DE1668539C3 - Process for the production of polysaccharides and polysaccharide derivatives suitable for food and the use of the products produced - Google Patents

Description

The invention relates to a process for the production of polysaccharides and polysaccharide derivatives of glucose or maltose suitable for food by mixing and heating glucose or maltose with an acidic catalyst at a pressure of between ΙΟ * ⁵ and 100 Torr and the use of the polysaccharides produced in this way or polysaccharide derivatives of glucose and / or maltose as an additive for food or sweeteners,

The products produced according to the invention are, as substitutes with no nutritional value, for carbohydrate-sugar as well as flour and starch products useful in food.

Many substances have been proposed for the preparation of foods suitable for those who need to restrict their intake of carbohydrates or calories or both. In general, the substances to be added to the food must have no significant caloric value and no nutritional value. In addition, the dietary foods made with these ingredients must be the same in structure, taste and appearance as high-calorie foods. It goes without saying that the components must not be toxic. A variety of materials have been proposed for such purposes, but all non-j ( "all directions are satisfactory.

If a synthetic sweetener such as saccharin or cychimate is used in diet foods instead of sugar, the other physical properties - apart from the sweetness - which <"> are normally given to the food by the sugar, must be through other components (including synthetic sweeteners) The additional ingredients proposed so far are often nutrients themselves and consequently undesirably increase the caloric value of the food in the mile of the sugar it is intended to replace change the quality of the food so that it becomes similar or convenient, as these additional components can have a negative impact on the color and taste of the food.

According to the invention, products are produced which when used in dietetic foods, give them the physical properties that normal, sugary foods are inherent without increasing the Nillir value of the foods. The dietary Food contains artificial sweeteners that replace the flavor of the sugar, while the Ingredients produced according to the invention give the food the other physical properties (except sweetness) caused by sugar.

Natural foods, especially baked goods, generally contain, besides sugars, siaik nourishing carbohydrates, which give the baked goods their consistency and the Ilaupi part these foods make up. In cakes and bread is the flour that is present in the mince mixture. the main ingredient of the finished baked dough. As a result, people who use their coal hjdra- and / or have to limit calorie intake, their consumption of such foods to a large extent restrict. Attempts to replace the starch or flour in baked goods have so far been unsuccessful stayed because the substances that have been used as substitutes for flour are often the physical ones Change the properties of the baked goods in such a way that the appearance and taste of the same are disadvantageously changed will.

The ingredients for dietetic foods proposed according to the invention and producible according to the invention Food, on the other hand, can also be used as a substitute for flour or other starchy materials without affecting the structure and taste of the food.

It is known that glucose polymers can be prepared by heating glucose in the presence of acidic catalysts. Glucose polymers made by known processes are not suitable for use in food unless the inedible acidic catalysts used in the polymerization are removed. If the inedible, acidic catalysts cannot be removed completely enough, the glucose polymers which they contain are unsuitable for food at all. Another difficulty which arises in connection with the known processes lies in the fact that the polymers produced often have to be separated from aqueous or non-aqueous reaction media before they can be used for the production of low-calorie foods. Most known methods require the use of an aqueous reaction medium. In addition, the polyglucoses that are produced with the aid of the known processes are often strongly colored and for this reason, too, are not suitable for food without further cleaning.

The known mode of operation is shown, for example, in US Pat. No. 2,719,179, in which the manufacture

3 A

, " _R polysaccharide by! .Rliii / en from Sacchand in subsequent Wilrmepolymerisiuion to the Ausmali,

• «πι liquid medium in the presence of an acidic dall between 40 and 67% l ^; osts in water

S i.ilv * ilörs have a temperature of -80 ¹¹ C ¹ to 21, PC a viscosity of 20 to 100 poise,

vW and a pressure of 10 "to 100 Torr, and saccharin or cyclamai as

ύ wrote isi. ^{1) lis} ut'findiingsgcmilße process s contain sweeteners.

In an inventive way, it differs from the In US-PS 28 7b 105 irodeiie sweeteners are ·

According to this US-PS, according to the invention is the mixture with a low calorie content, which at least

α nnduiii 'additional oils. in which the 20% by weight of the de described in U.S. Patent 2,876 HM

α ι mers for the production of edible polyglucose and glucose polymers. Up to 30% by weight of a gum, up to

Ι ι ηnltosen of the acidic Polymciisationskaialysa io / ti 20% by weight of a water-soluble Ccllulose-Deriva

And separated from the liquid core, a small amount of surfactant

Γη have to be like gcmilß the known process and an alkali cyclamate or an alkali cyclamate / sac

mi necessary. Contained by means of the channel mixture according to the invention, and in US Pat. No. 28 7h 106

We can use edible polyglicoses and polymalies to become solid dietetic foods that J.

(If desired, either water insoluble or 15 to 85% by weight of the mixture in US-IS

^ are soluble, can be prepared directly, 28 7b HM described glucose polymers and 0.00 j

\ ifcr US-PS 19 99 380 are processes for up to 5 wt .-% of a mixture of saccharin and

ipllunii containing water-soluble and water-insoluble resin cyclamal, described.

·, He products by mixing and heating one The ^c used in these patents; ^lllL ' ^ÜSC '

■ ι '«ρ with an organic dicarboxylic acid or 20 polymers are according to the US Pat. No. 2j 63 014

• Λι hvdrid of an organic dicarboxylic acid in the process described in the presence of an acidic

" ^f · Ι7Ο (temperature or catalyst such as hydrochloric acid or boric acid and at

" ^Cr ., _r temperature known below 175 C. Manufactured from starch according to atmospheric pressure. Acid cata-

iwn process will use large amounts of dibasic lysers of this kind, however, tend to glucose and

JhT Siuren or deivn anhydrides and under 2s Mallose to decompose and thus dark-colored

■ λ? ^ Nh r pressure worked. The thereby obtained 'products to form what through the Arbe.ien bei

j ί Se be itzen thermoplastic liigenscnar.cn and atmospheric pressure and in the presence of air still

^ ΐη in 1 acken and impregnating compounds is favored. Are therefore according to this Vc. f I-

In ^{US Pat} . No. 19 W 3B0, glucose and maltose are used in this way

Now conditions will include dark, sticky, and dark-colored products. The brilliant uei

/ u get handling tar products, the US-Paienlschrirt used starting maierul. to be there

Ai hi has a low dextrose equivalent as a non-nutritive carbohydrate fuel and already has a

Large number of natural starch acetai bonds can only be used

the process of this US patent contains obtained, in addition, provides polymers which

rv.o paccording to the behavior of these urw '.- i crnaiicnen tmiwn, nucu u «iu _U u,", "...,." _{v r} ; n, iii, .h "-

_Pr E mainly glucose esters what by., 5 large number of opposite enzymes emprndl ^

ifXl wedge is confirmed in alcohols - which are only contained in bonds, thus compared to enzymatic

Jacket u d η signing compounds use cleavage less stable and thus kaonen-rich, are.

Laoten uiiu MM ₁ / &., U prfinHiini7 «irpmäl producible products.

Varnishes and waterproofing hooded vciwl-u- _Jpa , _lu " ₆ ,, ^," _b ^,

can find application. as products which can be produced according to the invention.

Other methods of polymerizing molten- The method according to the invention is thereby gener Glucose and maltose, / .. B. that in US-PS 40 indicates that a dry anhydride or

24 36967 described, are only for the production of hydrate of d-glucose or d-maltose at Temreratu-

soluble polyglucose and polymallose. In reu from 140-180 ⁰ C and a pressure between 10 '>

In contrast to those produced according to the invention and 100 Torr melts and with the exclusion of water

Products, these soluble products must be a little and air in the presence of 0.1-10 mol% of a little 45 volatile, food grade organic

are suitable for use in food. In the case of polycarboxylic acids or their anhydride in gesehmolze-

The further processing is about the π en state polycondensation and at the same time that

Removal of the acidic catalysts that were used in these during melting and polycondensation

older procedures are used. In both cases water formed under the above temperature process The products produced can be strongly colored 50 and removed from printing conditions. In the process

they then require further treatment before becoming edible, i.e. H. acids suitable for food

you can use them for dietetic foods. as catalysts, polymerisation activators or

According to the invention, the constituents which the crosslinking agent uses. In this way, the

According to the invention are added to foods, previously necessary removal of the acidic catalyst

Easily and economically produce and require this 55 1 cn or excess acid from the polycondensates

Products have little or no cleaning before they are used in dietetic foods

added to dietetic foods. switched off. The with the help of the invention

The ingredients produced according to the invention for process-produced polyglucoses or polymaltoses

Dietary foods are not for the consumer call in the dietary foods they are

harmful, give the food no unnatural ho are added, no unnatural discoloration

before color and preserve the physical properties.

ten of the food even with a long storage time and in The method according to the invention is also of the

Connection with other foods. Vc drive technology is superior to known processes,

From US-PS 28 76 104 dietary frozen because the production of polyglucoses and polymaltoses

Food mixtures known to be produced between 5 and ^ s by melt polycondensation in an anhydrous

30% by weight of the mixture is carried out on a non-nutritional medium, thereby reducing the disadvantage of the

Glucose polymers as the freezing point lowering co-separation of the polymers from a reaction medium, that is eliminated from strength by depolymerization and around:

With the help of the inventive method * iM us possible to use 2 arias by iOlyglucosc and Pulyniiillcj.su to be prepared simultaneously next to one another or separately from one another by adding the initial acid concentration tion, the Heaktion & daiier and the Rcaklionslcmperiilur s adjusts accordingly.

The two arias of Polyglucuse or Polymaltose are soluble Polygliieosc or Polymiillo.se, which are used to replace sugar in dietetic foods can serve if the ■ SüßolTekl is achieved with synthetic sweeteners, as well as insoluble polyglucose or polymaltose, in which the acidic polycondensation active agent is Contains a proportionate share. Chew the insoluble form of the polymers. as a flour or starch consultant (Litetic foods are used.

Among polyglueosc, polymaltose and polysaccharide are understood in the present context polymeric Miiieriiilicii, in which the main part of monomeric units ims glucose. Maltose or other Siiccharidcn exists. Also fall under the term polymeric materials in which the Glucose. Maltose or Saceharidcin uniteii mn [annealing are esterified, as seen from polycarboxylic acids derive, which dwell as polycondensation activators will.

The starting materials for the polycondensation melting process are mallose or glucose. The sugars are subjected to the process in dry anhydrides or dry dehydrated Ieststoile w and should be in powdered form.

The acids used according to the invention as catalysts. Crosslinking agents or polycondensation activators can be used, any low volatile organic polycarboxylic acids. Especially who the citric acid, fumaric acid, tartaric acid, succinic acid. Maleic acid, adipic acid. Oxalic acid, phthalic acid. Isophthalic acid, itaconic acid or terephthalic acid are used. The anhydrides of maleic acid. Succinic acid, Adipic acid, itaconic acid and phthalic acid can also be used. Inedible acids are although chemically suitable for carrying out the process, for the production of edible polyglues or Polymalioscn not useful. The selection of the acidic catalyst must therefore unier from the point of view of Non-toxicity to the human body. Inorganic acids are for use as catalysts in the anhydrous melt polycon Densation not suitable because they are not used in the production of insoluble polyglucoscn and polymaltoscn Can serve crosslinking agents. Monocarboxylic acids are also not effective as crosslinking agents; in addition, they are not as effective as catalysts in anhydrous melt polycondensation Polycarboxylic acids. The selected acid must be relatively less volatile because it is more volatile Acids evaporate too much during the heating and melting of the mixture to be polycondensed. The polycarboxylic acids that are used according to the invention are used in the polycondensation because but not completely esterified by the polyglucose or polymallosc, with P > Form iyglucosecstcr or acidic polymallose eggs. This fact can be accepted by the residual acidity of the polyglucoses and polymallose after dialysis and the recovery of the in the < > Prove s procedure used acid after hydrolysis of the product. The Einverleibui.g the acid antci-Ic in the polyglucose or polyma pants!

Their refinement for the miniscule lirnflhriiiii » ⁿⁱⁱ j;>! c, Siltireaniciles serve as crosslinking agents -between different folyglwcose · or polymilm iemolcules in the insoluble in polycondensates. wiiKCj'on in the soluble polycondensates of .Aure umI is used to esterify only one polymer molecule.

For the implementation of the invention, 1iien Verhih Rons are dry-powdered (glucose or maltose niii the corresponding amount Siiurc vcnnisehi.das so The mixture obtained is v. under reduced pressure MtifL'cmelted, with the .melting / conditions under Exclusion of water can be maintained until polycondensation in the desired Scope has occurred; the individual polymers Proclucle become clanuiibgeireniil.

The knowledge-free Sihniel / polycondensalion muli at A pressure / wipe IO »and 100 Torr carried out herden fin negative pressure of this order of magnitude using a vacuum pump, steam nozzle jekiors. an aspiwitois or other means can be achieved The V.ikuum isl exclude the polycondensation and the Ihdratwasser and d.is in the FoUkondeiisatioiisrcaklion Ireii-eset / le Wassei to learn ΛικΊι, his dei Surrounding iles Pul \ kuiidcnsaliunsammlungcs should Lull 'lusgeschlosseii to be a Veilarbiing de! at your polycondensation gcbildcieii PoUglucescn odei l'olv maitosen to% crrint; a. Is has proven to be beneficial a weak snom of Slickstoifgas ubei the lOlvkoiKifiisatsehmelze to direct l.ufiaussihlull and learning about the water. Becomes a Sticksloftsirom used, so bniudii not in Hoclnakuuni to be worked on, but in this case too, prints over 100 mm Hg should be avoided.

The reaction time and the keaklion temperature are critical variables in the process according to the invention. The temperature for the melt polycondensation is between about 140 and 180 ° C. The precise temperature for the anhydrous Schmelzpolvkondensation depends on the initial ratio of glucose or maltose n \ of the acid used, the reac lonszcil and the ratio of soluble to insoluble polyglucoses or Polymalioscn vcrnel / th polyglucoses or Polymahosen. that should be present in the end product. away.

The preparation of a mixture with a high proportion of soluble glucose or mallose polymers requires generally an acid concentration between 0.1 and 10 mol percent, preferably between 2 and 7.5 mole percent. If the amount of acid is increased, it decreases the extent of crosslinking and thus also the proportion of water-insoluble polyglucose or polymaltose. if the acid concentration is unnecessarily high, problems arise with regard to the neutralization of the excess acid which is then present in the final product. It is easily recognizable for the person skilled in the art that the amount of acid required for a specific polycondensation, the polycondensation time and the Polycondensation temperature and the nature of the desired end product are interdependent factors are. The determination of the amount of acid must therefore be made with the other factors in mind will.

The reaction temperature should be used in the production of soluble polyglucoses or polymahoses Molecular condensation should be as low as possible because of the extent of the discoloration, d "r Karamclisicrung

and the degradation increases with increasing temperature. If the polycondensation temperature is increased, the duration of the polycondensation decreases until the process is completed. Preferably, the method, therefore, is carried out at a Polykondensalionstemperatur of about 160 'C. and a reaction time of about 8 hours or at a temperature of about 140 ^r' C and a Rcaklionsdaucr of about 24 hours, with about the same degree of polycondensation is achieved .

When producing insoluble polyglucoses or polymaltose, the initial molar ratio of glucose or maltose / acid / can be between about 1: 1 and 20: 1. If the initial ratio of glucose or maltose / acid is increased, the temperature required for the polycondensation also increases and the duration of the polycondensation. With a molar ratio of glucose or maltose / u acid / between about 1: 1 and about 5: 1, insoluble polyglucoses or polymaltoses are obtained in an amount / between 80 and 90%: with molar ratios above about ^r ) ·. 1 the content of insoluble polyglucoses is reduced. When carrying out the process according to the invention for the production of insoluble polyglucoses or polymallose wendel ιί; ιπ preferably molar ratios of glucose or maltose / acid / are about 12: 1 and about 20: 1. These ratios are preferred despite the high reaction temperature required and the relatively long reaction time, because the total yield of soluble and insoluble polyglucoses or polymaltoses at these sugar / acid ratios / is between about 90 and 99%. Using these higher ratios, it is possible to achieve a yield of between about 50 and 60% of insoluble polyglucoses or polymaltoses and / of about 40 and 50% of legible polyglucoses or polymaltose in one reaction mixture. Water-soluble polyglucose or polymaltose can be separated from the corresponding insoluble compounds by action with water and subsequent centrifugation. Another advantage of carrying out the reaction at high molar ratios of glucose or mallose / u acid arises from the fact that the resulting products require little or no neutralization.

I mc- dry cleaning is furrow products that are made with Milk of the crushing process generally not necessary. Become insoluble or soluble glucose or mallose produced together, a separation may be necessary.

1 (For certain purposes of application, a neutralization of the polyglucoses or polymaltoses is advantageous. If the polyglucoses are to be used in diet foods that contain whole milk, excess acid, which is present in non-neutralized polyglucoses, can lead to coagulation of the M. ch In the case of soluble polyglucoses or polymaltoses, the solutions of the same can be directly neutralized. This neutralization can be achieved by adding carbonates of potassium, sodium, or magnesium to the polyglucose or i'cilytti.fltosr solutions Sodium and I. »liumcarbonatc used together, so Ivniii /: τη« oinc physiologically balanced balancing • icr. ViiscUiing The alkaline sound of a typical i'oht.'lu -i.se io <u ig. Which is based on a pH value of about 5 li .. ⁽ > ι .'even · «or · cn is about 0.5 to 1.0%.

Other materials used to adjust the pH of soluble polyglucose or polymaltose solutions can be used are l-lysine, d-glucosamine, N-methylglucamine and ammonium hydroxide. The first two of the compounds mentioned are natural Substances so that there are no objections to their use as an ingredient in dietetic foods should. The latter compound is quickly excreted from the body in the form of urea, see above

ίο that even against them, no hesitation in using them should consist in dietetic foods. N-methylglucamine is used as a solubilizing agent in Pharmazeuüka is used and is therefore also safe for dietetic foods. Other methods dialysis is used to reduce the acidity of polyglucose or polymaltose solutions and in ion exchange: these methods are preferably used according to the invention.

For certain purposes, a decolorization of the soluble and prepared according to the invention is insoluble polyglucoses and polymaltoscn attached. Soluble polyglucose or polymaltose can be discolored by bringing together solutions of the substances with activated charcoal or bone charcoal or slurries the solutions with a solid adsorbent or the solutions through a bed of such Adsorbent conducts. Soluble and insoluble polyglucoses and polymallose can also be used with sodium chlorite or similar materials used for flour bleaching will. The insoluble polyglucose is before bleaching a yellow powder that in many cases does not need to be bleached at all.

If the insoluble polyglucose is to be used as flour cereal / in dietetic foods, then so it can be ground or otherwise mechanically crushed so that it has a consistency which corresponds to that of wheat flour. As a wcizenmchlersat / the material should preferably have a fineness have a clear mesh size of 0.044 mm is equivalent to.

The solutions of soluble polyglucosc or maltose are practically tasteless, the insoluble polyglucosc is a practically tasteless yellow powder before bleaching.

Most of the polyglucoses produced according to the invention have average molecular weights between about 3,000 and about 36,000. the soluble polyglucoses being average molecular weights between about 3,000 and about 18,000 and the insoluble polyglucoses between about 3,000 and about 36,000.

The experimentally determined average Molecular weights of the polyglucoses produced according to the invention are between about 2000 and about 24,000, with most values in the range between 4000 and about 12,000. The determination of the average molecular weights were carried out with the aid of the modified reducing end group

fio method according to I s b c 11 (J. Res. Nail. Bur. Standards 24,241 [1940]). This method is based on the reduction of an alkaline copper-citral reagent. The average Molecular weights are calculated on the basis of the standardization with anti-biobiosis, namely assuming that equimolar amounts of polyglucose and Gcnliobiosc have approximately the same reducing power and one reducing end group per Own molecule. Determined in this way

709 640/53

Obviously, the number average molecular weight is a misleadingly low number because this approach favors the low end of the molecular weight distribution of polycondensation products with broad molecular weight distribution ranges. When the modified reducing end group method was used to determine the average molecular weight of a commercially available clinical dextran with a known average molecular weight of 40,000 ± 1,000, only one average molecular weight was obtained! of 25,600. It was therefore considered permissible to multiply the number average molecular weight determined by the modified reducing end group method by at least 1.5. The number average molecular weights given in the following examples are therefore referred to as apparent average molecular weights or apparent number average molecular weights; they have been determined in the manner described here. The apparent number average molecular weights are referred to as «Λ / _η .

The bonds that are predominant in the polyglucoses are 1-6 bonds; but it can other bonds also occur. In the soluble polyglucoses, each acid decinitol is with an or esterified several polyglucose units. If the acidic unit is combined with more than one polyglucose unit, this is how networking occurs.

Synthetic polyglucoses, which with the help of the erfindungsgeniäßcn Process can be produced by starch-degrading enzymes, such as amylo- (l, 4) -glucosidases, Amylo-1,4; 1,6) -glucosidases, aniylo- (1,4) dextrinases and amylo- (1,4) -maltosidases as well as λ- and fJ-glucosidases. Sucrasc and Phosphorylase not degraded.

The soluble polyglucoses and polymaltoses are suitable for dietetic foods in which the Sugar has been replaced by artificial sweeteners. does; to impart other properties besides sweetness that otherwise they are bestowed by the natural sugar. Typical uses for the soluble Polyglucoses are low-calorie jellies, jams, and canned foods. Jams and friichtcaiifsti ichc; dietary frozen edibles, such as ice cream, ice milk, 4s I ruchie ice cream and water ice cream, baked goods such as cakes, biscuits, Cakes and other foods that contain wheat flour or other flour in l'ondanl, confectionery and , Chewing gum, in beverages, / .. B. non-alcoholic, "Soft" beverages and root extracts, in syrups, in coatings, sauces and puddings, in salad dressings as well -jits Medium for increasing the volume of dry low-calorie sweets, such as cyclamate or saccharin contain.

ν The insoluble polyglucoses can be used as flour substitutes can be used in cakes, biscuits, bread, tarts and other baked goods, whereby corn, rice or potato flour, but graham, rye, soy, oat or bean flour can also be substituted. The insoluble Polyglucoses are suitable for .inch / ur use in yeast-free foods, such as Spaghetti and noodles, eggs as binders for meat dough and Karloffelbrci as well as for other purposes, in which flour is used as an ingredient.

If the polyglucoses and polymaltoses according to the invention are added to dietary foods, so these - compared to the products made with natural ingredients - keep the same tasty and appetizing qualities. The calorie content of diet foods but is achieved by using the products according to the invention instead of natural sugars and starches considerably reduced.

The invention is illustrated in more detail by means of the following examples. Examples I to 11 relate to Production of the polyglucoses or polymaltoses, Examples 12 to 19 their application. Due to the in Amounts of polyglucoses given to these examples for certain dietetic foods can easily determine what amounts of polyglucose or polymallose in foods other than those described are to be used. The products were manufactured in the usual way.

Example I.

Soluble polyglucose containing 2.5% citric acid by melt / polycondensation

An intimate mixture of 500 g powdery, anhydrous glucose and 12.8 g finely ground citric acid was placed in a flat stainless steel dish and placed in a vacuum oven at 160 "C and heated to a pressure of 0.1 torr for 8 hours, after which the polycondensation was essentially ended. The light yellow product was completely soluble in water and contained only a trace of unreacted glucose. the The following data could be obtained for the polycondemat be determined:

Reduklionsweri (RV) = 7.0 (Hagedorn- | ensen-J <> Cathedral method),

apparent average molecular weight (uM _n ) = 9100,

pH value (5% aqueous 1st solution) = 2.9,

Acid equivalent = 9.6 mg NaOI l / g, i optical rotation = +63.6 (c = I, water).

Viscosity / ahl [i;] = f

Example 2

Mixture of soluble and insoluble polyglucose containing 6% citric acid

A batch of 320 g of dextrose monohydral and 20 g of powdered citric acid was carefully mixed, placed in a flask and melted with stirring at a pressure of 14 torr. The melt was held for 25 hours at 17O ⁰ C. The crude polycondensation was ground and separated into soluble and insoluble polyglucoses by extraction with water. The following data were observed:

Knlipolykorulcnsul Insoluble Soluble l'olyglucosc l'olyglucoso Yield ("M) 100 68 32 RV 5.1 2.6 5.1 aMn 6100 10 500 6000 pH (5%) 2.75 2.65 26th Acid equivalent (mg NaOH / g) 12.8 12.8 12.0

Example 3 _;

j soluble containing 75% fumaric acid
Polyglucose

A mixture of 275 g dextrose monohydrate and> IOG fumaric acid was melted in a flask, without stirring, and then maintained for 17 hours at a pressure of 23 Torr at 16O ⁰ C. The pale yellow colored polycondensate had an R V value = 7.7 and a - // Vf ,, = 5100. The pH of a 5% aqueous solution was 2.6, the acid equivalent was 19.2 mg NaOH / g. The optical rotation was + 60.2 ° (c = \. Water) and the Gardner color index was 2.5 (10% wt% aqueous solution).

Example 4

Soluble containing 5% succinic acid
Polyglucose

A ground mixture of 190 g glucose and 10 g succinic acid was in a glass bowl in a Vacuum oven heated at 140 ° C for 24 hours at a pressure of 0.2 Torr until the polycondensation in the was essentially complete. The water-soluble polycondensate has a /? V value = 14.2 and a ^ 5 3Ä7 "= 2630. The pH of the 5% aqueous Solution was 3.1, the acid equivalent was 11.2 mg NaOH / g. The raw material had a Gardner color index of IO (IO% w / v solution).

Example 8 Example 5

Soluble containing 7.5% adipic acid
Polyglucose

Fm Ansal / from 306 g of dextrose hydrate was 22.5 g Adipic acid mixed and stirred in a flask for 12 hours at 153 C and a pressure of

Treated 19 torr. Ks became a stream of nitrogen

10 ml per minute initiated. The completely water-soluble polycondensate had a / VV value = 25.7, an .iM "= 1550. a'-T pH value (5% aqueous solution) = 3.0. an acid equivalent = 20 mg / NaOl ^f 'g and an optical rotation of +44.3 (c = I. water).

Example 6
Soluble polyglucose containing 5% tartaric acid

A mixture of 38Og powdered glucose and

20 g of powdered tartaric acid was placed in a glass bowl melted in a vacuum oven and 4.5 hours ugly at I42 ° C and 0.2 tone. The thus obtained Product contained 68% non-dialysable polycondensate with a /? V value = 6.5 and a 3 / V / „= 7500. The Viscosity number [/;] was 0.04 dl / g.

Example 7

Melt polycondensation of maltose with

5% citric acid

A mixture of 300 g of maltosc monohydrate and 5% citric acid was melted in a flask. The melt was 7 hours at 160'C and

Held at 11 torr. The product was completely water-soluble polymaltose with ejncm /? V value = 19.6 (maltose standard) and an aÄ7 _r = 220O. The pH of the 5% aqueous solution was 3.2 and the acid equivalent was 18.4: ng NaOH / g, while the optical rotation was +1195 ' (c = water) and the Gardner color index was 73 (10% wt. Solution) was.

30th

15th

40 Melt polycondensation of glucose with 5% maleic anhydride

A mixture of 500 g of powdered glucose and 12.8 g of finely ground maleic anhydride was ernitzt about 6 hours in a glass dish in a vacuum oven at about 140 ⁰ C and a pressure of 0,4Torr. Some of the maleic anhydride was lost from the mixture through sublimation. The pale yellow polymer that formed was completely soluble in water and had an acid equivalent of 1.6 mg HaOf l / g, an R V value = 15, an aM “= 2000 and a pH value of 2 in 5% solution , 9 on. The optical rotation was + 68 ° (c = \. Water) and the Gardner color index was 2 (10% aqueous solution, weight percent). After about 24 hours of dialysis against running tap water, 49% non-dialysable polycondensate could be obtained, which had the following data: /? V = 8.5, aW "= 5200, pH (5% aqueous solution) = 6.5, optical rotation = + 59.2 ' (c = 1st water).

Example 9

Melt polycondensation of glucose with 5% succinic anhydride

An intimate mixture of 300 g of powdered dextrose ionohydrate and 15.8 g of finely ground succinic anhydride were placed in a flask and rapidly melted at a temperature of between 160 and 165 ° C. and a pressure of 100 torr. The rapid melting, which required about 45 minutes, was necessary to reduce the loss of the anhydride from the mixture by sublimation / u. Thereafter, the temperature was lowered to 142 ° C. and the pressure was lowered to 26 torr. The mixture was left under these conditions for 16 hours, after which the polycondensation was essentially complete. The yellow product was completely water-soluble. The following data were determined for the pole ·, condensate R \ =? JS. .-, M _n - 1240. pH (S '^ oige aqueous solution) = 2.H. Saurcaquiva-Icrit = 14.4mg NaOH / g. optical rotation = + 52 ff = 1st water). Gardner color index = 7 (10% by weight aqueous solution).

Adipin was used instead of succinic anhydride satire anhydride was used, a Completely water-soluble poly condensate. which in others had similar properties.

Example 10

Shrnel / polycondensation of glucose with 5% itaconic anhydride

An intimate mixture of 300 g powdered dextrose monohydrate and 15.8 g of finely ground haconic anhydride were placed in a flask and at a temperature / between 160 and 165 ° C and pressure melted by 100 torr for 45 minutes. The rapid melting was necessary to prevent the loss of the Prevent itaconic anhydride from the mixture through sublimation. After that the temperature was up Lowered 142 ° C and lowered the pressure to 26 Torr. The mixture was kept under these conditions for 16 hours. Then there was the polycondensation essentially completed. The yellow thus obtained

Product was completely soluble in water. The following data were determined for the polymer: RV = 15.5. üM "= 2420, pH (5% aqueous solution) = 2.85, acid equivalent = 13.2 mg NaOH / g, optical rotation = + 55.2 °, Gardner color index (10% weight / volume aqueous solution) = 4.5.

Example 11

Melt polycondensation of glucose with 5% phthalic anhydride

An intimate mixture of 300 g of powdered dextrose monohydrate and 15.8 g of finely ground phthalic anhydride was placed in a flask and melted for 45 minutes at a temperature between 160 and 165 ° C. at a pressure of 100 torr. The rapid melting was necessary to prevent loss of the anhydride from the mixture through sublimation. The temperature was then lowered to 142 ° C. and the pressure was lowered to 26 Torr. The mixture was kept under these conditions for 16 hours. The polycondensation was then essentially complete. The yellow product thus obtained was completely soluble in water. The following data were determined for the polycondensate: RV = 4.2, a / W "= 2360, pH (5% aqueous solution) = 2.7, acid equivalent = 14.4 mg NaOH / g. optical rotation = 60.3 ° (c = \, water), Gardner color index = 5.5 (10% weight / volume aqueous solution).

Example 12 cakes

another vessel was made of flour, insoluble l'olyglucosc. the rest of the baking powder and the sodium bicarbonate mixed together. Then all the ingredients were combined and Stirred and beaten for 10 minutes until a homogeneous, crcmigc mixture was formed. This cake batter was poured into a mold and baked at 210 "C for 20 to 25 minutes.

Example 13
pudding

A pudding was made from the following ingredients:

Laudable polvglucoscitrate,
invention gciiiai. », ..>», t u '' ·
Cornstarch
Calcium cyclamate
Sodium saccharine
Artificial vanilla flavor concentrate
Sodium chloride
Whole milk

20 6.0 g
"\ 5f
0.240 g 0.02 jg

0.02 g
45.0 g

25 All ingredients except the milk were mixed well. The milk was heated moderately while the blended ingredients were added. The mixture was then allowed to boil gently for 10 to 15 minutes. The mixture was poured into pudding mold and left to cool and set.

Example 14
sweets

Using the inventive method 35
The following ingredients became hard

Ingredients made: candies made:

Oleo margarine '2g Skimmed milk 15 g Volicipulvcr 25 g water 90 g salt 0.6 g Soluble, discolored Polyglucose citrate 25.5 g Bleached cake flour 24.6 g Insoluble polyglucosc (Feinhei 'according to a clear machine tools of 0.044 mm) 24.0 g Sodium bicarbonate 0.5 g baking powder 2.0 g Calcium cyclamal 0.783 g Sodium saccharine 0.093 g Artificial vanilla flavor 0.1 E

Soluble polyglucosciidipal,
manufactured according to Ij-invention

water

Calciumcyclam.it

Sodium saccharine

citric acid
Himbccr flavor

Himbccrfarbsloff FDC

45 g

20 "
0.90 g 0.09 g 0.3 g
0.06 g 0.01 g

The volicipulvcr was mixed with 75 g of water and turned off for one hour. In another vessel, oleomargarine, milk, salt, soluble polyglucose and 1 gram of baking soda were mixed together. The mixture of water and volicipulvcr svtirdc carefully added in small amounts little by little, stirring well after each addition. Then the remaining water and the vanilla flavor / ugcsct / l. The mixture was stirred for 5 minutes. Sacccharin sodium and calcium cyclamate, which were dissolved in a small amount of water, were added to this mixture. The mixture was stirred well. In a polyglucosc and water were mixed. The mixture was heated to 140 ° C. to make the polyglucosc soluble. In a separate vessel, sodium cyclamate and saccharin-sodium were added to a small amount of water. In a third vessel, citric acid, the Himbccr flavor and the Himbccr dye FDC were dissolved in a small amount of water. The Polyglucosc- and Wasscmiiscluing was cooled to HO ⁰ C. Then the mixture of sweeteners and water and the mixture of flavors, citric acid, colors and water were added to the polyglucosc and water mixture. That so

The resulting mixture was poured onto a plate coated with mineral oil, on which it is partially can solidify. After solidification, the mixture was poured into a fruit drop cream which gave the product the desired candy shape.

ft.s was used instead of soluble polyglucoscadipai soluble polyglucose succinate or soluble polyglucose cfumaral were used, corresponding ones were obtained Products.

Ii e i s ρ i c I 15

Maple syrup the following ingredients became a maple syrup

M.
nip made:

Soluble Polyglucosezitnii

water

Maple extract

Niilrium cyclamate

Sodium saccharine

Example 18 Low calorie salad dressing

From the following ingredients a diiiteti * see salad dressing made!

9.0 g 8.0 g 0.08 g 0.45 g 0.05 g

IQ

The sweeteners were dissolved in water and the polyglyucose and maple extract were added. the Mixture was heated to a syrup.

Example 16

Diet carbonated drink

A carbonated drink was made from the following ingredients:

20th

Calcium cyclamate 0.456 g Sodium saccharine 0.040 g citric acid 0.9 g Strawberry flavor 0.9 g Soluble polyglucose citrate 30.0 g water 30.0 g

Whole milk

Cream (40%)

Soluble neutralized

Polyglucose citrate

Sodium carboxymethyl cellulose calcium cyclamate

gelatin

Artificial vanilla flavor

57.4 g 57.4 g

39.2 g 0.78 g 0.25 g 0.3 g 0.52 g

The ingredients were mixed completely and the mixture frozen in appropriate shapes.

Calcium cyclamate

Dryer mustard

vinegar

tomato sauce

Soluble polyglucose citrate

Sodium chloride

Insoluble polyglyucose

(with a delicacy

according to a clear

Mesh size of 0.074 mm)

Paprika onion powder cr

Garlic powder

Black pepper

Lemon juice

(natural strength)

water

Pectin (from th rn to

Gel formation 1 part by weight for

150 parts by weight of sugar are required will, d. H. a pectin with a

Degree of gelation of 150)

0.2 g

1.2 g 36.0 g

4.0 g 14.0 g

3.0 g

8.0 g LOg LOg LOg LOg

6.0 g 72.3 g

1.3 g

30th

The ingredients were combined and mixed with 237.7 grams of carbonated water to form a beverage.

Example 17

Dietary ice cream

An ice cream was made from the following ingredients, manufactured:

The dry ingredients were combined and added to the water with constant stirring. To At the end of this work, lemon juice, vinegar and tomato sauce were added. The mixture obtained was stirred until completely homogeneous.

Example 19 Dry, low calorie confectionery

A dry, low-calorie sweet milk is made from the following ingredients:

40 calcium cyclamate
Sodium saccharine
Soluble polyglyucose

10.0 g

Log

189.0 g

The ingredients were mixed in a mixer until a completely homogeneous, dry powder was obtained. One level teaspoon of this mixture corresponded in sweetening power to one level teaspoon Sugar (sucrose).

The exploitation of the invention can be based on statutory provisions, in particular the Food Act, be limited.

709 640/53

Claims (3)

Piiteniiinspruehe: 1. Method of manufacturing for food! suitable polysaccharides and polysaccharides derivii "of glucose ("'er ivliilio.su by mixing and lirhir / .cii of glucose · or miillo.sc with an acidic Kn in lysine or at a pressure of /' between IO '· and 100 Torr, dad ii rc Ii geke η η / eich η e ι that mim a dry anhydride or lydnite of d-glucose or d-miliosis at temperatures of MO-180 C and a pressure between 10 and 100 torr melts and below Exclusion of water and Ι.ιιΓι in the presence of 0.1 - IOMol-% of a slightly iliichligen, suitable for food organic polycarboxylic acids or their anhydride in the molten state polycondensed and at the same time the water formed during the felling and the polycondensation among the above temperature and pressure bcdingiingen jo removed. 2. The method according to claim I _1, characterized in that a molar ratio of 111,111 and glucose or maltose / 11 organic Polvcarbonsäurc of 12: I to 20: I applies. 3. Use of the hergesielllen according to claim I. Polysaccharides or polysaccharide derivatives of glucose and / or mallose as additives for detergents or sweeteners.