DE2050849A1 - Sulphatisation of carbohydrate rubber (polysaccharides)- - without appreciable modification of molecular structure - Google Patents

Abstract

Sulphation of carbohydrate gums (poly-saccharides) without significantly modifying the basic carbohydrate structure is carried out in a solvent contng., as sulphating agent, the reaction product of SO3 and a Lewis base. The carbohydrate is made ready for this process by the following treatment: Water-swollen gum particles are suspended in a water-miscible substitute liquid. This liquid does not exhibit an irreversible reaction with the sulphating agent. Its vapour pressure is below that of water and it is miscible with the solvent for the sulphating agent or is the same as this solvent. When the substitute liquid is removed, water-free particles which are suitably activated for the above sulphation process are obtained. Claimed uses include application as suspension agent in a beverage comprising cocoa particles, milk and sweetener, and as binding agent in toothpaste. Mol. structure of the starting carbohydrates is largely preserved. Characteristics are improved, including suspension props in water.

Description

Process for sulfating gums, in particular carbohydrate gums Different polysaccharides can be converted by one reaction using different Sulphating agents are sulphated, with one or more of the hydroxyls through the sulfate group .0. 03 to be replaced. Depending on the type of polysaccharide it is the average number of hydroxyl groups per sugar residue is not always the same. For example, guar, locust bean gum, starch, and cellulose have on average per sugar residue three hydroxyl groups and a complete sulfation is considered one DS 3 referred to. Algin and pectin each have only two hydroxyl groups and each sugar residue complete sulfation results in a DS 2. EEr gum arabic is the value between 2 and 3.

It is known to use different types of polysaccharides, such as cellulose, Pectin, amylopectin, amylose and algin, in both aqueous and non-aqueous Sulfate systems. In a non-aqueous sulfation system, the Example the following sulfating agents used: the reaction product of N, N-dimethyliormamide (DMF) and SO3 (DMF: SO3) in solution with anhydrous DMF (USA patents 3.200.110, 3,349,078, 3,401,160, British patent specification 1,110. 335) triethylamine sulfur trioxide dissolved in DMF (Whistler et al., Arch. Biochem.

hiophys., 95, 36-41 (1961)); Chlorosulfonic acid in solution with pyridine (U.S. Patents 2,599,564 and 3,271,388); Dimethyl sulfoxide containing sulphurous trioxide (Whistler et al., Arch. Biochem. Biophys., 121, 358-363 (1967)); and formamide: SO3 (Swiss patent 305v572) In aqueous systems are for Example the following sulfating agents have been used: an aqueous solution of brimethylamine sulfur trioxide and with or without further addition of sodium sulfate (USA patents 2,786,833, 2,967,178 and 3,077,373).

In the known processes, the sulfation is practically so far driven as theoretically possible, keeping the original molecular structure of the Rubbers should be largely preserved; however, it has been found in practice that carrying out a sulfation with an attack on the original Molecular structure is connected, so that the reaction products obtained are practical have not proven to be valuable because they have stabilizing and gel-forming properties that of a naturally occurring sulfated polysaccharide hydrocolloid like carrageenan correspond. Polysaccharides such as locust bean gum, guar, and starch are abundant and, as a result, cheaper than carrageenan extracts and a method for successfully sulfating such gums while maintaining the molecular structure that the addition of sulfate groups to suspension and gel properties Leads that correspond to those of carrageenan has considerable economic Meaning. So far, however, sulfated rubbers of the type in question have had them Properties not.

The present invention is based on the object of practically complete sulfation of Coals tummis while largely retaining the molecular structure of the original gum, thereby achieving improved properties including water suspension and milk reactivity.

The invention is also based on the object of such rubbers in to sulfate in a predetermined manner so far that thereby the sulfation product for particular uses is given desirable properties.

It is also an object of the invention to produce novel sulfated gums useful in food, cosmetics and other products. In accordance with one feature of the present invention, there is provided a carbonate ae £ tegummi brought into such a state that it can be sulfated with the slightest attack on the molecule. If such rubbers are sulfated in the dry state by known processes, they withstand sulfation to such an extent that the original molecule is excessively attacked when a desired DS is achieved.

According to the present invention, rubber particles are sulfated in the presence of a sulfating agent which is present in the form of the reaction product between SO3 and a Lewis base in a solvent; In accordance with an essential feature of the present invention, these objects are achieved by making rubber particles such that they can be easily sulfated by the sulfating agent without undue degradation or loss of viscosity affecting properties. If the sulfation is carried out with a sulfating agent of the type specified, the sulfation must be carried out under anhydrous conditions, because the water present is extremely reactive with the SO3, which is kept in a reversible state by the Lewis base, with sulfuric acid being formed, and as far as this occurs, the SO3, which otherwise causes the sulphation of the rubber, is removed from the reaction zone, and the sulfuric acid formed as a result can lead to the breakdown of the rubber. It is therefore essential when using a sulphating agent of the type indicated that the rubber particles are practically free of water. In addition, the reaction mass must be free of any other material, such as a lower aliphatic alcohol, which reacts rapidly and irreversibly with the SO present in the sulfating agent. If particles are a Carbohydrates If the gum is air-dried prior to sulphation, it will no longer be rapidly sulphated, and if sulphation occurs at all, sulphation is associated with excessive degradation so that the product of the process is practically worthless, whether the gum is swollen or otherwise stretched and then dried.

It was found that Coal = rubber particles enwgsser; cr can be prepared in such a form that they can be easily sulfated by converting the rubber into hydrous particles elongated by water, forming a sludge of the particles in a liquid, water-miscible surrogate which does not undergo irreversible reaction with the sulfating agent and which is miscible or substantially the same as the solvent for the sulfating agent and whose vapor pressure is lower than that of water. If the sludge is subjected to a treatment in which evaporation of the volatile liquid occurs, the water content of the particles is virtually completely removed, and it has been found that, when the water has been removed in this way, the resulting, practically anhydrous gum in is in such a state that it can be sulfated very easily without causing excessive degradation of the polymeric molecular structure or even causing further opening of the molecular structure, so that sulfated rubbers can be obtained which have viscosities higher than non-sulfated ones Have rubbers from which they are obtained. The particles subject to sulfation should also be free of any other substance which will irreversibly react with the sulfating agent. It is a further advantage of the present invention that when the wet gum particles have combined with any liquid other than water, such as a lower aliphatic alcohol, which has a higher vapor pressure than the liquid surrogate, the removal of such alcohol, for example, is concurrent with it the removal of the water takes place during evaporation. The slurried particles should be free of any liquid or substance which can irreversibly react with substantial amounts of the sulfating agent and which will not be removed on evaporation due to a vapor pressure equal to or less than that of the liquid surrogate.

The rubber particles can be produced in different ways, to be in a water-containing, water-extended state. According to a particular embodiment of the present invention that works in a very effective manner causes the desired elongated state of the particles, rubber is in an aqueous Medium is dissolved to obtain a liquid solution of the gum, and the gum becomes then from the aqueous solution with the formation of a particle coagulate in an aqueous one Medium deposited. The term particles is intended to be used in the broadest sense of the word be understood to include every possible particle shape that may be formed, including fibrous particles. The coagulation is generally achieved by staggering the rubber solution achieved with a water-miscible hydrophilic liquid, in the gum is insoluble to provide a medium in which the gum coagulates. the But coagulation can also, as will be described in detail below, done in other ways.

The rubber particles can optionally be made to water and be stretched without going into solution. This can be done through a sufficient amount of aqueous medium can be obtained to prevent the swollen Excessively agglomerate particles. In the case of more soluble gums, the particles without stretching or excessive agglomeration by applying a mixture of water and a hydrophilic liquid in which gum is insoluble are swollen.

It is believed that the improved ease of sulfation is based on the fact that the rubber coagulates from a liquid solution or the rubber is swollen or otherwise stretched and the polymeric complexes of the original Gums are opened, albeit this favorable condition of the gum by drying is lost again in a known manner as a preliminary stage of sulfation can go. It seems, however, that when the particles are still moist with a water-miscible, liquid surrogate that is essential has a lower vapor pressure than water and in which the sulfating agent is soluble or is present in the solvent for the sulfating agent, the water gradually removed during evaporation and replaced by the liquid surrogate in such a way can be replaced so that the rubber retains a slight sulfation.

The invention also relates to the conditions under which the sulfation is carried out, and it is a feature and advantage of the invention that by the Choosing the sulfation temperature the DS can be predetermined to suit for a specific use to achieve desired properties; this temperature is generally in the range from room temperature to about 1000 C.

It is another feature of the invention that before the start of the In the sulfation reaction, a base is preferably present in an amount that is preferably is between 1 and 2 moles per mole of sulfating agent, the one commonly used Amount is more than 1 mole per mole of sulfating agent. When the rubber particles subjected to the sulfating action of the sulfating agent in the presence of the base is the propensity of the sulfating agent, the molecular structure of the rubber attack, significantly reduced. Even if the amounts given above If the base is preferred, even smaller amounts can reduce the breakdown of the rubber molecules reduce in a favorable manner.

After the sulfation has ended, excess reaction medium becomes available removed from the sulfated particles and the sulfated gum is recovered by either dissolving it in water and then coagulating it, or the sulfated particles suspended in a liquid medium in which they are insoluble are and in which the remaining sulfation medium is soluble.

In any case, the area around the rubber is neutralized and thereby further degradation of the rubber is reduced.

According to the process of the invention, gums which are in the natural state or which are substantially or completely free of sulfate groups can be sulfated; such gums are, for example, locust bean gum, guar, taro, gelatinized starch, agarose, cellulose, carboxymethyl cellulose, gum arabic, psyllium mucilagines and pectin. According to the method of the invention, a carbon already containing sulfate groups can wEYz s ew st O ff rubber sulfated when the rubber in its natural state does not have the properties suitable for a particular use and it is desired to increase the sulfate content of the rubber. The gum may be subjected to the process of the present invention either in the raw state or after impurities have been removed, for example after clarification.

When the water-containing water-stretched rubber is made by first dissolving the rubber and then coagulating it, the concentration of the rubber solution is not critical; the main limiting factor is due to the tendency of most Carbon rubber 5, to form highly viscous solutions. If the solution is extremely viscous, it will be difficult to handle. For example, in the case of guar, if the concentration exceeds 3% of the solution, it becomes difficult to handle it without the aid of a strong mixer. A 20 percent solution of gum arabic, on the other hand, has a viscosity below 100 cps. In general, the gum solution is first prepared at a concentration that the solution can be easily handled and the gum can be coagulated. Concentrations on the order of 1 are particularly suitable for gums that form high viscosity solutions. With gum arabic, a solution on the order of 10 to 13% is particularly useful. Most Carbon / hydrogen rubbers are water-soluble in the cold or with the application of heat0 The dissolution of cellulose can be accelerated by a cuprammonium salt.

The rubber solution is generally made by adding the rubber solution coagulates into a hydrophilic liquid that is completely miscible with water and in which the gum is insoluble, such that when the addition is finished, the Concentration of the hydrophilic liquid causes the rubber to coagulate. the hydrophilic liquid to which the rubber solution is added to bring about coagulation may be reactive with or inert to the sulfating agent be. For economic reasons, a lower aliphatic is generally used Alcohol or a ketone such as isopropyl alcohol, methanol, or acetone. Other examples hydrophilic liquids of this type are ethanol, tertiary butyl alcohol and tetrahydrofuran. In any case, the vapor pressure of the hydrophilic liquid of this type should be greater than the vapor pressure of the liquid surrogate with which the coagulate is slurried is so that when the water evaporates the hydrophilic liquid before sulfation can be removed.

When the hydrophilic liquid against the sulfating agent is essentially inert, it can be a tertiary amine such as pyridine or an amide be like DMF. A hydrophilic liquid of this type is called a liquid surrogate suitable to water by evaporation from the slurry of rubber in the liquid Remove surrogate. Other examples of this type of hydrophilic liquid are Formamide and dimethyl sulfoxide.

The type of hydrophilic liquid used for the activating precipitation due to a small extent the DS, which under otherwise identical conditions can be obtained.

For locust bean gum, the achievable DS is when using DMF slightly larger than when using an alcohol. On the other hand, methanol promotes a higher DS than DMF when guar or starch is activated for sulfation.

In practicing the method of the invention, will one volume of the gum solution to about 1.5 to 2 volumes of the hydrophilic liquid added. Because of the cost of recovering the hydrophilic liquid, it is uneconomical, the volumes of the hydrophilic liquid over the required to increase the final quantity. A larger amount can of course also be used will. When about 9 volumes of the hydrophilic liquid per volume of the gum solution are applied, the obtainable DS is slightly lower than when the amount of the hydrophilic Liquid is close to the minimum required to cause coagulation of the Rubbers is required.

In the case of a hydrocarbon such as cellulose, with the help of a cuprammonium salt is transferred into an aqueous solution, the coagulation can be effected by that the rubber solution is added to a liquid medium which induces coagulation, like a dilute aqueous acid.

After coagulation, the remaining liquid is removed from the coagulated Gum left wet is deposited. This can be done, for example, through drainage done, which one promotes by squeezing the coagulate, whereby one cares for it must bear that the coagulate remains moist and the elongated fibrous character of the coagulated rubber is not destroyed.

The conversion of the rubber into a water-containing, water-extended state is ensured with optimum effectiveness by coagulating the rubber in an aqueous medium under conditions such that the coagulum occurs in particulate form. However, this necessarily requires the handling of relatively large volumes of liquid and also requires the recovery of the hydrophilic, coagulating liquid. It is a further advantage and feature of the invention that effective sulfation can also be achieved when the hydrocarbon rubber f occurs in a swollen or water-stretched state, if thereafter the rubber particles are slurried while being in a water-containing water elongated state, with a liquid surrogate, and when volatile liquid is evaporated from the slurry until the water is virtually completely removed, while some liquid surrogate still remains associated with the elongated rubber particles. If particles of hydrate swell, they also tend to agglomerate. With a suitable ratio of the aqueous medium with which the rubber particles come into contact and the size of the medium, agglomeration, which would interfere with the removal of the water, can be avoided. With a gum such as guar, because of its water solubility, the gum tends to go into solution when one tries to use enough water to keep the guar in a particulate form.

If the amount of water is decreased, then there is a tendency to agglomerate; it has been found, however, that this inclination is eliminated by the application of a Mixture of water and a hydrophilic liquid such as alcohol or DMF decreases can be, from which the omega particles take up water under springs, without, however Too much to agglomerate. Preferably, the amount of hydrophilic liquid can be adjusted to achieve the desired properties. If for example DMF makes up more than about 40% of a water DMF mixture, the DS of a rubber falls like guar very quickly. When the concentration of isopropyl alcohol is around 60% the D6 is also low. On the other hand, when hydrophilic liquid missing or under-applied to try and swollen guar gum To bring state without dissolving, the rubber is brought into a stand that the Removing the water becomes difficult.

After the rubber is in a water-containing, water-stretched state is brought, excess aqueous medium is removed, but - as indicated - the rubber particles are retained so that they have water attached to them when converted into a slurry with the liquid surrogate will. In general, the rubber particles contain a sufficient amount of water to so that they weigh two or three times as much as the completely dry gum.

After the production of the rubber particles in a hydrous, water-extended Condition can have a high degree of ease of sulfation without excessive degradation can be achieved when the water and any other reactive material is removed from the Gum can be removed by slurrying the gum with the liquid surrogate and the liquid material evaporates until the water and any material like alcohol are practically completely removed. The preferred surrogate liquid is DMF.

Other suitable surrogate liquids are pyridine, formamide, dimethyl sulfoxide, dimethylacetamide, diethyl formamide, the picolines and the lutidines. As already mentioned, it is crucial that the surrogate liquid is water-miscible and has a lower vapor pressure than water and any other material, such as a lower aliphatic alcohol, which must be removed by evaporation together with the water. The surrogate liquid is usually the same as the solvent used for the sulfating agent during sulfation, but it is not necessarily the case. So it is moz - .. lih to use pyridine as a surrogate liquid, but then Pyridine could not be used as the solvent for the sulfating agent when trying to use pyridine: SO3 as the sulfating agent, since pyridine: S03 is insoluble in pyridine. If, however, pyridine is used as the surrogate liquid and is partially removed during the evaporation of the moisture, sulfation can be used using DItF as the solvent for the sulfating agent and DMF: SO3 as the sulfating agent, with retained pyridine being advantageously indicated below Reasons for the sulfation reaction proves. If the surrogate liquid is not the same as the solvent for the sulfating agent, it may be miscible with the solvent for the sulfating agent.

The evaporation is preferably carried out under a vacuum of about 5 mm Mercury column and carried out at an elevated temperature of about 800 C. The vacuum conditions are not essential, but in the absence of a vacuum evaporation takes time longer, and if the absence of any vacuum by maintaining it a higher temperature is compensated, care must be taken that local overheating can be avoided. The application of vacuum and elevated temperature serve only to accelerate the removal of water and any liquid, which have a higher vapor pressure than the surrogate liquid.

The evaporation is carried out until the rubber particles are removed practically all of the water and any liquid is removed is irreversibly reactive with the sulfating agent and has a higher vapor pressure than the surrogate liquid has. As stated in connection with example 9, if the DS is kept at substantially the same concentration, the viscosity of the sulfated gum increases as the water concentration increases decreases in the reactants and the parent gum.

There must be a considerable amount of surrogate fluid with the rubber particles remain associated because in the complete absence of the liquid medium in which the Rubber particles are suspended, the sulfation of the rubber completely or largely is impossible. That does not mean, however, that the evaporation does not go so far can be carried out until the surrogate liquid is no longer in a free-flowing State is present, that is about half the weight of the rubber. the Surrogate liquid tends to replace the aqueous medium that was originally leads to the fact that the rubber is in a water-containing, water-extended state is located, and the rubber can be in a corresponding swollen or stretched state in which it swelled or swelled by the surrogate liquid. is stretched, and it can be kept in that state even if there is any free flowing surrogate liquid has been removed by evaporation.

The amount of surrogate liquid with which the gum is slurried, is not critical as long as there is a sufficient amount, so that the water can be removed as much as desired, and at least some of the surrogate liquid remains attached to the rubber for the reasons given above. It is generally sufficient when the surrogate liquid covers the slurried particles.

The preferred sulfating agent is the reaction product of DMF and sulfur trioxide (DMF: S03) dissolved in excess DMF when the surrogate liquid DMF is. However, other known sulfating agents can also be used, for example the reaction products of Yke-tertiary amines with sulfur trioxide such as pyridine : S03, trimethylamine: SO3 and triethylamine: SO3. Reaction products of sulfur trioxide and amides other than DMF such as dimethylacetamide, formamide and diethylformamide can also be used0 In general, any sulphating agent can be used which is an anhydrous reaction product of sulfur trioxide and a Lewis base is.

The type of liquid surrogate has already been discussed above and any of them can be used as solvents for the sulfating agent can be used provided that it is a liquid that is a solvent forms for the sulphating agent used in each case, and which are practically inert opposite to the gum and the sulfating agent.

The amount of sulfating agent should be at least the theoretical Correspond to equivalents to enable the desired DS. Something is excess necessary.

As stated above, the sulfation is carried out in the presence of a base which is at least partially soluble in the reaction medium. The base can be an organic, preferably a tertiary amine such as pyridine. Other examples are triethylamine, quinoline, the picolines and the Lutidines. The choice of a base is not restricted to nitrogen-containing organic compounds; it has been found that other substances are effective and particularly desirable because of their odorlessness and palatability, and are less costly chemical compounds. The main requirement is that they can take up a proton from the reaction mixture to form an acid which is weaker than that in the reaction between the £ Coal rubber and the sulfur trioxide is formed. On the other hand, the base must not be so strong as to react irreversibly with the sulfur trioxide complex used as a sulfating agent. Examples of suitable compounds of this type are sodium acetate and disodium hydrogen phosphate. Of course, other salts such as potassium and calcium acetate or potassium phosphate can also be used. If sodium acetate is used, sodium polysaccharide sulfate and acetic acid are formed during sulfation; but acetic acid is a weak, only slightly ionized acid, and does not cause any appreciable degradation of the polysaccharide, while without the use of a base the reaction product would be polysaccharide sulfuric acid, which is a much more strongly ionized and a much stronger acid which can significantly degrade the polymer. When using disodium sulfate, the reaction products are sodium polysaccharide phosphate and monosodium phosphate. Other salts which have the same reactivity are known and can be used as suitable bases.

During the sulfation reaction, 1 w> l of the sulfating agent reacts with sugar to form 1 Nbls of acid, around the base that is used according to the invention does not increase the acid released to the extent that it is formed and so closes a reduction in the breakdown of the polysaccharide during sulfation. the preferably the minimum amount of base used is 1 mole per mole of sulfating agent. The base can be in two forms. When the sulfating agent is the product is a combination of a tertiary amine with SO3, then the tertiary amine serves as a base to the extent that the S03 is transferred to the rubber during sulfation, the tertiary amine is used for the reaction with that released during the reaction acid available. In other words, when the sulfating agent is a complex formed from the tertiary amine and SO3, is the complex itself such a nature that 1 mole of base is present and for reaction during sulfation is available.

If, on the other hand, the sulfating agent is the reaction complex is between DMF and SO3, then it must, since DMF is not basic enough to deal with to connect the protons released during sulfation, 1 mole of a base such as pyridine or disodium phosphate can be added so that one mole of the base is present and is available for implementation.

If one tries in general, during the pre-sulphation evaporation takes place the water and any reactive with the sulfating agent, reduce hydrophilic liquid such as isoperopropyl alcohol to a minimum, there may be a small amount of the reactive hydrophilic liquid that is reactive with the sulfating agent to 1 mole of acid per mole of sulfating agent to build. If the entire amount of sulphating agent is to react with the water, 2 moles of organic base would be sufficient to react with released acid, and the presence of 2 moles of base per mole of sulfating agent is theoretical Maximum amount to correspond to such a ratio, although another Excess is not detrimental. Indeed, it is desirable to have any water or any irreversible reactive hydrophilic liquid to a minimum to reduce and in practice a little more than 1 mole of base per mole of sulfating agent to use for any minor retention of water or any other equalize irreversible reactive fluid, with at least 1 mole of base in the sulfating agent can be present when the sulfating agent is the complex Is the reaction product between SO3 and a tertiary amine. If it is also for the Practicing the procedure is usually preferable to a breakdown by the presence of a base during sulfation is this not necessary if one wants to consider other features of the invention. As below as demonstrated by examples, greater degradation can occur in the absence of a base enter than when a base is present during sulfation. By getting different amounts the base can be used in the range of less than 1 mole per mole of sulfating agent, you have the size of the mining in your hand.

When performing sulfation, the sulfating agent is used added to the anhydrous slurry of the coagulated gum containing the base, avoiding the entry of any moisture during sulphation got to. The slurry is gently agitated during the reaction.

It has been found that in practicing the invention, the temperature plays a critical role with regard to the DS obtainable, while other process conditions stay the same. For example, when locust bean gum sulphated at room temperature should be, a maximum of about 0.5 DS is obtained, regardless of whether the Amount of sulfating agent slightly larger than that theoretically required to maintain this DS required amount or even a multiple of this amount was, The upper DS limit remains practically the same, although the implementation only a few hours or continues for many hours.

If, however, the rubber sulphated for a long period of time the rubber tends to degrade somewhat. Lie at higher temperatures the same conditions with the exception that the DS is significantly higher, namely about 1.0 if the sulfation of the locust bean gum is carried out at 700 ° C and about 2.24 when the reaction is done at 900C.

The ratios shown above are important for the properties of the sulfated rubber, as this largely differs from that obtained by the rubber DS are dependent, and a DS or another may be special for certain applications be desirable. Particularly useful properties are achieved when that DS of the rubber in question in the range from about 0.1 to the theoretically possible Maximum value is.

If desired, a sulfated gum with a DS to get that rubber for a specific application particularly Gives valuable properties, then sulfation takes place at temperature performed that for the rubber in question the predetermined DS as the upper one The sulphation limit is guaranteed under the sulphation conditions used, in the presence of at least the theoretical amount of sulfating agent, which corresponds to the predetermined DS. This way you can be under effective control Rubbers with predetermined DS values can be produced. It's harder to get the DS of a rubber by other means, for example by limiting the sulfating agent or to control the duration of sulfation.

In most cases it is desirable to only use sulfation a minor degradation or other attack on the molecular structure of the rubber perform, and it is one of the features and advantages of the present invention that this task can be solved successfully. When the temperature of sulfation is increased with a resulting increase in DS finds a certain Degradation of the molecular structure takes place, but even under such conditions new ones become and valuable properties achieved 0 If, on the other hand, is desired, Carrying out the sulfation with a simultaneous degradation of the rubber, the Sulphation at higher temperatures and / or at partial or complete In the absence of a base. For example, locust bean gum found in a slurry prepared as described for sulfation was, a sulfation using DMF dissolved in DMF: S03, in the presence as well as in the absence of pyridine, subjected and the sulfated gum for determination of the DS and the viscosity in one percent solution at 250 C analyzed. The test results are listed in the following table: Sulphation with pyridine Without pyridine conditions -DS viscosity cps DS viscosity cps 4 hours, room temperature 0.46 1,300 0.47 250 4 hours, 450 C 0.65 800 0.76 9 The table shows the Importance of the presence of the organic base in preventing a serious Impairment of the viscosity of the sulfated rubber, as well as the effect an increase in temperature with respect to the increase in the DS limit. Even if the viscosity if the sulfation temperature drops somewhat at an elevated temperature, the obtained are Viscosities good and higher than that obtained by the known method Achieving a corresponding DS can be obtained.

When the sulfation has been carried out to the desired degree the reaction conditions are monitored to allow the sulfated gum with the to get the least possible attack on its molecular structure. The bulk of everyone Residual sulfating agent is preferably removed by draining the reaction liquid removed from the sulfated gum coagulum. If not essential, it can the coagulate can be washed with a liquid that is opposite to the sulfating agent is inert, for example with an additional amount of as a reaction medium for the sulphating agent used surrogate liquid. The mixed gum coagulate is dissolved in water that has an indicator such as phenolphthalein or a BDH universal indicator contains to determine the pH, which can also be done electrically, so that a suitable Alkaline material such as sodium hydroxide can be added to approximate the solution keep neutral. Other alkaline materials such as sodium carbonate can also be used or bicarbonate, or the carbonate or hydroxide of potassium, ammonium, or calcium be used. The addition of alkali also sets any present residual pyridine or another base free from the sulfated gum, which is special because of the bad smelling pyridine is desirable.

After dissolving the gum in water, it preferably becomes light alkaline (pH about 8) made solution of a volatile hydrophilic liquid added, which is preferably a lower aliphatic alcohol such as isopropanol or acetone in an amount of about 1 part of the solution to 1.5 to 2.5 parts of the hydrophilic liquid. The resulting coagulate becomes more hydrophilic with additional Liquid, for example with 60 to 85 percent alcohol or Aoton, washed. It can then be dried and powdered in some way. Instead of the sulfated rubber particles after their separation from residual sulfation liquid To base, the particles can be suspended in a water-miscible liquid in which they do not dissolve, such as in isopropyl alcohol, the one Contains sufficient amount of an aqueous base to reduce the acidity of the initially obtained Neutralize rubber particles.

Sulphated gums produced by the process of the invention have a desirable viscosity range and reactivity which can be influenced as a function of the DS and which can be predetermined by the selection of the reaction conditions. Carrageenan for the production of lambda-rich carrageenan Use. If lambda-carrageenan or a similar material is not available, but the available material does not have certain desired properties, the present invention enables the sulfation of another gum to obtain a gum with the desired properties. It is an advantage of the present invention that it is virtually free of sulfate groups from sulfation Carbon xefru Çrubber of land plants in order to obtain gums with valuable properties which the mother gum does not have, and to adapt the properties to the intended use.

The present invention enables the sulfation of rubbers of the type indicated Kind, with a sulfation while maintaining the properties that determine the viscosity can be carried out. The viscosity tends again after reaching a maximum to fall as sulphation increases and as it does As the sulfation is increased, the water solubility and the ionic activity increase.

The synthetic sulfation of a gum so that it has properties particularly suitable for a particular use is illustrated below with respect to guar and locust bean gum; each gum was sulfated in such a way that the DS increased gradually. Solutions of the unsulfated rubbers and the sulfated rubbers were prepared at a concentration such that the rubbers and water were heated on a water bath for 15 minutes with vigorous stirring, then cooled to 25 ° C. and if necessary, the weight was added by adding the during Lost water evaporation has ceased. Viscosities were measured with a Brookfield Model LVF Viscometer at 6 rpm and a suitable spindle used in accordance with standard R practice. The various viscosities given gradually increased DS values are listed in the following table: Table 1 Guar: Locust bean gum DS Vis. (cps): DS Vis. (cps) O (not sulfa-6,600: o (not sulfa-3,000 ante) 0.36 6,600: 0.35 1,600 0.60 3,925: 0.44 1,150 0.87 3,150: 0.59 830 0.97 2.150: 0.94 595 1.16 1.350: 0.94 400 1.51 1.200: 1.08 475 1.79 710: 1.35 340 1.65 300 The gradual transition to lower viscosities with a higher DS is clearly evident From the table. The gums are made more soluble by the introduction of the ester sulfate group. It was found that for locust bean gum with a DS above about 0.6 the viscosity was essentially the same as that of the mixture at room temperature or heated.

Unsulfated guar is soluble in cold water, the solubility in cold water, the sulfation increases significantly. Locust bean gum is not soluble in cold water and making one soluble in cold water sulfated locust bean gums is a major advantage of the present invention.

According to the invention, guar and locust bean gums can have DS values of be brought about 0.3 to about 1.8, the viscosity of a one percent aqueous solution at 25 C progressively compared to that of the dissolved non-sulfated Gums decreased, but not less than about 1/10 of the non-sulfated gum when the DS is increased to about 1.8. With DS values between about 0.1 and 0.3, the viscosity of the rubbers can actually be increased compared to that of the mother rubber. As will be explained in Example 12, this viscosity can can be increased to three or four times the amount.

According to the invention, the sulfation can be controlled so that X predetermined ratios of DS and viscosity can be achieved for certain Applications are of particular importance. Carboxymethyl cellulose and carrageenan for example used to formulate toothpastes to soften a stable paste To maintain consistency. Ordinary guar is unsuitable for this purpose as it does not contain any soft paste results.

If, however, guar sulfate has a DS of 0.36 and a viscosity of 6,600 cps, then it is very suitable for the formulation of a toothpaste. He also has advantages compared to the known binders, since means Sulphated guar formulated toothpaste resists thermal shocks as none Gelation Occurs when the toothpaste has cooled to room temperature after three Was kept at 490 C for days.

The consistency of the chilled toothpaste was practically the same as that of a control sample left at room temperature in a known manner formulated toothpaste contains one or more abrasives, a humectant, a surfactant, a binder, a fragrance oil, a preservative and a sweetener. The aforementioned toothpaste had the following composition: Dicalciumpho sphat 270 g calcium carbonate 18 g glycerin 156 g water 132.6 g sodium lauryl sulfate 9 g of sodium guar sulphate 5 g of aromatic oil 6 g To the extent that the sulphation becomes larger, there is also increased ionic activity, which results in properties which are characteristic of lambda carrageenan, especially milk reactivity, which makes carrageenan so valuable in the dairy industry. According to the invention Sulphated gums are very useful as stabilizers to prevent settling to prevent cocoa particles in chocolate milk beverages and at the same time the desired physical properties. Land plant hydrocolloids sulfated according to the invention are very suitable for additives that are to be added to cold milk. One to The mixture widely sold for this purpose is a chocolate syrup containing cocoa particles, Contains sugar or other sweeteners and a stabilizer that is sufficient Amount of water dispersed to give a syrup consistency. The syrup is so composed that, when added to a given quantity of milk, the Cocoa and the sweetener gives the desired taste, and an X sufficient amount Stabilizing agent prevents excessive sedimentation of the cocoa particles and gives a creamy consistency and the desired sense of touch in the mouth. Mixtures in dry, reduced form, the cocoa particles, a sweetener and containing a stabilizer are also widely sold. The dry mixture is only added to cold milk, in which the Stir dissolves. For a mixture of this type, the stabilizer must be cold Milk be soluble.

The usefulness for dairy products of the above type can be demonstrated using the example of guar, which according to the invention has a DS of 1.79 with so little degradation has been sulfated that the viscosity is one percent Solution at 250 C is about 710 cps. When adding the sulfated guar to one Standard chocolate milk syrup in an amount that contains 450 ppm guar sulfate, when the syrup is added to the milk to make a chocolate milk drink and the milk had been left to stand overnight at 10 ° C no sedimentation of cocoa particles is observed. The chocolate milk was complete liquid and gave excellent tactile feeling in the mouth, and its aroma was good. The viscosity measured in a Zahn cup was 46 seconds. The Zahn cup viscosity measurement is widely used in the dairy industry to measure the viscosity of a chocolate milk beverage applied. It became a Krim-Ko cup with the diameter of the outlet opening of 22.6 mm is applied. Comparatively, there was a carrageenan in an amount vcii 500 ppm gave the same results with a flow time of 40 seconds. Guar with a lower DS and a higher viscosity can also be used, however, to allow the chocolate milk has the viscosity considered to be preferred, the DS should be at least about 0.87 and the viscosity does not exceed about 3,150 cps.

Another example is that carob guprmi with a DS of 1.35 and a water viscosity of 340 cps / amount of 450 ppm Resulted in chocolate milk that also showed no settling and one in the tooth cup measured viscosity of 43 seconds.

In the production of a mixed milk drink, guar sulfate turned out to be more effective than carrageenan with a DS of 1.79 and a water viscosity of 710 cps. Carrageenan is usually added to the cocoa-sugar mixture in an amount of 0.5 g for use with 8 ozs of milk applied to a foam stabilization, cocoa suspension and developing a full, creamy feel in the mouth. To achieve A quantity of 0.1 g of sulfated guar is sufficient for the same quality.

The invention is generally related to sulfation of land - hydrate Vegetable hydrocarbons Egu nmis which cannot prevent the settling of cocoa particles in chocolate milk preparations, so that they become more effective in preventing such settling when they are dispersed in the preparation at a concentration of not more than 0.1% by weight of the preparation.

It follows from the data given in Table 1 that in the execution of the invention achieved properties desired for various applications can be that, given the sulfation conditions, the degree of sulfation certainly. For example, if desired, the water viscosity at a given To change DS, this can be done by changing the temperature at which the Sulphation takes place. The guar sulfate given in the table above, the has a DS of 1.79 and a viscosity of 710 cps was determined by sulfation at Won 700 C; sulfation at 950 C under otherwise identical conditions until the DS was 1.74 gave a guar sulfate with a water viscosity of 73 cps. When a sulfated gum obtained by the method of the present invention has too high a viscosity, this can be done by known methods such as by acid hydrolysis, oxidation with hydrogen peroxide or sodium hyfiochloride, or simply reduced by prolonged heating.

In order to achieve properties that differ to a considerable extent and are useful compared to the properties of the non-sulfated rubber, the DS of the sulfated gum should be at least about 0.1 and most desirable Combination of properties generally useful for the application achieved if the DS does not exceed about two thirds of the theoretical maximum0 The viscosity of the sulfated rubber depends largely on that of the starting rubber away. Guar is also accessible to achieve high viscosities when it is is present in a small amount, and as stated above, the usefulness of the guar to achieve high viscosities are largely retained when the sulfation is carried out in accordance with the method of the present invention. On the other hand, a rubber like Gum arabic has very low viscosity properties, whether sulfated or non-sulfated.

The invention is further described in the following examples.

In the examples, the DS is according to the following equation for rubbers such as guar, locust bean gum and cellulose determine which polysaccharide is a complex of hexose units with three hydroxyl groups per hexoe unit have: N = 1625 9000-1025 'in which N is the degree of substitution (DS) of the sodium salt of sulfated rubber and S is percent SO4.

For polysaccharides that have different equivalent weights or one have different numbers of hydroxyls, a more general formula must be used Calculation of the DS of the sodium salt must be taken into account, namely: weight x% SO4 N = 9600 - (102 x% SO4), in weight the molecular weight is the repeating molecular unit that is characteristic of the complex is and is included in this.

EXAMPLE 1 10.8 grams of a commercially available locust bean gum were obtained dissolved in water by dispersing and heating to make a one percent solution obtain. The hot solution was used to promote precipitation with sodium chloride up added to a concentration of about 0.1% and then submerged in 2 volumes of DMF Stir poured. The fibrous coagulum was from the bulk of the liquid separated by peeling this off and then squeezing to liquid as much as possible to remove. The solid fibrous mat was torn in a flask and DMF added until the fibers were practically covered. The obtained slurry became subjected to vacuum distillation on a water bath in which the temperature from room temperature to about 800 C was increased to practically all of the water and remove most of the DMF. The pressure in the system was during this Procedure about 5 mm. 125 ml of 1 M DMF: SO3 in DMF (1.88 Moles per mole of hexose) and 36 ml of pyridine (stoichiometrically equivalent to 3.65 times Number of moles of DMF: SO3) was added and the resulting slurry became twenty-four Maintained at room temperature for hours with occasional gentle agitation. The piston remained closed during this period in order to be dry in it, that is Maintain anhydrous, atmosphere. After the end of the reaction time the sulfated gum coagulum was removed from the liquid reaction mixture by filtration separated and the coagulum was washed twice with DMF. The coagulum was then dispersed in water kept at room temperature with agitation, whereupon it immediately began to resolve. There were a few drops of 1, phenolphthalein indicator and then immediately added 1.0 N sodium hydroxide solution until a rose color occurred, which indicated the solution was no longer angry. When the pink Color became faint as more gum dissolved and the solution made acidic additional amounts of sodium hydroxide added to the neutral to weakly basic reaction to maintain. When the gum had almost completely dissolved, was the solution warmed, sodium chloride was added to a concentration of 0.196 and the sodium carob gum sulfate from solution by adding 99 Xigem Isopropyl alcohol is precipitated in an amount equal to 1 volume of solution to 2 volumes of alcohol. The concentration of the neutralized product at the time of precipitation was about 1.6 96. Excess liquid was removed from the coagulated gum by pouring it off, the gum was then squeezed off and poured into a sufficient amount of 85% proprietary isopropyl alcohol given so that it was covered by the alcohol. The gum was later removed from the washing liquid separately, again washed twice in a corresponding manner, then separated again and dried in a circulating air oven at 660 ° C. The yield was down to 20.7 g; the product was then pulverized.

The sulfated gum had a DS of 1.65 and a one percent Solution in water had a viscosity of 300 cps as determined by a Brookfield Model LVF viscometer at 6 rpm using a # 2 2 spindle.

A cold chocolate milk made using this process this sulfate at 350 ppm in the finished beverage had a flow time of 40 seconds; no cocoa settled.

The sulfation was repeated using 5.4 g of locust bean gum and the quantities of the other materials changed proportionally, with the deviation, that for DMF: SO3 and pyridine a ratio of 3 moles of sulfating agent per mole Hexose and 2 moles of pyridine per mole of DMF: S03, 100 ml of 1 M DMF: S03 in DMF and 16 ml Pyridine were used. The product ee had a DS of 1.67 and a one percent Water viscosity from 310 cps, and when using the product for a cold mixed chocolate drink in an amount of 350 ppm one resulted Flow time of 38.5 seconds and no cocoa settling occurred.

This example not only illustrates the implementation of the invention, but also proves the fact that given temperature and time conditions there is a limit to the achievable DS, because the DS obtained remained practically the same, although the molar ratio of sulfating agent to hexose is from 1.85 was increased to 3. This example also shows the repeatability of sulfation, which is possible according to the method of the present invention.

EXAMPLE 2 This example shows the influencing of the DS, which is brought about by influencing the temperature at which the sulphation takes place. Activated Carob Beheee lat was prepared according to Example 1, with the difference that 99 pointers isopropyl alcohol took the place of DMF in the initial precipitation stage. After squeezing out excess liquid, the coagulate was mixed with DMF and the solvents were removed by vacuum distillation. The coagulum was then treated with sufficient sulfating agent at various temperatures to achieve a DS of 3.0 in each case. All samples were treated for four hours.

The work-up was carried out as in Example 1. The test conditions and the results of the tests are listed in the following table: 4 o h 2 0 k Ii w approx s zipM) Fr d approx (1) k Co H No. g ml ml \ g | . . A 5.4 100 16 250 5.65 0.46 B 21.6 400 64 450 25.27 0.65 c 10.8 200 32 700 14.88 0.99 D 5.4 100 16)> 900 12.74 2.24 EXAMPLE 3 The effect of various hydrophilic liquids for the precipitation on the final DS, which is obtainable under otherwise identical conditions, is shown in the following table, in which the test results obtained with potato starch are listed. In each case 5.4 g of potato starch were mixed with cold water and the resulting slurry was added to 500 ml of boiling water. Heating was continued briefly until no significant further thickening was observed.

The mixture was cooled somewhat and the precipitating hydrophilic Liquid in the amount of 1 volume of starch sol to 2 volumes of precipitant liquid admitted. The flocculation and coagulation of the starch took place and the protruding Liquid has been decanted. The coagulated starch was squeezed out and mixed with DMF covered. The mixture was subjected to vacuum distillation while rotating the flask, so that the contents of the flask moved. After the water required for the Coagulation used hydrophilic liquid and removed almost all of the DMF the activated starch with a for a complete sulfation of the starch, that is, sufficient quantity to produce a starch sulphate with a DS of 3 from DMF: SO3 (dissolved in DMF) sulfated and then a stoichiometric the amount of pyridine corresponding to twice the number of moles of DMF: SO3 was added. The reaction mixture was left to stand at room temperature for 24 hours. The sulfated gum was separated from the reaction mixture, washed with DMF and water with good stirring added. Sufficient 1N sodium hydroxide was then added to ensure that when using Phenolphthalein maintain a pink color. After almost complete dissolution and neutralization, the solution was heated and sodium chloride to a concentration of 0.1 96 admixed. The solution was then twice its volume 99 added to an isopropyl alcohol to precipitate sodium starch sulfate, which twice Washed with 85% isopropyl alcohol, at 600 C in an oven with circulating Air dried and then pulverized. The results of this experiment were the following: sample hydrophilic liquid DS A DMF 0.31 B acetone 0.57 c isopropyl alcohol 1.37 D methanol 1.65 The sulfated starches in this table were one percent Water viscosity from about 250 to about 700 cps as measured at 250 C with a Brookfield Model LVF viscometer at six revolutions per minute and a # 1 spindle. the Products had moderate shear sensitivity. The starch sulfate with a DS of 1.37 (Sample C) had a viscosity of 590 cps at 6 rpm and a viscosity of 248 cps at 60 rpm.

EXAMPLE 4 A one percent aqueous solution of 5.4 g Carob lavender Gum was added to two times its volume of an isopropyl alcohol and the coagulated gum, after the supernatant had been separated off, was prepared for sulfation by treating it with DMF and then removing all water and alcohol in vacuo as indicated in the previous examples. A solution of 18.1 g of triethylamine sulfur trioxide in 100 ml of DMF was added to the activated gum and the mixture was heated to 700 ° C. and the temperature was maintained for four hours with gentle stirring of the reaction mixture. After the reaction had ended, the sulfated locust bean gum was separated from the excess liquid as triethylammonium salt, washed with DMF, dispersed in water and neutralized with sodium hydroxide. After coagulation in isopropyl alcohol, washing, drying and grinding, 8.39 g of sodium guar sulfate containing 43.28% ester sulfate was obtained. The DS was calculated to be 1.35 and the viscosity of a one percent water solution was 340 cps according to the stated method of determination. The sulfated gum was suitable in an amount of 450 ppm for a cocoa suspension in a cold chocolate milk drink. The chocolate milk showed no settling and had a viscosity of 43 seconds as measured in a Zahn cup.

This example illustrates the use of a sulfating agent, wherein the addition of a base is not required to ensure the presence of a base Ensure during sulfation, as the sulfating agent is the reaction product is between a tertiary amine and SO3 and because the tertiary amine is on a mole-by-mole basis is released when the SO3, as stated above, enters the sugar molecular structure of the gum enters to absorb the proton made by the hydroxyl of the sugar molecule according to the following equation: ROH + R 3N S03 ROSO 3 + R'3N: H +, in the ROH denotes the sugar molecule and Rt3N: denotes the tertiary amine.

EXAMPLE 5 Even if degradation occurs at higher temperatures, this is not necessarily detrimental to the end product. To this fact To clarify, 20 grams of guar was dissolved in about two liters of water and out of solution precipitated with isopropyl alcohol. The coagulate was squeezed out and vacuum distilled dehydrated with DMF. A mixture of 59 ml pyridine and 370 ml 1 M DMF: SO3 in DMF was added to the activated gum and the reaction mixture at water temperature held for four hours. The liquid was then separated from the sulfated guar and the gum with constant neutralization with 1 N sodium hydroxide in Dissolved in water. The solution was heated, then twice the volume of isopropyl alcohol added to precipitate the product. After washing twice with 60% isopropyl alcohol and once with 85% the sodium guar sulfate was dried and ground; the The yield was 41.4 g of a free flowing powder. Although the one percent viscosity of the product was only 13 cps, it is noteworthy that with an association of more than 50% sulfate plus more than 12, sodium with the ester sulfate group the actual Polymer concentration in the test solution was only about 0.38 96. The DS of the product was 2.19. The tests showed that the product as a toothpaste binder and as Stabilizer was unsuitable for cold mixed chocolate drinks. The product was also checked for its usability for mixed milk beverages, for what in general 0.5 g of carrageenan are required. It was found that only 0.3 g of the invention Sodium guar sulfates were required to achieve comparable results, Namely, pure settling of cocoa, a good volume and foam prevention. This Example shows that products according to the invention take the place of known products may occur when applying the same or a lower amount. This example further shows that one possible by one according to the method of the present invention predetermined viscosity and DS products with one for a specific application can produce desired property.

EXAMPLE 6 For the previous examples, galactomannan gums were made without prior removal of the insoluble ones usually present in such gums Fabrics used. The method of the invention, however, is not applicable to raw rubbers limited, as products can also be manufactured that have completely clear solutions form, which is possible by either sulfating a clarified gum or clears the sulfated gum.

It follows from the following statements that one can obtain the same results Achieved in both ways, and experiments were carried out with locust bean gum; other gums that do not form clear solutions after sulfation can be used in treated in the same way. Starch and cellulose sulfates form clear solutions, when the DS is high enough, while guar and locust bean gum sulfates are not clear Solutions help.

A. Add lo g of locust bean gum to 800 ml of water by boiling for 30 seconds and the solution is then diluted with a further 200 ml of water. The solution was purified with 20 g of diatomaceous earth as filter aid and the combined The filtrate and wash water of the filter cake became after the addition of sodium chloride up to a concentration of 0.1% 1 l / 2 times the volume of 99% isopropyl alcohol added. The resulting fibrous hagulated gum became as dry as possible pressed and put into a flask with a round bottom after tearing it apart. 94 g of anhydrous DMF were added and the mixture was subjected to vacuum distillation subjected to remove all but about 17 g of DMF. For sulfation a solution of 23.5 ml of pyridine in 145 ml of 1 M DMF: SO3 in DM-F was activated Gum added and the mixture held at 700 ° C. for four hours. It was a 3rd : l molar ratio of sulfating agent to hexose used to check a how high DS at 700 C can be obtained as a comparison with that in part B of this Example described material. It was believed that the The yield of clarified gums was 78% of the starting material, i.e. 7.8 g for this calculation. In order to simplify the analytical work, the following was made Technique followed when working up the reaction mixture. (In practice, washing can be omitted, which only increases the production costs.) The sulfated gum was filtered off, washed with DMF to remove the bulk of the remove remaining unreacted sulfating agent, and then with 99 Washed in alcohol. These washes prevented inorganic build-up Sulphate in the end products. The washed gum was then turned into something universal dispersed containing water and immediately neutralized with 1 N sodium hydroxide. Frequent addition of a base ensured that the pH was safely maintained at a height of 6 to 9. When the gum was completely dissolved, it became clear The solution is heated and 1.5 volumes of an alcohol are added to precipitate the product, then washed twice with 85% alcohol, dried at 600 ° C. and then was pulverized.

B. A solution of 7.8 g Carob Gum in 1 liter of water (to comply with the conditions given in Part A of this example with regard to the rubber concentration) as indicated in the previous examples to obtain an activated coagulate which, as in Part A - 145 ml of 1 M DMF: SO3 in DMF - was sulfated with 23.5 ml of pyridine. After sulfation, washing, dissolving and neutralization, the mixture was filtered with 20 g of diatomaceous earth as a filter medium. The cake was washed, sodium chloride was added to the combined filtrate and wash water, and all of 1.5 volumes of 99% alcohol were added to precipitate the gum which was then washed and dried as indicated in Part A.

The products obtained were assessed for their appearance, DS and water viscosity compared. The results were as follows: A B yield 13.3 g 12.4 g color white white DS 1.25 1.41 appearance of a one percent solution clear, colorless clear, colorless one percent solution viscosity 456 cps 360 cps EXAMPLE 7 Even if cellulose is sulfated with a slurry of DMF: S03 in DMF this reaction generally gives products with a high DS (for example 2 to 3). 1 M DMF: SO3 solution in DMF is used for sulphation of in usual form Cellulose completely ineffective. Use of the method of the present invention the activation of rubber by precipitation from an aqueous solution is described below illustrated by the production of freshly precipitated cellulose from an aqueous solution. Cotton wool was dissolved in a cuprammonium hydroxide solution and the solution was mixed with aqueous hydrochloric acid.

A solution of 64 ml of concentrated aqueous ammonia was with Dilute water to about 270 ml and slowly add this solution to a solution of 122 g Copper sulfate (CuSO4'5H2O) in 600 ml of water is added. The precipitated copper hydroxide was centrifuged off, washed once with water, and again to recover the centrifuged precipitated product. This was then concentrated in 633 ml of aqueous Dissolved ammonia and diluted the solution to 1 liter, thus obtaining a solution which contained 31 g copper per liter and 165 g ammonia per liter.

Under a nitrogen atmosphere, 8.1 g of cotton were in 250 ml of the copper reagent just prepared dissolved. The viscous solution obtained was concentrated with stirring a solution of 245 ml, diluted to 3 liters Hydrochloric acid was added. The precipitated cellulose was separated from the liquid and washed twice with water. The second wash gave no precipitate if she did was treated with silver nitrate solution, suggesting the absence of chloride and a adequate washing indicated.

The wet cellulose (92 g) was covered with 200 ml of DMF. It was an acidic reaction was determined by means of a universal indicator. Was pyridine added to neutralize the mixture, then the volatile substances in vacuo removed until 212 ml of distillate had been absorbed. The refractive index of the distillate indicated that some water remained in the fibers. An additional 100 ml amount of DMF was mixed with the cellulose and vacuum distillation repeated0 As the remaining DMF and cellulose reduced to a weight of 93 g the material was considered ready for sulfation.

This activated cellulose was 16 ml of pyridine and 100 ml of 1 M DMF: SO3 added in DMF, an amount sufficient to achieve a DS of 2 if they was completely absorbed by the rubber. Some warmth developed, reflecting that indicated possible retention of water in the cellulose. After the reaction mixture After standing at room temperature for 24 hours, the liquid was removed by filtration removed, and the solid washed with DMF and then washed with absolute ethanol, in order to remove residual, possibly unreacted sulfating agent. The gum was dispersed in water and 1N sodium hydroxide solution was added to maintains a slightly alkaline reaction indicated by a universal indicator to obtain.

Insoluble particles were removed from the solution as none other Solution occurred more. These particles (product B) were with water washed and the wash water added to the original filtrate undoas whole two times the volume of 99 an alcohol added to the easily water-soluble Part (Product A) to be felled. There were three volumes of the above alcohol to the muddy Product B added. The two products were then removed from the supernatant alcohol separated, washed twice with the above alcohol and dried.

Analyzes indicated that product A had a DS of 1.04 and product B had a DS of 1.04 Had a DS of 0.78. Product A dissolved quickly but formed an unclear solution, which had a one percent viscosity of 1,850 cps, measured at 250 C with a Brookfield Model LVF viscometer using the 2-spindle at 6 rpm.

Product B swelled quickly in water, but it did not completely dissolve. Under the same conditions as for product A with the variation in use a 4-spindle, the viscosity was 21,000 cps.

It can be assumed that the product A thanks to the good equilibrium its DS and viscosity has properties corresponding to those of carrageenan; the Product B can be used for new applications because of its unusual properties be. It had an unusual sensitivity to shear, for example, and although its viscosity at 6 rpm was 21,000 cps, it was only 3,600 cps at 60 rpm, and if a same viscometer (model LVT) with a larger speed range was used at -0.3 rpm, the measured viscosity was 200,000 cps. A product with such properties can be used for certain types of suspensions Find.

EXAMPLE 8 This example illustrates the extent to which the Sulphation is controllable according to the method of the present invention. That Process served to introduce sulfate ester in agarose in one Extent that there was one sulfate group per disaccharide unit. That way it was made a polysaccharide that had a chemical analysis that practically found the same as that of the Gloiopeltis slime (Funoran, a very valuable one in the Orient used seaweed extract).

However, because of the low molecular weight of the agarose, it cannot it is expected that the physical properties, especially the viscosity, would be the same.

Agarose was prepared according to the method known from US Pat. No. 3,281,409 including coagulation of the purified agarose solution Adding to isopropanol and washing with isopropanol, but without drying4 Das vor the drying isolated braid of agarose is characteristic of the ie for the Sulphation of the present invention coagulated gums. It became a mixture of 36 g Hyflo Super-Cel, 12 g agar and 2.4 g carrageenan 800 ml water with stirring added and the mixture heated to a boil for five minutes. Then it became 200 ml a 5 show solution of benzethonium chloride added.

The precipitation was complete, the mixture was filtered, the cake washed with hot water and the wash water added to the filtrate. That would then with 1.5 times its volume 99 added to an isopropyl alcohol. After gentle agitation, the fibers were allowed to settle, followed by a moderate increase formed a solid network. After cooling, the braid was removed from the alcohol, squeezed out and washed three times with 60% isopropyl alcohol to remove the remaining remove quaternary ammonium salt. The braid, which is damp because of the watery alcohol was placed in 200 ml of DMF, whereupon it dissolved immediately. The volatile liquids were removed in vacuo until all free liquid was removed and the residue taken up in 80 ml of DMF. To this end, 4.5 ml of pyridine and 100 ml of 0.275 M DMF: SO3 in DMF, a 10 pointer but shot) was added. This crowd was based on the usual yield (about 66) agarose selected to obtain the agar selected in each case can be. Thus the amount of agarose in the mesh was calculated to be about 7.9 g or h - = 25 meq.

Agarobiose units that contain a primary alcohol function per agarobiose. The implementation with 25 meq. Sulphating agent takes place, as is believed, at the primary alcohol site, after neutralization with sodium hydroxide a derivative is obtained which has the following repeating structure: Such a polymer would contain 23.28% sulfate on an anhydrous basis.

After allowing the sulphation mixture to stand for 16 hours at room temperature, with occasional shaking, 10 ml become anhydrous Methanol for reaction with sulphating agent which has also not yet been consumed added. After two more hours there will be ice and water, and at the same time some Drops of universal indicator added and then with a sufficient amount of 1 N Sodium hydroxide maintain neutrality. The solution became twofold Amount of their volume of 99% isopropyl alcohol added. The coagulated gum was separated from the alcoholic solution, three times with 50% isopropyl alcohol and washed once with 85% alcohol, then at 600 C in a circulating Airflow dried and then pulverized. On a moisture-free basis the sodium agarose sulfate had a sulfate content of 25.52%, i.e. about 10% 96 excess over the assumed amount, which shows that the conversion is so complete was that even the excess sulfating agent was consumed by the polysaccharide became. The product described in this example differs from the usual Agarose because of its solubility in cold water and because it does not form a gel.

The infrared spectrum of the sodium agarose sulfate obtained was measured with compared to that of the Gloiopeltis slime. Lay the almost identical spectra it very closely suggests that Gloiopeltis extract is essentially sulfated agarose, though the high viscosity of Gloiopeltis extract, around 270 cps at 1% and 25 ° C, on it indicates that it has a much higher molecular weight than that described here Sodium sulfate agarose has, namely 20 cps at 1% and 25 ° C. The sulfate content of the Gloiopeltis polysaccharides was found to be 24.7% as the sodium salt.

This example not only illustrates effective sulfation according to the method of the present invention, but also the versatility by adding known polysaccharide sulfates can to a certain extent be duplicated.

EXAMPLE 9 Following the previous example, using various gums, sulfating agents and the like polysaccharide sulfates with the the usual care to maintain anhydrous conditions that is, no extreme caution was exercised in this regard. Accordingly, you can the viscosities of the end products are not considered to be maximum values.

Tests were carried out in such a way that in the activated coagulate by removing different amounts of DIF 'and aqueous alcohol different Lots of moisture are present. The same amount of a sulfating agent (a known excess - 2 moles per mole of hexose under reaction conditions such that a DS of about 1.25 should be achieved) was added in each case. After completion the reaction was the supernatant liquid to its remaining content of sulfating agent and analyzed for free sulfuric acid (as the pyridine salt).

From the known amount of the sulfating agent used sulfuric acid present and from the amounts that are absorbed by the remaining water in when gum coagulum was formed, the total amount present was calculated. The viscosities of the isolated products and the total meqO of the sulfuric acid present were entered in a coordinate system to indicate the zero concentration of the acid to extrapolate, so that the highest possible viscosity for the into consideration upcoming DS could be appreciated. In the table below are the crucial ones Dates listed; an extrapolation of points to the zero concentration of sulfuric acid indicates that if the reaction conditions are carefully observed Sodium guar sulfate having a DS of about 1.25 and a viscosity of about 5,000 cps (1 96, 250 C) can be produced, while a Viscosity of around 1,700 cps can be expected.

meq. H2S04 1% H2O Developed from Develop from viscosity Ds 0 der Solution Developed from total viscosity DS DMF: SO3 H2O in rubber cps.

5.23 5.17 10.4 2375 1.27 5.24 6.96 12.2 2175 1.27 5.22 13.18 18.4 1725 1.22 5.27 19.13 24.4 1525 1.24 This example illustrates that by a Control of the moisture content of the activated rubber is a means to determine the viscosity of the end product.

B E 1 5 P 1 E L 10 To illustrate that the temperature of the Reaction plays a bigger role than the duration of the reaction, so was sulfation of guar at 700 C and 900 C with an excess of sulfating agent during Periods between 0.5 hours and 4 hours. In any case it was Prepare guar gum for sulfation as described above and add 3 Moles of sulfating agent treated per mole of hexose present, each hexose unit Contained 3 hydroxyl groups. In each case there was accordingly a sufficient amount of reactant to fully sulfate the gum to a DS of 3.0. From the following It can be seen from the table that the temperature is much higher than the DS determines the duration.

700 900 Time (hours) DS Time (hours) DS 0.5 0.87 0.5 1.77 1.0 0.97 1.0 1.74 2.0 1.08 2.0 2.09 3.0 1.16 3.0 2.32 4.0 1.24 4.0 2.19 B E 1 5 P 1 E L 11 Four gums were after dissolution, precipitation and dehydration by distillation treated with DMF with a calculated amount of sulfating agent to give a DS obtained, which lead to new and valuable properties of the sulfated rubbers would. Minor deviations in the pretreatment of the rubbers are shown below described up to the sulfation stage. The sulfation conditions are in one Table reproduced.

The sulfated rubbers were worked up as described above, namely by filtration, dissolution, neutralization and precipitation with alcohol.

A. 10.9 g of carboxymethyl cellulose (CMC, Hercules Powder Co.) dissolved at room temperature in such an amount that a one percent solution sodium chloride was added to a concentration of 0.196 and mixed the solution with 1.63 volumes of isopropyl alcohol to precipitate the gum. The liquid was squeezed out, leaving 28.6 g of the moist gum placed in a round bottom flask and covered with 88 g of DMF. The fleeting ones Liquids were removed in vacuo to the extent that dry, but with residual DMF stretched particles remained.

B. Because of the low viscosity and poor precipitability of rubber Arabic in alcohol became gum arabic to a concentration of about 13 % dissolved by dissolving 9.4 g in about 62 ml of water by gentle heating and then pieces of bark etc. filtered off. The filtrate was made with 1 ml of 10% sodium chloride added and the mixture added 125 ml of isopropyl alcohol. The precipitate was separated by means of a Dacron cloth and vacuumed under a rubber sheet until a moisture weight of 15 g was reached; the wet precipitate was then mixed with 71.5 g of DMF and vacuum removed from most of the volatile liquids freed.

C. Psyllium slime was made by temporarily intermittently stirring 15.4 g of whole psyllium husks in one liter of water for three hours and centrifuged after heating to 600 C in a disk cup centrifuge, to remove the bulk of insoluble matter. 842 g of the thick, almost gelatinous Centrifugates were reheated to 700 and after adding sodium chloride Add two volumes of isopropyl alcohol to a concentration of 0.1%. That Accruing coagulate was tested up to 18.6 g (estimated Weight of dry mucus based on one test = 8.1 g) and by evaporation dehydrated by DMF in vacuo (117 ml of DMF were used).

D. 9.34 g of pectin were dissolved in 460 ml of water and used for precipitation one liter of isopropyl alcohol is used and the precipitation is carried out by adding 5 ml of 10 N hydrochloric acid supports the hot pectinsol. The frayed, shredded coagulate weighed 96.5 g. After treatment with 137 g of DMF and evaporation, another Evaporation performed with a few ml of DMF to remove alcohol and from Ensure water.

The reaction conditions followed for sulfating the activated gums are shown in the following table: Rubber Weight Approx.No. M1. IN temp. Time Yield SO4 g m mole DMF: SOD OC h g A CMC 10.9 50 50 70 4 9.85 20.4 B rubber Arabic 9.4 60 105 45 2 15.5 38.9 C Psyllium 8.1 60 90 70 4 10.4 47.2 D Pectin 9.3 50 50 55 4 10.8 28.5 Since the rubbers used for this example are molecular different from those used for the previous examples, by hexose units marked rubbers, was used to calculate the DS according to the formula weight (FW) of the rubber in question, the formula given above is used. That FW used for the calculation and the resulting DS sinu in the following Table listed: Rubber FW DS used to determine FW Data gum product A CMC Substituted with CH2COONa to 0.7 218 0.59 B gum 3 arabinose : 1 Rhamnose: 3 Ga-Arabicum lactose: 1 Na Glucuronate 153.5 1.05 C Psyllium range of galacturonic acid: xylose = 1: 9 to 1: 36 Arbitrarily chosen 1: 22 135 1.33 D pectin degree of methylation = 67.5 166.8 o, ao The gums were in suspensions tested of cocoa in milk.

This experiment clearly proves that of all available Only carrageenan gums have the required properties, namely cocoa to suspend, to cause a rich, creamy taste in the mouth, a bring about suitable viscosity and in an economically reasonable amount sufficient to achieve these purposes. Other rubbers were used, however in general they lack at least one of these qualities. The fact that the gums sulfated by the process of the present invention are combined in one behave in a manner corresponding to carrageenan justifies the statement that they are new connections.

Sodium carboxymethyl cellulose sulfate was used to make a chocolate syrup used which, when mixed with milk, had a concentration of 700 ppm of the derivative revealed. After standing for 18 hours at 100 ° C., the milk was tested.

There was no trace of cocoa on the bottom of the bottle or the The viscosity of the milk, tested with a Zahn cup, gave a flow time of 41.6 Seconds, i.e. a deviation of 2 seconds from one stabilized with carrageenan Standard chocolate milk.

The sodium psyllium sulfate was tested in the same way, but it the usual amount was not chosen. With a lot from At 1,000 ppm, the milk was somewhat over-stabilized, as it had a flow time of 54.7 seconds would have; at 600 ppm the milk was slightly under-stabilized - some cocoa set off and the flow time was only 27.3 seconds. If one extrapolates these values, calculation results in a suitable amount of about 820 ppm.

The psyllium sulfate was also tested and a milk mix drink from 20 g sugar, 2 g cocoa, 0.01 g artificial vanilla, 0.35 g of a 270-mesh gum and made 283.5 g of milk.

The mixture was shaken for 15 seconds and then transferred to a 400 ml Berzelius beaker poured. The mixed milk drink filled the cup to the brim and retained its volume longer than five minutes. The creaminess and fullness of the drink were excellent and no cocoa settled. The amount used was only 70 96 of the carrageenan used for the same experiment.

The same results were achieved with an appropriate mixture, which contained 0.5 g of sodium pectin sulfate instead of psyllium sulfate. It was the usual amount used for carrageenan, but the effectiveness of the synthetic one Material was unambiguous, B E 1 5 P 1 E L 12 According to the previous examples was the activation of the rubbers by the formation of relatively weak rubber solutions and precipitation of the gums is achieved by mixing the brine with miscible solvents, in which the gums are insoluble. This example illustrates an implementation of the invention, according to which the rubber is in a water-containing, water-extended condition by absorbing water without going into solution, causing it to become there is no need to produce the rubber particles by coagulation from a solution of the rubber.

A solution of 30 ml of DMF and 70 ml of water became 8.1 g of guar gum added and the mixture heated to 62.00C. During this period welled up the rubber is considerable due to the absorption of water from the mixed solvent. The gum was separated from the liquid by filtration and the determination the refractive index showed that the filtrate contained 31% DMF, which indicates that water is preferably removed from the solvent system. To the filtered Gum was added to 100 ml of DMF. A vacuum distillation of the solvent briefly until the dry state was reached, the rubber was left in a more compact form, than is the case with the precipitation method, but activated in the same way State. The activated gum was diluted with 17 ml of pyridine and 92 ml of 1.11 M DMF: SO3 in DMF offset. The sulfation was carried out by heating the mixture to 700 C during carried out for four hours. The sulfated gum was filtered off, with DMF and Washed alcohol and dissolved in water with continuous neutralization. After Alcohol precipitation was washed and dried and 11.1 g of sodium guar sulfate obtain. This had a DS of 1.09 and a viscosity of 4,240 at 250.degree cps.

Lower concentrations of DMF in water (10% and 20%) allowed the gum to swell to a point where removal of the water was very difficult. On the other hand, concentrations in excess of 30% reduced swelling, and so was found IlktiiR 4d eLneLLU only a DS of about 0.25 as well as treatment with 50,96 DMF. Appropriate treatment with aqueous alcohol also led to activation, but led to a lower DS, although this fact could be used to great advantage in an extreme case. 8.1 g of guar powder were soaked in 100 ml of 60% isopropyl alcohol under reflux for 15 minutes. The aqueous alcohol was removed by filtration and replaced by DW, most of which was removed by vacuum distillation in order to ensure complete removal of the water and alcohol. The gum was then treated with 80 ml of 1.3 N DMF: 503 and 17 ml of pyridine and heated to 70 ° for 1.5 hours. The sulfated gum was filtered off, dispersed in water and neutralized with an aqueous sodium hydroxide solution, then coagulated by adding isopropyl alcohol to the solution. After washing, drying and grinding, the product was analyzed and checked to see whether it led to a high viscosity. The 1% viscosity was 29,000 cps, four times greater than that of the guar gum used in its manufacture. In another experiment, the activation was again carried out with 60% isopropyl alcohol, but 14 hours at room temperature. The sulfation took place at 700 for four hours. The process product was nearly identical in that it had a DS of 0.2 and a viscosity of 26,000 cps which was four times the viscosity of the unsulfated guar.

B E 1 5 P 1 E L 13 It was found that also another method when using the aqueous alcohol to produce a highly concentrated Guar gum solution is effective before sulfation.

A slurry of 8.1 g of guar in 100 ml of 50% by weight isopropyl alcohol was prepared with stirring by rapid heating to the boiling point. The alcohol and some of the water evaporated in a few minutes. The gum solution obtained was swollen granules. These were dissolved in 150 ml of DMF dsIiiorrf slide 6w vç w the mixture was subjected to distillation to dehydrate the gum. The sulfation at 700 ° C. for four hours resulted in a guar sulfate with a DS of 1.46 and a 1% water viscosity of 3,400 cps. Much lower concentrations of alcohol gave less satisfactory results. At 3096, however, a DS of 1.25 and an 850 cps viscosity were achieved. A 40% concentration gave a DS of 1.26 and a viscosity of 1,450 cps after sulfation. At higher alcohol concentrations the DS began to drop; 60% alcohol resulted in a DS of 0.88 (liquid viscosity 5,700 cps); 70% alcohol resulted in a DS of 0.21, viscosity 7,300 cps.

B E I S P I E L 14 To determine the applicability of the swelling in aqueous DItF and to further illustrate activation by solvent distillation, 8.1 g of potato starch were soaked in warm 30 5 / gem D and filtered off, then for sulfation by mixing with anhydrous DMF and distillation prepared in vacuum to remove all solvents except a small residue of Remove DMF to keep the starch moist.

The activated starch was with 92 ml 1.11 M DIMF: SO3 in DMF and 17 ml of pyridine are added. The mixture was heated to 700 ° C. and at this temperature held for four hours. Then the gum was filtered off, pouring into water at the same time Solution and neutralize dispersed. The neutral solution was reduced to about half their volume concentrated and mixed with a sufficient amount of isopropyl alcohol, to precipitate the sulfated gum out of solution. He was then severed and Washed three times with 85% alcohol and at 600 C in an oven with ornamental Air dried; 13.7 g of sodium starch sulfate with a DS of 1.87 were obtained. Using a W2 spindle with a Brookfield Model LVF viscometer gave At 6 rpm of a one percent solution, a viscosity at 250 C of 575 cps and a weak shear sensitivity at 60 rpm; the viscosity was 255 cps.

There were 0.5 g of the process product with 20 g of sugar and 2 g of cocoa mixed and the mixture shaken with a mug of cold milk for 15 seconds b; the result was a rich, creamy mixed milk drink, and even after one No settling of the cocoa could be detected for half an hour.

B E 1 5 P 1 E L 15 This example shows that a solution of the sulfated Gums for neutralization with a metal hydroxide is not required.

8.1 g of guar gum were obtained from an aqueous solution of 1.5 volumes Isopropyl alcohol precipitated and dehydrated with DMF.

The sulfation was carried out with 2 moles of DMF: 503 per mole of hexose at 700 ° C. performed four hours. The reaction product was filtered off, but not in Dissolved water and neutralized with an aqueous base, but simply in 650 ml of 70% isopropyl alcohol suspended and neutralized with an aqueous base. The results are comparable in every respect with a correspondingly through sulfated guar obtained by dissolution-reprecipitation: DS = 1.27 and 1 46 water viscosity (250) = 2,610 cps.

B E 1 5 P 1 E L 16 This example shows that sulfation up to can be achieved to a given extent by just having the particular one Amount of sulfating agent incorporated.

In almost all of the preceding examples, however, a shot of Sulphating agent applied. It has been shown to have a DS of 1.2 to 1.3 im generally achieved when using either 2 or 3 moles of sulfating agent with guar gum has been applied at a temperature of 70 ° C for four hours. Of that assuming that this DS is a "NormW" under these test conditions 8.1 g guar gum (50 meq.

Hexose) activated as indicated in the preceding examples and with 60 ml of 1 M DMF: 5O3 in DMF (60 meq., i.e. one to form a DS of 1.2 calculated amount) sulfated at 700 C for four hours. There was one Extract of 14.0 g of sodium guar sulphate with a sulphate content of 40.62% (corrected for the humidity). This is equivalent to a DS of 1.21 and clearly shows the effectiveness of this sulfation process. A 1% solution of the product had a viscosity of 2,660 cps as measured at 6 rpm on a Brookfield Model LVF viscometer.

B E 1 5 P 1 E L 17 A solution of 32.4 g of tare gum in 2.5 liters 4.5 liters of 99% isopropyl alcohol were added to water to precipitate the gum. The fibrous coagulum was squeezed out and mixed with 200 ml of DMF and the whole subjected to vacuum distillation on a rotary vacuum evaporator. The distillation was carried out until the fibers were only damp due to residual DMF was. Then 19.2 ml of pyridine, 100 ml of DMF and 120 ml of 1 M DMF: SO 3 in DMF were added and the mixture shaken at room temperature for 4 hours.

The sulfated gum was filtered off, washed with DMF and in Suspended in water. During the dissolution, a neutralization was carried out by careful Maintain addition of 1 N sodium hydroxide solution. After finishing the solution and the neutralization was the heated sol of a sufficient amount of alcohol added to precipitate sulfated gum. The product of the process, sodium tarasulphate, was washed with fresh alcohol, dried and put in a laboratory Wiley mill ground. It had a DS of 0.37 and a 1% viscosity, measured at 1,725 cps at 250 C at 6 rpm with a Brookfield LVF viscometer. It was then checked whether it is suitable for a formulation of toothpaste, for which usually Carrageenan is used in an amount of 1 70. It was found that the product of the process is a good binder at a concentration of only 0.65%, i.e. at a clearly lower amount than must be used in carrageenan.

B E I S P I E L 18 A slurry of 8.1 grams of guar gum was obtained and 100 ml of 30 fig. DMF heated to 63.80 ° C. and the gum filtered off.

Anhydrous DMF was added to the swollen gum and the mixture was added partially dried by removing the solvents in vacuo. The swollen one Guar gum particles were 6.8 g of anhydrous sodium acetate and 78 ml of 1.11 M DItF: SO3 solution added. The mixture was held at 50 ° for two hours, then the solids became filtered off and dispersed in water with constant neutralization. It was less Base required as if the same products were used using pyridine as the base getting produced. The obtained sodium guar sulfate had a DS of 0.6 and one 1% water viscosity of 3,580 cps.

3 E 1 5 P 1 E L 19 It was a sulfation according to Example 18 under Use 14.1 g of anhydrous disodium phosphate in place of sodium acetate carried out. The reaction was carried out at 70 ° for one hour and the sulfated gum was from the denser, settling on the bottom of the reaction vessel settling sodium phosphate is removed. The product had a DS of 0.59 and a 1% solution v had a viscosity of 600 cps.

Patent claims:

Claims (41)

PATENT CLAIMS 1. Method for sulfating a carbohydrate gum, in which the rubber is dissolved with a reaction product of SO3 and a Lewis base in a solvent, sulfated and the sulfated gum from the reaction mixture is recorded, characterized in that a slurry of water-containing, water-swollen particles of gum in a water-miscible surrogate liquid which does not react irreversibly with the sulfating agent with the solvent for the sulfating agent is miscible or this is itself and a vapor pressure which is much less than any borne by the particles with which Sulphating agent is irreversibly reactive liquid, the liquid the slurry evaporates until the rubber particles are practically irreversible free of any are liquid reacting with the sulphating agent, but a considerable one Amount of surrogate liquid left in the rubber particles and then that of the sulfating agent the surrogate liquid containing particles with # mixed and sulfated. 2. The method according to claim 1, characterized in that as Surrogate liquid NtN-dflmethylSormnmid formamide, tertiary amines, dimethyl sulfoxide, Dimethylacetamide or diethylformamide are used. 3. The method according to claim 1, characterized in that as Sulphating agent is the reaction product of SO3 and a tertiary amine or amide used. 4. The method according to claim 1, characterized in that as Surrogate liquid uses a liquid that is essentially identical to those contained in the solvent for the sulfating agent during sulfation Liquid is. 5. The method according to claim 1, characterized in that the surrogate liquid N, N-dimethylformamide, and N, N-dimethylformamide in the solvent for the Sulphating agent is included. 6. The method according to claim 1, characterized in that the surrogate liquid Is pyridine, and sulfation with the sulfating agent dissolved in N, N-dimethylformamide and is carried out in the presence of pyridine. 7. The method according to claim 1, characterized in that the sulfation is carried out in the presence of a considerable amount of a base, the protons and cannot react irreversibly with the sulphating agent. 8. The method according to claim 7, characterized in that the base is used in an amount of 1 to 2 molar equivalents of the sulfating agent. 9. The method according to claim 1, characterized in that the sulfated rubber after sulfation in solid particulate form in a water-miscible liquid dispersed containing a sufficient amount of an alkaline contains reactive material to make the acidity of the sulfated rubber practical to neutralize, and then collects the treated particles. 10. The method according to claim 1, characterized in that the sulphated rubber dissolves in water after sulphation, which is an alkaline substance Material is added which practically neutralizes the acidity of the sulfated gums and then adding the sulfated rubber to a water-miscible hydrophilic liquid, to coagulate the sulfated gum. 110 The method according to claim 1, characterized in that as Starting carbohydrate gum uses a gum free of sulfate groups. 12. The method according to claim 1, characterized in that the Rubber sulphated at a predetermined temperature, which is practically constant upright is obtained and sulfation continues until excess is present regardless Sulphating agent the rubber reaches the highest possible DS at this temperature and applies the sulfating agent in a narrow range at least equal to that that is required to achieve this DS, and in this way that DS of the rubber is predetermined according to the selected temperature. 13. The method according to claim 1, characterized in that the Slurry liquid evaporated under vacuum. 14. A method of sulfating a carbohydrate gum in which the rubber is subjected to anhydrous sulfation with a sulfating agent in the form of a reaction product of SO3 and a Lewis base, which in a solvent is dissolved, and the sulfating agent is absorbed, characterized in that that the gum is dissolved in an aqueous medium to form a liquid solution, the gum coagulates from the liquid solution, the coagulated gum from excess, The excess liquid separates the coagulated gum without drying the gum slurried in a water-miscible surrogate liquid that does not turn into an iriwersible Reaction with the sulfating agent occurs, which is miscible with the solvent for the sulfating agent or the solvent itself, and the one is lower Vapor pressure as any liquid carried by the particles Has, which reacts irreversibly with the sulphating agent, the volatile liquid evaporated from the slurry until the rubber particles were practically devoid of any Irreversibly reactive with the sulphating agent, liquids are, however leaves a considerable amount of the surrogate fluid bound to the rubber particles, and then the gum particles with which surrogate fluid is associated with the Sulphating agent mixes and the gum by reacting with the sulphating agent sulfated until the DS is at least about 0.1. 15. The method according to claim 14, characterized in that the rubber is a practically sulfate-free carbohydrate gum that is used to form a liquid solution is soluble in water with or without the application of heat, and that you can make the gum by adding the liquid solution of the gum to a water-miscible one hydrophilic liquid, in which the gum is not soluble, coagulates. 16. The method according to claim 15, characterized in that as hydrophilic flaa uses a lower aliphatic alcohol or acetone, further characterized in that during the evaporation in the presence of the surrogate liquid the hydrophilic liquid is practically completely removed with the water. 17. The method according to claim 15, characterized in that as hydrophilic liquid N, N-dimethylformamide is used. 18. The method according to claim 15, characterized in that as hydrophilic liquid pyridine is used. 19. The method according to claim 14, characterized in that cellulose is used as gum and the coagulated cellulose is produced in such a way that the cellulose is dissolved in a solution of a cuprammonium salt and by adding the cellulose solution obtained to a sufficient amount containing aqueous liquid, the cellulose coasulates. 20. A method of sulfating a carbohydrate gum in which a water-soluble and water-swellable gum with one dissolved in a liquid The reaction product of 503 and a Lewis base is sulfated and the gum is sulfated is obtained, characterized in that the rubber is in the form of solid particles brings into contact with an aqueous medium in which the particles are not dissolved, but are swollen by absorption of water, but remain as individual particles, the swollen particles of excess liquid without the swollen rubber particles to dry, separates the swollen rubber particles with a water-miscible surrogate liquid slurries, which does not react irreversibly with the sulfating agent, which with is miscible with the solvent for the sulfating agent or is itself, and which have a considerably lower vapor pressure than any of these particles carried fluid that is irreversibly reactive with the sulfating agent is, the liquid evaporates from the slurry until the particles are practically free of any liquid irreversibly reactive with the sulphating agent but a considerable amount of the surrogate liquid associated with the particles leaves, and then the rubber particles with which the surrogate fluid is attached is mixed with the sulphating agent and the sulphating is carried out so far, until the DS is at least about 0.1. 21. The method according to claim 20, characterized in that one Carbohydrate gum practically free from sulfate groups is used. 22. The method according to claim 20, characterized in that the rubber is water soluble and the rubber particles are swollen when in contact with stand in an aqueous medium, that's a sufficient amount of one Contains water-miscible liquid in which the gum is insoluble, in order to dissolve to prevent the rubber. 23. The method according to claim 22, characterized in that the Rubber swells at an elevated temperature. 24. The method according to claim 22, characterized in that the water-miscible hydrophilic liquid in which the gum is insoluble, a higher vapor pressure than water, and characterized in that it is mostly by means of heat drifts off, but leaves the particles damp with water before the swollen particles be slurried with the surrogate liquid and the water from the slurry is removed from the particles by evaporation. 25. The method according to claim 20, characterized in that as Use rubber sacks and the aqueous medium in which the starch is swollen is sufficient heated to open the starch and allow it to swell. 26. The method according to claim 20, characterized in that as Gum guar applies and the aqueous medium in which the guar is swollen is sufficient heated to open the guar and allow it to swell. 27. Synthetically sulfated carbohydrate gum according to claim 1, characterized by a DS of at least about 0.1. 28. Synthetically sulfated rubber according to claim 27, characterized in that that the starting gum is a carbohydrate gum practically free of sulfate groups. 29. Synthetically sulfated rubber according to claim 27, characterized in that it consists of Consists of guar, starch, cellulose, carboxymethyl cellulose, agarose, gum arabic, psyllium slime, tare or pectin, 30. Synthetic sulfated cellulose according to claim 19. 31. Synthetic sulfated carbohydrate gum characterized by and guar having a DS of from about 0.3 to about 1.8 and a viscosity in centipoise of a 1% water solution at 250 ° C. that gradually decreases over the range that varies from that of the unsulfated gum to a DS of extends about 1.8, is no less than about one tenth the viscosity of the unsulfated rubber. 32. Synthetic sulfated carbohydrate gum characterized by Carob FeEelcum or guar with a DS of about 0.1 to about 0.3 and a Viscosity in centipoise of a 1% water solution, which is much higher at 250 C. is than that of non-sulfated rubber. 33. Synthetically sulfated characterized by a DS of at least 0.6 and solubility in cold water. 34. Synthetically sulfated agarose, characterized by a DS of at least about 0.3. 5. synthetically sulfated starch, characterized by a DS of at least 0.1 and a viscosity of at least 250 centipoise of a 1% water solution. n6. Use of synthetic sulphated gums to prevent the settling of cocoa particles in a chocolate milk preparation in which the sulphate in an amount of no more than 0.1% has been. 37. Using a synthetic sulfated land plant carbohydrate gum with a DS of at least about 0.8 as an additive for the production of a cold chocolate-milk beverage, the cocoa particle, a sweetener and additives to increase viscosity of milk and suspension of cocoa particles. 38. Using a sulfated locust bean gum, guar, starch, Psyllium mucus or pectins according to claim 37. 39. Use of a dissolved, synthetic sulfated land plant carbohydrate gum with a DS of at least 0.8 for suspending cocoa particles. 40. Use of a synthetic sulfated guar as a binder in a toothpaste. 41. Use of a synthetic sulfated tare gum as a binding agent in a toothpaste.