharide material is disclosed in Yalpani et al. U.S. Patent No. 4,963,664. In the method described, a polysaccharide matrix containing at least one carboxyl group is reacted with an ammonium donor of general formula> NH to convert the carboxyl groups into amide groups. However, this method does not seem feasible. The process described in the Examples contains unusually long reaction times and the conversion obtained is low, which altogether prevents the process from being used on a commercially acceptable scale. Further, although the process described provides quaternary ammonium-modified polysaccharides, it fails to achieve the desired amidation result. Typical ammonium donors shown include ammonia, ammonium salts, primary and secondary amines, polypeptides, proteins, etc. Although Yalpani thus directs a person of ordinary skill in the art to use a variety of amines as an ammonium donor, there is no mention in the publication of a carboxy-containing modification is rendered hydrophobic.

U.S. Patent 4,988,806 (Griining) discloses a process for esterification of carboxymethylcellulose (CMC) with alkyl chloride and reacting the ester thus obtained with diamine to form the amine amide of CMC 106207 2, which is then quaternized. The process is relatively complex and the use of alkyl chloride should preferably be avoided as it is a less pleasant and relatively expensive compound which eventually ends up as a waste product. In addition, the process is limited to short-chain amines and does not appear to be suitable for converting CMC to hydrophobic.

Generally, it is extremely difficult to react hydrophilic materials, such as carboxyl-containing polysaccharides (especially CMCs), with hydrophobic agents such as fatty amines. However, hydrophobic polysaccharide derivatives are known in the art.

U.S. Patent 4,228,277 (Landoll I) discloses cellulose ethers having a degree of substitution of 15 nonionic groups (methyl, hydroxyethyl, hydroxypropyl) sufficient to render them water-soluble and further substituted with about 10 to about 24 carbon atoms in the hydrocarbon group. 0.2% by weight to an amount which renders said cellulose ethers slightly insoluble in water (less than 1% in water). The coupling of the hydrocarbon group to the cellulose ether is accomplished by reaction with a long chain modifier which may be an alkyl halide, epoxide, isocyanate, acid or. an acyl halide. The materials disclosed in this publication have an effect on increasing viscosity and also have some surfactant properties.

U.S. Patent 4,243,802 (Landoll II) discloses similar cellulose ethers having a C10.24 · ·· · hydrocarbon substitution such that cellulose ether has become insoluble in water. . These materials are used to increase the viscosity of surfactant solutions: 3 or as emulsifiers for aqueous systems.

«« E «· 1« • · • · · · · · · · 2 • · 3 • · · ♦ • 106207 3

Similar cellulose ethers wherein the C10-24 substituent is an alkylaryl group are disclosed in U.S. Patent 5,120,838 (Just et al.).

Hydrophobically substituted, water-soluble cationic polysaccharides are known from EP 189 935. An essential part of these materials is the side chain which contains one or more quaternary ammonium groups and may also include a C12-18 hydrocarbon chain. These materials are substantially water-soluble and provide aqueous solutions with increased viscosity, parented foaming properties, and surfactant properties. Their uses include personal care products, emulsions and cleansers.

EP 512 319 discloses urethane derivatives of polysaccharides prepared by reacting a polysaccharide containing carbonate groups with a protic nucleophile such as an amine. The polysaccharide containing carbonate groups is obtained by reaction between polysaccharide and phosgene. Amidation and process are not recommended in any way in this publication because of the use of hazardous chemicals such as phosgene and pyridine and the low yield (about 25%).

• · ·. *, ·. EP 566 118 (unpublished) describes the formation of crosslinked polysaccharides. In the disclosed methods, the polysaccharide is mixed with the crosslinking agent in solution, the polysaccharide is recovered from the solution and then heated to obtain crosslinking.

The invention now seeks to provide an amidation process which, contrary to Yalpan's method: - **, is easy to implement and commercially acceptable. The invention also seeks to provide a process for rendering carboxyl-containing polysaccharides hydrophobic. It is a further object of the invention to provide a process for modifying a substantial portion of carboxyl groups, or at least a method whereby almost all of the ammonium donor is added. can be incorporated into the compound. In particular, the invention seeks to provide a process for the preparation of an amide-modified carboxyl-containing polysaccharide which can be applied to fatty amines.

These objects are achieved by the process of the present invention for the amidation of a material having 10 polysaccharides containing at least one carboxyl group which comprises reacting the carboxyl groups with an ammonium donor of general formula> NH, which is carried out in two successive steps to react the carboxyl and forming a polysaccharide ammonium salt, and in a second step heating the polysaccharide ammonium salt to convert the ammonium groups to the corresponding amido groups.

Using this method, many different products can be prepared from polysaccharides having different carboxyl groups (i.e. based on cellulose, starch, guar gum or other polysaccharides) with varying polymer chain lengths. (e.g. CMC is available in a variety of polymerisation stages) • · 25 and having an anionic character varying (due to the different degree of carboxyl substitution «I«).

Suitable carboxyl-containing polysaccharides include the polysaccharides mentioned in Yalpin's patent, supra. carboxylic · · «V 1 30 celluloses, especially carboxymethylcellulose (CMC), starches, especially carboxymethyl starch, guar gum: 1 '1 mit, especially carboxymethyl guar gum, chitins, chitosan, glycans, galactans, glucans,. , polymannuronic acids, polyglycosuronic acids, 35 polyglucuronic acids, mannans, dextrins, cyclodextrins, 106207 nit and other synthetically carboxylated or naturally occurring carboxylated polysaccharides which may be straight or branched.

According to the invention, it is preferable to select a carboxyl-5-containing polysaccharide from the group: carboxymethylcellulose (CMC), CMC cellulose mixed ethers such as carboxymethylhydroxyethylcellulose, hydroxypropylcarboxymethylcellulose (HP-CMC), -10 nitrogen-containing carboxymethylcellulose (QN-CMC) such as CMC etherified with glycidyltrialkylammonium chloride, carboxymethylethylsulfonate cellulose (CM-ESC), methylcarboxymethylcellulose (M-CMC), CMS-carboxymethyl-starch (QS), carboxymethyl-starch, 15 Cimethyl guar gum (CMG), CMG mixed ethers such as HP-CMG and QN-CMG, carboxymethyl inulin and carboxymethyl inulin mixed ethers. Mixtures of these polysaccharides may also be used.

These carboxyl-containing polysaccharides 20 are readily available or can be prepared, for example, by etherification with monochloroacetic acid. The ability to obtain or prepare carboxyl-containing polysaccharides is well known in the art and does not require further explanation here.

I («: 25 Ammonium donor can also be widely varied, i v t" V, which greatly increases the number of products being manufactured.

For example, the ammonium donors mentioned by Yalpan may be used. Ammonia · «and butylamine have been used with particular success, but aromatic amines, •yy · · *. Mixtures of amines may also be used, ·· «:! e.g. a mixture of an alcoholic amine such as ethanolamine and a fatty amine ··· '· 1 n. Thus, mixed amide carboxime - (polysaccharides of the style). Suitable amines include aminoethylpiperazine, ethanolamine and di- or% -I-. 106207 6 Examples of the latter are ethylenediamine oligomers sold under the trade name "Delamine", such as pentaethylene hexamine.

With regard to the possible use of polyamines, it should be noted that the above mentioned EP-A-566 118 discloses the use of polyamines as crosslinking agents. This publication is limited to crosslinked polysaccharides, whereas the present invention seeks to provide many different modifications. Although it is possible to produce crosslinked carboxyl-containing polysaccharides according to the invention in a process embodiment using polyamines as ammonium donors, the present invention is primarily directed to the modification of carboxyl groups, eg by attaching long carbon-carbon chains or by adding cationic groups. Cross-linking of polysaccharides containing carboxyl groups, which can be carried out with relatively small amounts of cross-linking agent, is completely different from forming modifications in which a substantial portion of the carboxyl groups are reacted. This result cannot be achieved by the process described in EP 566118 but requires a two step process in which the corresponding carboxylammonium salt is formed according to the present invention.

* · ·:. ·. 25 This process is particularly suitable when using fatty amines • · · IV · '. The present invention thus provides the solution above

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• · * \ problem with respect to the reaction between hydrophilic and hydrophobic substances by hydrophobically modified polysaccharides (in this case, fatty amide-polysaccharides). lysaccharides), since the reactive groups of hydrophilic and hydrophobic molecules are already attached to one another through relatively simple formation of the polysaccharide ammonium salt.

Fatty amines suitable for the formation of the fatty amide-modified h. 35 carboxyl-containing polysaccharide fatty amide groups of the present invention include: usually saturated or unsaturated hydrocarbon groups having from 8 to 30 carbon atoms. Branched hydrocarbon groups are not excluded, but straight-chain groups are more preferred. The fat radical is preferably derived from a C12-24 fatty amine. Fatty amines are well known in the art. Particularly preferred results are obtained when the fatty amine is selected from: n-dodecylamine, n-hexadecylamine, n-octadecylamine, cocoamine, thalamin-10, hydrogenated thalamine, oleylamine, N-size-1,3-diaminopropane, N- tallow 1,3-diaminopropane, N-hydrated tallow 1,3-diaminopropane, N-oleyl-1,3-diaminopropane. Such fatty amines are known under the trade names Armeen and Duomeen (Akzo Chemicals).

Still another means of varying the products obtained by the process of the present invention is to control the number of carboxyl groups converted to the carboxylammonium salt. Most often, this conversion is accomplished by exchange of sodium (or other salt counter ion) with an ammonium donor. The degree of exchange is defined as ctr and indicates the degree of amine substitution and the degree of carboxyl substitution. For fatty amine (FA) and carboxymethyl groups (CM), the following formula (where DS is the degree of substitution) applies: «« · «· 1. . This method using a salt of a carboxyl-containing polysaccharide, preferably the sodium salt, is used in the preparation. is one of the preferred methods for carrying out the first step. This is accomplished by dispersing said salt in an aqueous alcoholic medium, i.e. a medium containing both water and an alcohol, preferably an alcohol miscible with water, such as ethanol, to form a slurry having a concentration of up to about aa 50%, preferably about 10-40%, by addition of an ammonium donor as well as an acid, e.g. hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and then dilution with water. In particular, the addition of water has been found to promote the formation of the carboxylic ammonium salt, probably because it dissolves the sodium chloride used in the exchange reaction and shifts the equilibrium in the water-enriched alcohol medium thus formed in the desired direction. The dissolved salt (NaCl) can be washed off, for example, by filtration of 10 polysaccharide ammonium salts.

Suitable alcohols include, for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, tert-butyl alcohol, ethylene glycol, propylene glycol, glycerol. Ethers and ketones (eg acetone) may also be used.

In another preferred method for carrying out the first step, a polysaccharide containing carboxyl groups is used in an acid form which is simply mixed with the ammonium donor 20 in the form of the free base. Polysaccharides containing carboxyl groups are usually available in salt form, which must first be converted to the free acid form (e.g., by addition of an acid such as hydrochloric acid and / or purification thereof). The advantage of this method is that pure polysaccharide carboxyl ·; The 25 liammonium salts are obtained without the loss of any unreacted amine.

In order to obtain an acceptable conversion of the carboxylammonium groups to the amido groups, the second step ··· ••• yleensä should generally be accomplished by heating the polysaccharide salt preferably · · · ·. at least about 100 ° C, more preferably about 140-250 ° C. The upper limit is determined by the temperature at which the polysaccharide actually begins to decompose. Preferably, the temperature is further maintained below the point at which the well-known 35 · polysaccharide Maillard reaction (about 150 ° C) begins. resulting in polysaccharide products starting to brown, which is usually considered less desirable, and is preferably carried out within a few hours at 140-150 ° C. C.

Although many different media, including air and nitrogen, may be used to heat the quaternary ammonium salt of the polysaccharide, including air and nitrogen, the possibility of a Maillard reaction is minimized if the heating is carried out in an organic solvent medium having a boiling point at or above normal temperature. Both semi-polar and non-polar media have proved to be suitable. Polar media such as glycol and glycerol may dissolve some types of polysaccharides and polysaccharide ammonium salts with low α coefficients, which may result in sticky products and high viscosities. High alpha coefficients, on the other hand, are insoluble in glycol and glycerol. The choice of medium will generally depend on the end use of the product. In many cases, preferred media are non-polar solvents (or non-solvents) such as xylenes, of which o-xylene is most preferred because of its high boiling point (145 ° C) and its ability to remove water (initially present and liberated during amidation). ) azeotropically with distal * · · ·: 25, which advantageously affects the conversion.

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The process of the present invention generally aims to avoid ester linkages. Ester formation usually occurs as a side reaction, particularly when carboxyl groups present in the acid are reacted intramolecularly or intermolecularly with hydroxyl groups also present in the polysaccharide. Intermolecular ester formation results in a · ··· 1. · 1 "; coagulation, which renders the polysaccharide insoluble and, in most cases, harmful. However, the esters # 9 1 35 can serve as an intermediate in amidation and the formed ester linkages can be converted to amides when used in amidation. some excess amine. If the ester linkages cannot be completely changed, they must preferably be removed by post-treatment, e. G., Equimolar amounts of sodium hydroxide or ammonia, which are effective.

The invention also relates to novel and useful hydrophobic polysaccharide derivatives obtainable by the process described herein. The materials prepared according to the invention form a new class of amidated carboxyl-containing polysaccharides, characterized in that the amidated carboxyl groups are fatty amide groups. The combination class of hydrophobic carboxyl-containing polysaccharide derivatives of the present invention provides numerous possibilities for varying the materials of the material, as well as the reaction conditions and media, by tailoring the properties of the material to the desired purposes. As to the specific ingredients of these products, reference is made to the 20 explanations above.

Preferred materials comprise a polysaccharide selected from: carboxymethylcellulose (CMC), CMC cellulose mixed ethers, carboxymethyl starch (CMS), CMS mixed ethers, carboxymethyl guar (CMG),. 25 CMG mixed ethers and mixtures thereof, and a fatty amine selected from dodecylamine, tridecylamine, • myristylamine, laurylamine, thallamine, cocoamine, **** oleylamine, N-size-1, 3-diaminopropane, N-tallow-1,3-dia- ······· minopropane, N-hydrated-tallow -1,3-diaminopropane, ♦ 1 · *. 2 N-oleyl-1,3 diaminopropane and mixtures thereof.

The amide-modified carboxyl-containing polysaccharides of the present invention, especially the fatty amine-3: derivatives, can be widely used.

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Thus, the products prepared in accordance with the present invention can be used in biodegradable forms. 1 ♦ 1 • 2 2 1 2 • 3 2. 106207 11 in the manufacture of. While it is possible to make biodegradable plastics from the materials of the present invention, the most preferred use in the art relates to the use of biodegradable polymers, e.g.

5 starch based additives. This includes in particular hydrophobic (fatty amide modified) CM starch or CMC. Such a hydrophobic starch-compatible additive solves the problem of excessive hygros-10 opacity for many applications of starch-based polymers. By adding the products of the invention to starch-based plastics, it is also possible to avoid cleavage of the starch polymer strand. The fatty amide modified carboxyl groups-containing polysaccharides of the present invention can also be used to coat the surface of starch-based plastics to hydrophobize said surface. Additionally, fatty amide dicarboxymethyl starch or fatty amide carboxymethyl cellulose, both of which are water insoluble, may be dissolved in water containing additional solvent 20 (e.g., about 10% butyl glycol ether). The water resistance of starch-based plastics coated with such a solution has been improved. The products of the invention are also useful as compatibility enhancers. as substances in starch-based polymers, i.e. they • «·« · ·. 25 facilitate the mixing of starch based polymers with other polymers such as polyethylene.

The products of the present invention are also anti-redeposition agents for · · · · · · · · · · ... synthetic fibers suitable for use with synthetic fibers. For example, CMC is widely available

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·. 2 1 3 0 used to prevent dirt from re-precipitating on cotton fibers, but less effective in the case of synthetic fibers. Non-ionic cellulose ethers are somewhat better, but still less satisfactory and also relatively expensive. The products of the present invention, in particular the fatty amide-modified fatty acid amide-modified 106107 12 CMC. advantageous results as dirt re-precipitation inhibitors for synthetic fibers. Compared to CMC, their adsorption to synthetic fibers is better. Due to their compatibility with liquid detergent compositions, polysaccharides containing fatty amide-modified carboxyl groups such as fatty amide-modified CMC can also be used therein as anti-redeposition agents. Further, fatty amide-modified polysaccharides, in particular CMC, can be used as dispersants for zeolites, especially in concentrated liquid detergent compositions.

The dispersion properties of amide-modified carboxyl-containing polysaccharides, particularly fatty amide-modified CMC, can also be utilized in dispersing Pigment-15 in aqueous coatings. It is possible to design the adsorption capacity of the products of the invention individually for different pigments by modifying a polysaccharide containing carboxyl groups using amines having functional groups improving the adsorption properties, such as benzylamine or 1- (2-aminoethyl) piperazine.

Other uses include use as polymeric emulsifiers, anti-settling agents and rheological agents. as modifiers for these properties, in particular bitumen 25 in emulsions, for use in cosmetics, as associative coagulants, · · · 1 as drilling fluids, as superabsorbents, in mineral processing, and in a variety of other uses.

e '2! The invention is further illustrated by the following non-limiting examples of the invention ****.

Example 1 (a) In a 1 liter reactor equipped with a stirrer, 100 g of 80% ethanol was suspended in 100 g.

M1 *, 1,1 sodium carboxymethylcellulose having a degree of carboxymethylation (DS4) of 0.77 and a moisture content of about 6%. To this suspension was added 16.6 g of ArmeenRHTD, which is commercially available ( Akzo Chemicals) a mixture of primary alkylamines containing 64% C18, 31% C16 and 5% C14 and C12 alkylamines. An equimolar amount of the hydrochloric acid 5, in this case 19.5 g of a 12% aqueous HCl solution, was also added to the suspension with the primary amine. To completely dissolve the fat amine, the reaction mixture was heated at 40 ° C. Then 150 ml of water was added and stirring at 40 ° C was continued for one hour. After cooling, the product was filtered and washed with aqueous 10% ethanol. The nitrogen content of the dry product was determined by the Kjeldahl nitrogen analysis method and was 0.64% by weight, which corresponds to a degree of substitution (CMFA salt) of the CMC carboxylic fatty ammonium salt (DSFA salt).

(b) 90 g of the CMC fat ammo-15 nium salt prepared in 1a was suspended in 150 ml o-xylene and the suspension was heated at 140 ° C for 3 hours. After these 3 hours, an additional 4 g of HTD in Ar was added to the hot reaction mixture and the reaction was allowed to continue at 140 for a further 2 hours. The cooled mixture was filtered and washed with 50 mL of 20 o-xylene and then with ethanol (2 x 50 mL). The dried product contained 0.06% by weight of nitrogen.

(c) As shown by infrared analysis, the product prepared in Ib had, besides the amide, still some *:

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; ·. 25 carboxymethyl groups by suspending Ib product • V * in 200 mL aqueous ethanol. 10 g of 20 wt.% NaOH solution were added to the suspension and the mixture was heated at · *** 50 ° C for 45 minutes. The mixture was cooled and neutralized.

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The product was then filtered, washed with aqueous * * * '· * 30 ethanol and dried. Some of the reaction parameters and DSfa are shown in Table 1.

EXAMPLE 2 (a) In a 1 liter reactor equipped with a stirrer, 100 g • · · 35 sodium carboxymethylcellulose having a (DS ^) of 0.77 and • were suspended in 200 g of 80% ethanol. · Moisture content of 6% by weight. To this suspension was added 88.1 g of primary alkylamine, Armeen HTD. Then 108 g of 12% aqueous HCl solution was added with stirring. The reaction mixture was heated at 40 ° C, 5,500 ml of water was added thereto and stirring at 40 ° C was continued for 2 hours. The mixture was then cooled to room temperature, filtered and washed with water and then with ethanol. The dried CMC fat ammonium salt had a nitrogen content of 2.83% by weight, corresponding to a DSPA salt ratio of 0.70.

(B) 150 g of the CMC fatty ammonium salt prepared in 2a was suspended in 500 ml of ethylene glycol with stirring and the suspension was heated at 150 ° C for 2 hours. An additional portion (10 g) of Armee HTD was then added to the hot reaction mixture and heating continued at 15 to 150 ° C for a further 2 hours. To the mixture cooled to 50 ° C was added 15 g of a 20 wt% NaOH solution and stirring was continued for 30 minutes. The reaction mixture was then filtered and washed with water followed by ethanol. The dried product contained 2.50% by weight of nitrogen, corresponding to 20 degrees of DSFA of 0.72, as also shown in Table 1. Examples 3-5 The products of these examples were prepared by the method described in Example 1. The degree of amidation of the products varies.

: 25 The results of Examples 1-5 are also shown in the table «« * * ♦ ♦ · - | • · · X.

• · • ·

The CMC used in Examples 1-5 is a pure commercial grade high molecular weight CMC produced by Akzo Chemical Group (> 99% dry matter) with a Brookfield viscous solution of 1% solution. tea (30 rpm; demineralized water; 20 ° C) is 3,000 »··· · * ... * mPa.s, DScm is 0.77 and the moisture content upon saponification is • · ♦ 6%.

«« «• i« • «« • «• • • • • • ♦ • ♦ • ♦ • ♦ • 1S 106207

The amine used in Examples 1-5 is Armeen HTD, a commercial product produced by Akzo Chemical Group. The HTD composition of the arm is mentioned in Example 1.

The amounts of 5 amines and water used in the preparation of the CMC fat ammonium salt in columns 3 and 4 of Table 1 are based on the amount of CMC (100 g) initially suspended in 80% aqueous ethanol (200 ml).

The amounts of HCl used to prepare the CMC fat ammonium salt were equimolar with the amounts of amine.

Amidations of Examples 1, 3, 4 and 5 were performed under reflux in heated o-xylene. As seen in Example 2, the amidation of this product was performed in glycol.

15 Table 1

Eg Amine Water DSFA Salt Amine DSpA Water Amount Excess Amount? (g) (g) 20 1 16.6 150 0.12 0.03 0.06 is 2 88.1 500 0.70 0.09 0.72 no 3 56.0 500 0.42 0.04 0, 33 no 4 5.6 130 0.03 0.015 0.021 is. 5 4.2 110 0.022 0.009 0.013 on: 25 • · «·: 1.1 · Examples 6-11 • · • ·

To study the rheological properties of the prepared] J. by the method described in Example 1, a series of products, *! '.! whose properties are shown in Table 2.

The CMC used in the manufacture of these products is the same as that used in Examples 1-5. The amine used is * ... 1 commercial product of the Akzo Chemical Group Armeen CD, •, *, which is a mixture of primary alkylamines containing 6% C8, 6% C10, 50% C12, 19% C14, 10% C1S and 10%. 35 C18 alkylamine.

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Table 2

Eg N content DFA DS ^ / DSo, (a) Water soluble? (by weight) 5 6 2.05 0.46 0.60 no 7 0.46 0.08 0.10 have 8 0.29 0.051 0.066 have 9 0.071 0.012 0.016 have 10 0.046 0.008 0.010 have 10 11 0.015 0.003 0.004 is

The viscosity of the products of Examples 8-11 was measured as a function of shear rate, and it was found that as aqueous solutions, the false plastic behavior of the products increased as the hydrophobic content increased. These results are shown in Table 3, which in tabular form represents the rheogram obtained from these measurements.

Table 3 20 Viscosity (log mPa.s)

Example: 8 9 10 11

Shear rate (1000 / s): 25 Ο, ΟΟΟΟΙ 2.742 2.849 3.626 5.770 Γ · *: 0.0001 2.742 2.795 3.572 5.234 «·.:. 0.001 2,715 2,768 3,465 4,403 1:. 0.01 2,608 2,634 3,090 3,572 0.1 2,340 2,366 2,661 2,902 • · ♦ * 30 1 1,911 1,938 2,098 2,286 • · · ** .. * Examples 12 - 15 • · · (a) 50 g of purified NaCMC with The 1% solution had a Brookfield viscosity of 100 mPa.s (30 rpm; 35 demineralized water; 20 ° C), a DSq, of 0.56 and a humidity? 106207 17 was suspended in 150 ml of 80% aqueous ethanol in a 1 liter reactor vessel. To this suspension was added 100 g of a 50% by weight solution of Arme CD-HCl alkylammonium salt in ethanol. 800 ml of water were then added and stirring at room temperature was continued for 2 hours. The product was filtered and washed with water and then with ethanol. The dry product contained 2.55% by weight of nitrogen, corresponding to a value of 0.98.

(b) The CMC fat ammonium 10 salt prepared in 12a was heated in an oven at 145 ° C for 4 hours. The product was then suspended in 300 ml of 70% aqueous ethanol containing a small amount of sodium hydroxide. After heating for 1 hour at 50 ° C, the mixture was filtered and washed with 70% aqueous ethanol and then with 15% pure ethanol. The dry fatty amide CMC had a nitrogen content of 2.48% by weight.

Using the same NaCMC and the same amine in different ratios, the products shown in Table 4 were prepared by the method of Example 12. In each example, 50 g of CMC was initially suspended in 150 ml of 80% aqueous ethanol.

Table 4 ·. ·., Eg 50% w / w Water in DSPA DSFA / DSFC («)« ti; 25 amine HCl (g) · 1: 1: amount (g) • · · · · · - · · · · · · · · · · · · · · · · · · · 14 50 250 0.21 0.37 30 15 10 125 0.017 0.03 16 5 75 0.006 0.01 Example 16 (a) 100 g of purified NaCMC with A 1% solution of 35 had a Brookfield viscosity of 2000 mPa.s (3020 te 186 rpm; demineralized water; 20 ° C), DS (a) was 0.98 and the moisture content was 6%, suspended in 400 ml of 70% aqueous ethanol. To this suspension was added 100 g of 20% HCl solution. After stirring for 30 minutes, the suspension was filtered and washed with 20 g of 20% HCl solution and then 2 times with 250 ml of 70% aqueous ethanol.

(b) The HCMC prepared in 16a was suspended in 150 ml of 90% aqueous ethanol. Then 70 g of pentaethylene hexamine (PEHA) was added and stirring was continued for one hour. The mixture was filtered, washed with aqueous ethanol and dried. The dry product weighed 126 g.

(c) The product prepared in 16b was heated at reflux in 300 ml o-xylene for 3 hours.

25 g of PEHA was then added and refluxing continued for a further 1.5 hours. The product was then filtered and washed with ethanol and acetone.

Example 17 20 (a) 50 g of sodium carboxymethyl starch having a DS0 * of 0.25 were suspended in 100 ml of 80% aqueous ethanol. To this suspension was added 40 g of a 50% w / w solution of Arme CD-HCl. After stirring for 2 hours at room temperature, the reaction mixture was filtered and (washed with 80% aqueous ethanol. Dried: **]: the product had a nitrogen content of 1.28% by weight.

·· (b) The CMS fat ammonium salt prepared in step 17a was suspended in 100 ml o-xylene and the suspension was heated under reflux for 3 hours. The product was then filtered and washed and the ester linkages therein ... converted to sodium carboxymethyl groups by treatment with mild sodium hydroxide under mild reaction conditions. The purified product had a nitrogen content of 0.96% by weight, corresponding to an alpha value of 0.64.

• «I I <* · • ·« • «·« «« · • 106207 19

Example 18 (a) For a suspension of 50 g CMC with a DSch of 0.77, a moisture content of 6% and a Brookfield viscosity of a 1% solution at 3000 mPa.s (30 rpm; deminera-5 added) water; 20 ° C) in 200 ml of 80% aqueous ethanol, 12 g of concentrated HCl solution were added. The suspension was filtered and washed with 80% aqueous ethanol, the wet product was dried under vacuum at 140 ° C for 5 hours.

10 (b) The cross-linked CMC ester prepared in 18a was suspended in 150 ml o-xylene. To the suppression was added 75 g of Armee CD and the mixture was heated under reflux for 3 hours at 140 ° C. The mixture was then filtered and washed with o-xylene and ethanol. The IR spectrum of the dried product showed an amide bond at 1665 cm -1; the product had a nitrogen content of 2.05% by weight, corresponding to a DSFA of 0.44.

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Claims (16)

106207 20 A process for amidating at least one carboxyl group-containing polysaccharide-containing material by converting the carboxyl groups into amido groups by reaction with an ammonium donor of general formula> NH, characterized in that the reaction is carried out in two successive steps to react the carboxylic and, in a second step, heating the polysaccharide carboxylammonium salt to convert the carboxylammonium salt groups to the corresponding amido groups. A process according to claim 1, characterized in that, in the first step, the salt of the carboxyl-containing polysaccharide is dispersed in an aqueous alcoholic medium to form a slurry of about 5 to 50%, ammonium donor and acid are added and the slurry is diluted with water. 3. A process according to claim 1, characterized in that in the first step the polysaccharide containing free carboxyl groups is mixed with an ammonium donor. The process according to any one of claims 1 to 3, characterized in that, in a second step, the polysaccharide carboxylammonium salt is heated at a temperature of about 140-150 ° C. • · · · A process according to claim 4, characterized in that the heating is carried out in an organic solvent medium having a boiling point at or above the temperature used at normal pressure. The process according to any one of claims 1 to 5, characterized in that the ammonium donor 35 is selected from the following: fatty amines, benzylamine, amine. • · 1 • · 106207 21 Noethylpiperazine, Alcohol Amines, Diamines, Polyamines and Mixtures thereof. A process for the preparation of a fatty amide modified CMC according to claim 1, characterized in that the following steps are carried out: - reacting the CMC or a salt thereof with a fatty amine to form the corresponding CMC carboxyl fatty ammonium salt; - The CMC carboxyl fat ammonium salt is heated at a temperature of about 120-150 ° C to convert the ammonium groups to the corresponding amido groups. A process according to claim 7, characterized in that in the first step - the CMC alkali metal salt is dispersed in an aqueous alcoholic medium to form a slurry at a concentration of about 10 to 40%; - addition of a fatty amine and a strong mineral acid; - the slurry is diluted with water; and in a second step heating the quaternary CMC fat ammonium urea salt in xylene. 9. A material having at least one amidated carboxyl-containing polysaccharide, characterized in that the amidated carboxyl groups are fatty amide groups. • ·: 25 lO. Material according to claim 9, characterized in that the polysaccharide is selected from the following: carboxymethylcellulose (CMC), CMC cellulose ······· mixed ethers, carboxymethyl starch (CMS), CMS: ethers, carboxymethyl guar (CMG), CMG mixed ethers, and mixtures thereof. Material according to claim 9 or 10, characterized in that the fatty radicals contained in the fatty amide groups are saturated or unsaturated C8-30 hydrocarbon groups. <· «« «<« • «• · · · · · · · · · · · · · ··· · Material according to claim 11, characterized in that the fat radical is selected from dodecylamine, tridecylamine, myristylamine, laurylamine, thallamine, cocoamine, oleylamine, N-size-1,3-diaminopropane, N-talc. 1,3-diaminopropane, N-hydrated tallow-1,3-diaminopropane, N-oleyl-1,3-diaminopropane and mixtures thereof. Material according to claim 10, characterized in that it is a fatty amide modified carboxymethylcellulose (CMC). Use of fatty amide modified carboxymethyl cellulose and / or fatty amide modified carboxymethyl starch in polymers as a hydrophobic additive. 15. Use of fat amide modified carboxyl-containing polysaccharides as pigment dispersants in aqueous systems. Use of a fat amide modified carboxyl-containing polysaccharide to make starch-based polymers compatible with other polymers. «·« 1 · «« ·••••••••••••••••••••••••••••••••••• · ♦ · ♦ ♦♦ ♦ ♦♦ ♦ ♦ ♦ • · • 106 106 106 106 106 20 106207 23