SE123736C1

SE123736C1 -

Info

Publication number: SE123736C1
Authority: SE
Publication date: 1948-01-01

Description

KLASS 53 k:1/01 BEVILJAT DEN 4 NOVEMBER 1748 PATENTTID FRAN DEN 14 MA] 1946 PUBLICERAT DEN 4 JANUAR' 1949 H. PALLMANN, ZURICH/ZOLLIKON ocn H. DEUEL, nrRICH, SCHWEIZ. CLASS 53 k: 1/01 GRANTED ON NOVEMBER 4, 1748 PATENT PERIOD FROM MAY 14, 1946 PUBLISHED ON JANUARY 4, 1949 H. PALLMANN, ZURICH / ZOLLIKON ocn H. DEUEL, nrRICH, SWITZERLAND.

Satt for framstallning av pektinammen med forbattrad vattenlOslighet. Set for the production of the pectin name with improved water solubility.

Prioritet begard friin den 26 februari 1946 (Schweiz). Priority was given to Friin on 26 February 1946 (Switzerland).

Foreliggande uppf inning ayser ett Ioniaringssatt for forbattring av vattenliisligheten och avser dessutom forandringen av andra egenskaper sdsom elektrolytkansligheten hos pektinarnnen utan namnyard nedbrytning av peklinmakromolekylen. The present invention provides an ionization kit for improving the water solubility and also relates to the alteration of other properties such as the electrolyte sensitivity of the pectin without nameless degradation of the peclin macromolecule.

Vattenlosligheten och dispergeringsfOrmagan hos pektinpreparat av det slag, som fore- komma i handeln, dr sasom bekant ofta otill- fredsstallande. I synnerhet de svagt med metanol fOrestrade pektinerna och de metoxyl- fria pektinsyrorna arc ofta knappast losliga i yatten. En forbattring av vattenlosligheten och en. stegrad okanslighet gentemot elektro- lyter kan ernas enlist talrika, Hilda fOrf a- ringssatt genom olika tillsatser. Vid makro, molekyler sasom pektinamnena an det nu re- lativt latt mojligt att genom en. endast ringa kemisk forandring, som icke ails far stracka sig till makromolekylens alla kedieled, astadkomma vdsentliga forandringar med ayseende pa egenskaperna. As is well known, the water solubility and dispersibility of pectin preparations of the type which are commercially available are often unsatisfactory. In particular, the weakly methanol-esterified pectins and the methoxyl-free pectic acids are often hardly soluble in the yacht. An improvement in water solubility and a. Increased insensitivity to electrolytes can be quite numerous, Hilda proposed through various additives. In the case of macros, molecules such as pectin names, it is now relatively easy to get through one. only minor chemical changes, which may not extend to all chains of the macromolecule, bring about significant changes in the properties.

FOreliggande uppfinning är I synnerhet avsedd att komma till fmvandning yid pektin- syror, enar hogpolymcr pektinsyra i motsats till pektiner ãr praktiskt taget vattenoloslig. Forfaringssattet enligt foreliggande uppfinning bestar dari, att man upphettar pektin- amne med formaldehydvattenlosning, sit att utan namnyard nedbrytning av makromolekylen och under hogst ringa fornatning mellan makromolekylerna bildas oximetylpektinamnen (halyacetaler). In particular, the present invention is intended to be incorporated with pectic acids, one of which is a highly polymeric pectic acid as opposed to pectins which is practically water-insoluble. The process according to the present invention consists in heating pectin amene with formaldehyde aqueous solution, in that without nominal degradation of the macromolecule and during very little crosslinking between the macromolecules the oxymethyl pectin names (halyacetals) are formed.

Det har namligen visat sig, att vattenolosHg, hogpolymer pektinsyra blir vattenloslig genom upphettning till 7-100° G i relativt koncentrerad formaldehydvattenlosning (5040 % formaldehyd). Utan uppvarmning gar pektinsyran emellertid icke i losning. Den efter upphettning med formaldehyd erhallna s. k, oximetylpektinsyran bibehaller sin. vattenloslighet efter utfallning (med saltsyra, kalciumklorid, alkohol etc.), rening och torkRing. Det har haryid intratt en reaktion mellan pektinamnet och formaldehyden. En tillsats av katalysator ãr icke advandig for erhallandet av det onskade, vattenlosliga oximetylpektinamnet. Namely, it has been found that water-insoluble, high polymer pectic acid becomes water soluble by heating to 7-100 ° C in relatively concentrated formaldehyde aqueous solution (5040% formaldehyde). Without heating, however, the pectic acid does not dissolve. The so-called oximethylpectic acid obtained after heating with formaldehyde retains its. water solubility after precipitation (with hydrochloric acid, calcium chloride, alcohol, etc.), purification and drying. There has been a reaction between the pectin name and the formaldehyde. Addition of catalyst is not suitable for obtaining the desired water-soluble oxymethyl pectin name.

Behandlingen av oximetylpektinamnet med utspatt alkali eller mineralsyra vid rumstemperatur och de inom pektinindustrien vanliga reningsmetoderna skada knappast preparaten. Genom intensiv inverkan av alkali el her genom uppkokning med utspadda mineral, syror forstoras oximetylpektinamnena analogt med de vanliga pektinamnena. The treatment of the oxymethyl pectin name with dilute alkali or mineral acid at room temperature and the purification methods common in the pectin industry are unlikely to harm the preparations. Due to the intense action of alkali or here by boiling with diluted minerals, acids, the oxymethyl pectin names are enlarged analogously to the usual pectin names.

Vid foreliggande fOrfaringssatt for inyerkan av formaldehydvattenlosning pa pektinamne intrader en kemisk reaktion, i det att formaldehyden reagerar med pektinamnets alkoholiska hydroxylgrupper. Vid denna omsatt, ning forblir halten karboxylgrupper oforand, rad. FOr forbattrandet av vattenlosligheten. Or det viktigt, att reaktionen utfores ph system med relatlyt ringa pektinkoncentration (t. ex. 1 g pektinamne per 100 cm' total volym). In the present process for the effect of formaldehyde aqueous solution on pectin name, a chemical reaction occurs in that the formaldehyde reacts with the alcoholic hydroxyl groups of the pectin name. In this reaction, the content of carboxyl groups remains unchanged. For the improvement of water solubility. Is it important that the reaction is carried out in pH systems with a relatively low pectin concentration (eg 1 g pectin name per 100 cm 'total volume).

Sitlunda kommer det knappast till fornatning mellan pektinmakroxnolekyler, d. v. s. en formaldehydmolekyl reagerar i regel endast med en °eh icke med tva angransande pektin, rnolekyler. Alit efter reaktionens omfattning kan emellertid en pektinmakromolekyl reagera med flera formaldehydmolekyler. Det bildas alltsa pektinamnets oximetyletrar (halvacetaler). Vid pektinmakromolekylen anlagras sidokedjor (-0C1120H), som forma lea-- andra vattenlosligheten och andra egenskaper. Oximetylpektinsyrans vattenangadsorption Or icke Okad gentemot den vattenolosliga utgangspektinsyran. Det intrader alltsa visserligen icke nagon vasentlig stegring hos preparatets hydrofila egenskaper genom det beskrivna forfaringssattet. InfOrandet av sidokedjorna synes forsvara bildandet av olosliga forhindningar mellan makromolekylerna. Sitlunda hardly occurs at the junction between pectin macroxolecules, i.e. a formaldehyde molecule usually reacts only with one or not with two adjacent pectin molecules. However, depending on the extent of the reaction, one pectin macromolecule may react with several formaldehyde molecules. The oxymethyl ethers (semi-acetals) of the pectin name are thus formed. At the pectin macromolecule, side chains (-OC1120H) are deposited, which form lea-- other water solubility and other properties. The water-adsorption absorption of oxymethylpectic acid Or not Okad to the water-insoluble starting pectic acid. Admittedly, however, there is no significant increase in the hydrophilic properties of the composition through the process described. The introduction of the side chains seems to justify the formation of insoluble barriers between the macromolecules.

De vattenliisliga oximetylpektinsyrorna bilda sarskilt hogviskosa vattenlosningar. En direkt jamforelse med utgangspektinsyran dr har icke mojlig, da den sistnamnda till stk.- sta delen Or oloslig I vatten. En ungefarlig jamfOrelse med makromolekylstorlekarna kan ske ph losningarna av matriumpektat i utspadd natronlut (jamfor H. Demi och F. Weber, Helv.schim.acta 28, 1089, 1945). Det visar sig, att icke nagon nedbrytning ager rum genom formaldehydbehandlingen. Viskosite- 2— -- ten är tyartom mestadels nagot Okad efter formaldehydbe.handlingen. Detta kan vara betingat genom en ringa, anisotropien farstorande fornatning mellan makromolekylerna. Det ãr troligt, att de nyinfOrda oximetylsidokedjorna verka viskositets5kande. Vid pektinvattenlosningar torde ju tiven en Mining av -viskositeten genom metylestergrupperna vara att beakta. The water-soluble oxymethyl pectic acids form particularly highly viscous aqueous solutions. A direct comparison with the starting pectic acid there is not possible, as the latter to the first part Or insoluble in water. An approximate comparison with the macromolecule sizes can take place in the solutions of matriarch pectate in diluted sodium hydroxide solution (cf. H. Demi and F. Weber, Helv.schim.acta 28, 1089, 1945). It turns out that no degradation takes place through the formaldehyde treatment. The viscosity is usually somewhat increased after the formaldehyde treatment. This may be due to a slight, anisotropic magnification between the macromolecules. It is likely that the newly introduced oxymethyl side chains have a viscosity-increasing effect. In the case of pectin water solutions, a Mining of the viscosity through the methyl ester groups should of course be taken into account.

Ornfattningen av den astadkomna reaktionen mellan pektinamne och formaldehyd kan latt faststallas genom kokning av preparaten i utspadd svavelsyra och bestainning av den overdestillerade formaldehyden. En omfalld, renad oximetylpektinsyra avgav t. ex. 0,43 % formaldehyd, beraknat pa torrsubstansen. Detta preparat erh011s, i det att 10 g pektinsyra i 1 liter 20 % -ig formaldehyd upphetta{les under 15 min. till 95° C. The extent of the reaction between pectin name and formaldehyde can be easily determined by boiling the preparations in dilute sulfuric acid and maintaining the distilled formaldehyde. A precipitated, purified oxymethylpectinic acid gave off e.g. 0.43% formaldehyde, calculated on the dry matter. This preparation is obtained by heating 10 g of pectic acid in 1 liter of 20% formaldehyde for 15 minutes. to 95 ° C.

Oximetylpektinamnen kunna aven framstallas direkt ur uppslutet vaxtmaterial. Genom upphettning av dray med vattenhaltig formaldehyd utlbsas knappast mer pektinamne an med vatten enbart. Protopektinets forankring loses ants& icke. Behandlar man emellertid forst draven t. ex. med utspadd saltsyra, si att protopektinet overfores till pektinsyra och darefter med vatten for avIliggnandet av saltsyran, sa kan nu genom upphettning med tormaldehydvattenlosning pekiinsyran snabbt bringas 1 losning. The oxymethyl pectin names can also be prepared directly from digested plant material. By heating dray with aqueous formaldehyde, hardly any more pectin name is released than with water alone. The anchoring of the protopectin is lost ants & icke. However, if you first treat the drafts, e.g. with dilute hydrochloric acid, so that the protopectin is transferred to pectic acid and then with water for the deposition of the hydrochloric acid, so now by heating with formaldehyde aqueous solution the pecic acid can be rapidly brought to solution.

Liksom vid pektinamnen kan man vid olika hogpolymera polyaronider och polysackarider genom lamplig behandling med formaldehyd erna en forandring av losligheten och andra egenskaper. Salunda blir 1. ex. likenin, som är olosligt i kallt vatten, efter upphettning i formaldehydvattenlosning under nagra minuter till 75--100° C latt l&sligt i vatten. As with the pectin names, in the case of different highly polymeric polyaronides and polysaccharides, a change in solubility and other properties can be altered by suitable treatment with the formaldehydes. Salunda becomes 1. ex. likenin, which is insoluble in cold water, after heating in formaldehyde aqueous solution for a few minutes to 75--100 ° C slightly soluble in water.

Exempel. Example.

Overforingen av vattenoloslig pektinsyra vattenloslig oximetylpektinsyra intrader, om man upphettar 10 g pektinsyra i 1 liter formaldehydvattenlosning (med 15-40 % formaldehyd) under 10-30 min. till 90-100° C. Den losta halvacetalen av pektinsyran utfalles med saltsyra-alkohol, urtvattas med utspadd alkohol pa nutsch och torkas. Vid 80° C blir under samma betingelser endast ungefar 40 c,O av pektinsyran vattenliislig. Vid 70° C intrader joke flagon namnvard reaktion med formaldehyd. The transfer of water-insoluble pectic acid water-soluble oxymethylpectic acid enters, if 10 g of pectic acid are heated in 1 liter of formaldehyde aqueous solution (with 15-40% formaldehyde) for 10-30 minutes. to 90-100 ° C. The dissolved half-acetal of the pectic acid is precipitated with hydrochloric acid-alcohol, diluted with diluted alcohol on a cloth and dried. At 80 ° C, under the same conditions, only about 40 ° C of the pectic acid becomes water-soluble. At 70 ° C, joke flagon enters the nominal reaction with formaldehyde.

Claims

Patent claim:

Procedure for the preparation of the pectin names with improved water solubility, characterized in that the pectin hour is heated with aqueous formaldehyde solution, that without significant degradation of the macromolecule and during very low compaction between the macromolecules oxymethyl pectin form (semi-acetals) is formed.

2. A kit according to claim 1, characterized in that it is preferred to work with 2-20 g of pectin name per liter of aqueous formaldehyde solution.

3. Set according to patent claim 1 or 2, characterized in that it is preferred to work at 75-100 ° C.

4. Set according to patent claims 1-3, characterized in that the formaldehyde solution is allowed to act on the pectin names for 5-60 minutes.

5. sat according to patent claims 1-4, characterized in that the formaldehyde solution is allowed to influence the pectin names distributed in plant material.

Salt according to patent application 15, Milne - characterized in that the oxymethyl pectin names are isolated from the formaldehyde aqueous solution according to methods customary in the pectin industry. Stockholm 1948. Kungl. Boktr. 1 '. A. Norstedt & Slim 480089