CS261831B1 - Polymeric surfactants and methods for their preparation - Google Patents
Polymeric surfactants and methods for their preparation Download PDFInfo
- Publication number
- CS261831B1 CS261831B1 CS872698A CS269887A CS261831B1 CS 261831 B1 CS261831 B1 CS 261831B1 CS 872698 A CS872698 A CS 872698A CS 269887 A CS269887 A CS 269887A CS 261831 B1 CS261831 B1 CS 261831B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- weight
- parts
- polymeric surfactants
- hemicellulose
- amount
- Prior art date
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Riešenie sa týká polymérnych tenzidov tvořených hemicelulózou alkylovanou alky- \ . lovými skupinami s počtom atómov uhlíka 10 až 18 pri stupni alkylácie 0,1 až 1,0. Polymérne tenzidy podl'a riešenia sa pripra.vm jú tak, že sa na hemicelulózu v množstve 10 až 15 dielov hmotnostných působí alkylbromidom s 8 až 18 atómami uhlíka v alkylskupine v množstve 2,49 až 45 dielov hmotnostných v přítomnosti 3,3 až 4,54 dielov hmotnostných hydroxidu sodného v dimethyl· formamide.The solution concerns polymeric surfactants formed by alkylated hemicellulose. by left groups with the number of carbon atoms from 10 to 18 with a degree of alkylation of 0.1 to 1.0. Polymer surfactants according to the solution are prepared by treating hemicellulose in an amount of 10 to 15 parts by weight with an alkyl bromide with 8 to 18 carbon atoms in the alkyl group in an amount of 2.49 to 45 parts by weight in the presence of 3.3 to 4.54 parts by weight of sodium hydroxide in dimethyl formamide.
Description
261831 4 3
Vynález sa týká polymérnych tenzidov aspósobu ich přípravy.
Polymérne tenzidy nadobádajá stále vá-čší význam. Široké aplikačně spektrum má-já například blokové kopolyméry etyléno-xidu s propylénoxidom (Blažej a kol. Tenzi-dy, Alfa 1977, s. 85 a 92), májá vysoká e-mulgačná schopnost (Katalog výrobkov che-mických závodov W. Piecka, Nováky, 1977,s. 96 — Slovanik M 640). Z dalších látokmožno uviesť kopolyméry metakrylátu a a-krylamidu (USA pat. 4 089 987). Hydroxye-tylované akrylové kopolyméry ako vhodnéemulgačné prostriedky popisujá autoři Ga-linka J., Hase B.: Fette, Seifen Anstrichmit-tel 78 (1980) s. 362.
Nevýhodou tenzidov uvedených typov jeich čisté syntetický charakter a s tým sávi-siace nevhodnost, například pre potravinář-ské áčely, ako aj velmi nízká biologická od-stránitelnosť v odpadových vodách. .
Vysoká emulgačná áčinnosť májá niekto-ré polymérne tenzidy na báze polysachari-dov a to alkylderiváty hydroxyetylcelulózy(AO č. 214 392) a alkylderiváty hydroxyetyl-škrobu (AO č. 214 393).
Nevýhodou uvedených derivátov je fakt,že sacharidická zložka sa musí najskor o-xyetylovať do takého stupňa, aby sa zaisti-la rozpustnost vo vodě, ako i to, že výcho-diskové látky sa v tuzemsku nevyrábajá vovhodnej kvalitě. Táto nevýhodu odstraňujá polymérne ten-zidy podlá vynálezu, ktorých podstata spo-čívá v tom, že sá tvořené hemicelulózou al-kylovanou alkylovými skupinami s počtomatómov uhlíka 10 až 18 so stupňom alkylá-cie 0,1 až 1,0.
Podstata spósobu ich přípravy spočívá vtom, že sa na hemicelulózu v množstve 10až 15 dielov hmotnostných působí alkylbro-midom s 8 až 18 atómami uhlíka v alkyl-skupine v množstve 2,49 až 45 dielov hmot-nostných v přítomnosti 3,3 až 4,54 dielovhmotnostných hydroxidu sodného v dimetyl-formamide. Hemicelulózy sá polysacharidynachádzajáce sa v značnom množstve v dře-vinách a jednoročných rastlinách. Izolujása váčšinou alkalickou extrakciou. Sá pře-vážné rozpustné vo vodě. Zvlášť výhodnýmzdrojom sá dialyzačné lúhy pri výrobě vis-kózového vlákna, kde predstavujú nežiadú-ci odpad, ktorý zaťažuje odpadové vody. He-micelulózy můžu byť různého zloženia v zá- vislosti od zdroja: glukurónoxylány, gluku-manány (listnáče), arabinoxylány (ihlična-ny, kukuřičné oklasy). Příklad 1
Ako východisková látka sa použil xylánizolovaný z kukových pilin s priemernýmpolymerizačným stupňom 110. 10 g xylánu sa rozpustí v 600 ml bezvo-dého dímetylformamidu v trojhrdlej bankeopatrenej spátným chladičom, prikvapkáva-cím lievikom a miešadlom. K roztoku xylá-nu v dimetylformamide sa přidá 3,3 g NaOHrozotretého na prášok pod suchým benzé-nom v trecej miske. Zmes sa mieša na vria-com vodnom kápeli až do rozpustenia xylá-nu. Potom sa z prikvapkávacieho lievika po-stupné připustí 24,9 g dodecylbrómidu, pri-čom sa udržuje teplota 90 až 95 °C. Reakciaprebieha za zahrievania a miešania 12 ho-din. Roztok sa potom zahustí vakuovou des-tiláciou na objem 100 ml. Tento sa pretrepe3 X 30 mililitrami petroléteru na odstráne-nie nezreagovaného dodecylbromidu. Zahuš-těný roztok sa potom podrobí dialýze na od-stránenie solí. Zriedi sa na 1 000 ml destilo-vanou vodou. Bromid sodný sa odstráni di-alýzou. Po dialýze sa roztok vákuove zahus-tí pri teplote 50 až 60 °C. Po vysušení sa zís-ká 12,6 g dodecylderivátu xylánu vo forměsvetložltej látky. Zo závislosti povrchovéhonapátia od koncentrácie sa určila minimál-na hodnota povrchového napátia ymi„ = 31,3mNm-1 a kritická micelová koncentrácia2,25 kg . m~3.
Postup stanovenia emulgačnej áčinnosti
Emulzie sa připravili tak, že sa 1 g etnul-gátora rozpustil v 89 ml destilovanej vodya do tohto roztoku sa přidalo v mixéri zamiešania na prvom rýchlostnom stupni 10mililitrov příslušného oleja. Po vliatí olejasa miešalo ešte jednu minátu. Emulzia savliala do 100 ml odmerného valca a v ur-čitých Časových intervaloch sa sledoval ob-jem oddělených vrstiev: olejovej (x) a kré-mové) (y), označené v tabulkách ako x/y.
Ako oleje sa použili řepkový a slnečnico-vý olej (výrobky Palmy, n. p. Bratislava).Výsledky sú uvedené v tab. 1. Účinnost saporovnávala s monoglyceridom vyššej mast-né j kyseliny (Emulgátor C). 261831 Λ
CM
Tabulka
Emulgačná účinnost alkylderivátu xylánu R-5 v porovnaní s emulgátorom C při emulgovaní řepkového a slnečnicového oleja
Emulgátor Ole] Množstvo oddelenej vrstvy olej/krém po čase (min] 5 10 30 60 90 120 150 180 240
O OCM bv CM
O O O CD
rd CM rd CMO θ'O O
rd CM rd CMO O O CD
O rdrd CM rd CMO O O O
O COrd CM rd CM
00 θO CM rd CM o c?c5 c5' Ό o «3 ?> onon
Γ O
O CWN
ONOM o^ao o Μ o cm 1 >o Φ co O Utí a tiMd O O] o 1-4 +> i-( +>
►3 M >3 W)>4 a ►«'S< W <C M 261831 5 Příklad 2
Arabinoxylán izolovaný z kukuřičných o-klaskov má následovně charakteristiky: ob-sah pentóz: xylóza + arabinóza 92 %. Mó-lový poměr xylózy: arabinóza 10 : 1,2, prie-merný polymerizačný stupeň 206. Rozpust-nost vo vodě 90 °/o. 15 g arabinoxylánu sa rozpustí v 450 mlbezvodého dimetylformamidu v trojhrdlejbanke opatrenej chladičom, prikvapkávacímlievikom a spatným chladičom s chlórkalcl-ovým uzáverom. Zmes sa mieša na vriacomvodnom kúpeli, kým sa arabinóza nerozpus- tí. Potom sa přidá po častiach 4,54 g NaOHrozotretého na prášok v trecej miske podbenzénom. Ďalej sa za intenzívneho mieša-nia pomaly přidá 24,9 dodecylbromidu, pri-čom sa udržuje teplota 50 až 100 °C. Reak-cla sa ukončí behom 12 hodin. Roztok pro-duktu v dimetylformamide sa potom spra-cuje ako pri příklade 1. Získá sa 18 g pro-duktu vo formě tuhej žltohnedej látky. Zozávislosti povrchového napátia od koncen-trácie sa určila minimálna hodnota povr-chového napátia χ,ηίη = 31,0 mNm'1 a kri-tická micelová koncentrácia' 0,5 kg . m“3. 261331
Tabulka 2
Emulgačná účinnost na polypropylénový olej K-300 alkylderivátu arabinoxylánu v porovnaní so zmesným emulgátorom nonylfe-nolu oxyetylovaného 6 a 10 mólmi etylénoxidu v pomere 76 : 24
Emulgátor Množstvo oddelenej vrstvy olej/krém po čase (min) 5 10 30 60 90 120 150 180 240 24 h
CD CO O c5 m co"δ o' Φ co¢3 o
co coó CJ OJ OJO C3
OJ OJ o c3 in
rH O
261831 4 3
The invention relates to polymeric surfactants and to their preparation.
Polymeric surfactants are becoming increasingly important. For example, the broad application spectrum has ethylene oxide / propylene oxide block copolymers (Blazej et al. Tenzi, Alfa 1977, pp. 85 and 92), and a high emulsification capacity (W. Pieck Chemical Product Catalog, Novaky, 1977, p. 96 - Slovanik M 640). Other materials include copolymers of methacrylate and α-crylamide (U.S. Pat. No. 4,089,987). Hydroxyethylated acrylic copolymers as suitable emulsifiers are described by Ga-J. J., Hase B .: Fette, Seifen Anstrichmit-tel. 78 (1980) p. 362.
The disadvantage of the surfactants of these types is their pure synthetic nature and hence the unsuitable suitability, for example for the food industry, as well as the very low bioavailability in wastewater. .
Some polysaccharide-based polymeric surfactants have high emulsifying activity, namely alkyl derivatives of hydroxyethylcellulose (AO No. 214 392) and alkyl derivatives of hydroxyethyl starch (AO No. 214 393).
A disadvantage of said derivatives is the fact that the carbohydrate component must first be methylated to such a degree as to ensure water solubility as well as that the starting materials are not produced at a suitable quality in the country. This drawback is eliminated by the polymeric inventive compounds, which consist of hemicellulose alkylated alkyl groups having carbon numbers of 10 to 18 with an alkylation degree of 0.1 to 1.0.
The method for their preparation consists in treating the hemicellulose in an amount of 10 to 15 parts by weight with an alkyl bromide of 8 to 18 carbon atoms in the alkyl group in an amount of 2.49 to 45 parts by weight in the presence of 3.3 to 4, 54 parts by weight sodium hydroxide in dimethylformamide. Hemicelluloses are polysaccharides found in considerable amounts in woods and annual plants. It is isolated by an alkaline extraction. It is predominantly water-soluble. A particularly preferred source is dialysis liquor in the production of viscose fiber, where it is an undesirable waste that wastes wastewater. The micelluloses can be of different composition depending on the source: glucuronoxylans, glucanonans (broadleaf), arabinoxylans (conifers, corn hairs). Example 1
The starting material was xylan-isolated from corn sawdust with an average polymerization degree of 110. 10 g of xylan were dissolved in 600 ml of anhydrous dimethylformamide in a three necked bank cooler, a dropping funnel and a stirrer. To a solution of xylene in dimethylformamide was added 3.3 g of NaOH-powdered powder under dry benzene in a mortar. The mixture is stirred on top of a water drop until the xylene is dissolved. Then, 24.9 g of dodecyl bromide are gradually added from the dropping funnel while maintaining a temperature of 90 to 95 ° C. The reaction takes place with heating and stirring for 12 hours. The solution is then concentrated by vacuum distillation to a volume of 100 ml. This was shaken with X 30 ml of petroleum ether to remove unreacted dodecyl bromide. The thickened solution is then subjected to dialysis to remove salts. Dilute to 1000 ml with distilled water. Sodium bromide is removed by di-alysis. After dialysis, the solution is concentrated in vacuo at 50-60 ° C. After drying, 12.6 g of the dodecyl derivative of xylan are obtained as a light yellow solid. The surface tension versus concentration dependence was determined to be a minimum surface tension value of ymi = 31.3mNm-1 and a critical micelle concentration of 2.25kg. m ~ 3.
The procedure for determining emulsifying activity
The emulsions were prepared by dissolving 1 g of the digestion agent in 89 ml of distilled water and adding 10 ml of the appropriate oil in the first mixer to the solution. After pouring out the oil, it stirred one more minute. The savlable emulsion into a 100 ml volumetric cylinder and at certain time intervals was followed by the volume of the separate layers: oil (x) and creme (y), indicated as x / y in the tables.
The oils used were rapeseed and sunflower oil (Palmy products, np Bratislava). 1. Efficacy was compared with the higher fatty acid monoglyceride (Emulsifier C). 261831 Λ
CM
Table
The emulsifying effect of the alkyl xylan derivative R-5 compared to the emulsifier C in emulsifying rapeseed and sunflower oil
Ole Emulsifier] Separate oil / cream layer over time (min) 5 10 30 60 90 120 150 180 240
OCM bv CM
OOO CD
rd CM rd CMO θ'OO
rd CM rd CMO OO CD
About rdrd CM rd CMO OOO
About COrd CM rd CM
00 θO CM rd CM oc c c5 c5 Ό o 3 3> onon
Γ O
About CWN
ONOM o ^ o o Μ o cm 1> o Φ co O Utí a tiMd OO] o 1-4 +> i- (+>
►3 M> 3 W)> 4 and ► «S <W <CM 261831 5 Example 2
Arabinoxylan isolated from maize corn has the following characteristics: pentose content: xylose + arabinose 92%. The molar ratio of xylose: arabinose is 10: 1.2, the average polymerization degree of 206. The solubility in water is 90%. 15 g of arabinoxylan are dissolved in 450 ml of anhydrous dimethylformamide in a three-necked flask equipped with a condenser, a dropping funnel and a reflux condenser with a chlor-alkali cap. The mixture is stirred in a water bath until the arabinose is dissolved. Thereafter, 4.54 g of NaOH-powder was added in portions to the powder in a sub-benzene mortar. Next, 24.9 dodecyl bromide was slowly added with vigorous stirring while maintaining a temperature of 50-100 ° C. Reaction duties were terminated within 12 hours. The solution of the product in dimethylformamide is then treated as in Example 1. 18 g of product is obtained in the form of a tan solid. The surface tension dependence of the concentration was determined to be the minimum surface tension value χ, ηίη = 31.0 mNm'1 and the critical micelle concentration '0.5 kg. m “3. 261331
Table 2
Emulsifying activity on polypropylene oil K-300 alkyl arabinoxylan derivative compared to mixed nonylphenol emulsifier oxyethylated 6 and 10 moles of ethylene oxide 76:24
Emulsifier Separate oil / cream layer over time (min) 5 10 30 60 90 120 150 180 240 24 h
CD CO O c5 m co "δ o" Φ co ¢ 3 o
co co CJ OJ OJO C3
OJ OJ c3 in
rH O
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS872698A CS261831B1 (en) | 1987-04-16 | 1987-04-16 | Polymeric surfactants and methods for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS872698A CS261831B1 (en) | 1987-04-16 | 1987-04-16 | Polymeric surfactants and methods for their preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS269887A1 CS269887A1 (en) | 1988-07-15 |
| CS261831B1 true CS261831B1 (en) | 1989-02-10 |
Family
ID=5364824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS872698A CS261831B1 (en) | 1987-04-16 | 1987-04-16 | Polymeric surfactants and methods for their preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS261831B1 (en) |
-
1987
- 1987-04-16 CS CS872698A patent/CS261831B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS269887A1 (en) | 1988-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1151213A (en) | Surface active quaternary ammonium compound suitable for treatment of textile and cellulose material | |
| US4521326A (en) | Thickening agent based on polyether derivatives | |
| CN1662705A (en) | Method of dewatering pulp | |
| DE2127082A1 (en) | Process for the production of new polyether amines and their use | |
| US2239974A (en) | Detergent composition | |
| CH647022A5 (en) | AQUEOUS, LIQUID, CONCENTRATED TEXTILE SOFTENER AND METHOD FOR THE PRODUCTION THEREOF. | |
| US2133480A (en) | Production of ethers suitable as dispersing agents and of preparations therefrom | |
| EP0054231B1 (en) | Paper-sizing agents and a process for their preparation | |
| US3225028A (en) | Acrolein adducts of polygalactomannans and polyglucomannans and process of preparing same | |
| EP0032483A2 (en) | Stable aqueous formulations of stilbene brighteners | |
| EP0082823B1 (en) | Process for bleaching fibrous materials with oligomers of phosphonic acids as stabilizing agents in alcaline, peroxide-containing bleaching baths | |
| DE2025238A1 (en) | Powdered detergents and cleaning agents | |
| CS261831B1 (en) | Polymeric surfactants and methods for their preparation | |
| DE2502357C3 (en) | Polyoxyalkylenammonium salts and their use in cellulose and paper processing | |
| FI61221C (en) | SAETT ATT REDUCERA DEN MEKANISKA HAOLLFASTHETEN OCH / ELLER FOERBAETTRA MJUKHETEN HOS CELLULOSA ELLER PAPPER | |
| DE1570296A1 (en) | Process for the preparation of water-soluble derivatives of polyalkylenimines | |
| NL7915011A (en) | WASH CARE PREPARATION, CONTAINING STAGELIZED, VEGETABLE STARCH AND QUANTITY AMMONIUM COMPOUND. | |
| US3419405A (en) | Starch composition comprising souring agents and surfactants | |
| DK164106B (en) | PROCEDURE FOR PREPARING AN ALKYLARYL SULPHONATE CONCENTRATE AND USING IT IN A PROCESS OF INCREASED OIL EXTRACTION | |
| DE3415892A1 (en) | CONCENTRATED TEXTILE SOFTENING COMPOSITION AND METHOD FOR PRODUCING THE SAME | |
| FI94237B (en) | New quaternary ammonium type cationic surfactants, a process for their preparation and their use in the treatment of textiles and cellulosic materials | |
| WO2015079451A1 (en) | Alkylphenol ethoxylates and a process for preparing the same | |
| DE2238275C3 (en) | ||
| US3294703A (en) | Dispersing agents | |
| JP4226348B2 (en) | Anticide composition |