Ebringerová, Anna

Miníková, Slávka

Sasinková, Vlasta

Sroková, Iva

English

DSpace at VSB Technical University of Ostrava

.. : '.\ t t -1 ' ._·, � lil 1B' f - : l j; , i.,.,, v . , • , , .., , v , • , • • )bonde ndoa'FJ pract Vysoke skoly banske-Techmcke u01verz1ty Ostravačíslo I, rok 2008, rnčník LI, řada hutnickáčlánek č. 1405 POLYMERIC SURFACT ANTS PREP ARED BY TRANSESTERIFICATION OF HYDROXYETHYLCELLULOSE WITH METHYL ESTER OF RAPE SEED OIL AND TRIACYL GLYCERIDES S. MINÍKOVÁ 1 , I. SROKOVÁ 1, A. EBRINGEROVÁ 2, V. SASINKOVÁ2 1 Facu/ty o/ lndustria/ Technologies, University o/ A. Dubček in Trenčln, T. Vansovej 1054/45, 020 O/ Púchov,S/ovak Republic, minikova@lnt.tnuni.sk, srokova@fpt.tnuni.sk 1 Center o/ Excellence o/ the Slovak Academy o/ Sciences, Institute o/ Chemistry, Dúbravská cesta 9,845 38 Bratislava, Slovak Republic, chemebri@savba.sk, chemsasi@savba.sk ABSTRACT: Polymeric surfactants were prepared from O - (2 - hydroxyethyl) cellulose (HEC, DS = 1) by transesteritkation with methyl esters ofrape seed oil (MERO) with or without K2C03 as catalystand triacyl glycerides (rape seed oil) using potassium laurate as catalyst in sy�m H20/DMF underthe influence of microwave energy. The various reaction conditions were used to optimize thepreparation of water - soluble esters. Synthesis under microwave heating were realized analogical asdescribed by the preparation of cellulose stearate [l].The obtained esters of hydroxyethylcellulosewere characterized by FTIR spectral data. The surface - active and performance properties weredetermined (surface tension of water, emulsifying efficiency, foamability, washing performance,antiredeposition efficiency). The results suggested that the partially hydrophobized HEC esters arepotential biosurfactants, which might be exploited in various technical applications. Application ofmicrowave energy might .contribute to a more economic process due to substantial shortering ofr�action time.KEY WORDS: hydroxyethylcellulose, transesterification, microwave irradiation, Methyl ester of rap� seed oil, Triacyl glycerides, polymeric surfactants I. INTRODUCTIONDuring the last years, many research activities have been focused on hydrophobically modified polysaccharides because of the interesting functional properties of these derivatives, which provide uses as surfactants, associative thickeners, etc. over a wide field of application. Various commercial and non - commercial polysaccharides, such as alginate [2 , 3], chitosan [4,5], pectin [6], hydroxyethylcellulose [7-9], carboxymethylcellulose [IO], carboxymethyl starch [11,12], glucuronoxylan [13 ,14] have been used to prepare polymeric surfactants. O - (2 - Hydroxyethyl) cellulose (HEC) is water - soluble, nonionic ether, which represents a potencial source of biopolymers for furtlrer chemical modification. Recently, some altemative esterification methods, such as esterification with mixed.anhydrides prepared „in situ" [15] transesterification with vinyl carboxylic acid esters like vinyl laurate [ 16] and transesterification with fatty acid methyl esters [ 17) have been developed to avoid the use of acid halides. Partial hydrophobization of HEC using mixed anhydrides and vinyl laurate [9] was perforrned under relatively mild reaction conditions (low reactant to HEC weight ratios, low temperature and/or short reaction time). In contrast to cellulose, no special solvent systems or pretreatments were necessary owing to the solubility of HEC in aprotic solvents, which is an important advantage of these hydrophobization techniques. ln spite of the very low degrees of 256 to microwave heating 'for'.-1 - 2 min with power of 660 W. The reaction product was subsequently precipitated into a volume of acetone that was 5 tiJJleS larger than the reaction mixture, after 24 h was product separated by vacuum fihration over fritted glass, thoroughly washed with acetone and then purified by Soxhlet extraction with acetone for 8 h. In some experiments, the product was dissolved in distilled water and purified by dialysation and lyophilization. Reaction conditions and yields ofwater - soluble HEC esters are given in Table I.Tab. I: Reaction conditions and yields of water - soluble HEC derivatives obtained by transesterification with MERO and rape seed oil in H2O/DMF with controlled power of 660 W. Derivative SR Mass ratio HEC: MERO HEC/I SR- 355 I: I HEC/2 SR-337 2: I HEC/3 SR- 357 3: I HEC/4 SR- 347 4: I HEC/5 SR� 338 I: I HEC/6 SR-338/6 I: 2 HEcn•i SR- 372 I: 2 HEC/8a.)b.J SR - 373 I: I HEC: rape seed oil HEC/9 c.J SR - 377 I: I HEC/JO SR- 378 I: I HEC/I I d) SR- 382 I: I HEC/12 SR- 380 I: 2 HEC/13 SR- 381 2: I * expressed as g ofthe recovered derivative per g HECTime Temperature Yielď (min) (OC) {i:/!!) I 92 0.72 I 93 0.69 I . 96 0.71 I 88 1:05 2 96 1.06 2 90 . 1.00 I 100 0.95 2 90 1.05 5 177 0.86 2 90 0.86 2 90 0.73 2 91 0.75 2 85 0.81 a) reaction time was measured after 5 minutes and derivatives were exposed the controlled power of250 W in microwave reactore "MILESTONE"b) K:;CO3 was used as catalyst (24] c) derivative was prepared using „solvent - free" technique by classical heatingd) derivative was prepared without solvent DMF under microwave irradiation2.3 Characterization of the obtained HEC esters The prepared products were characterized by FTIR spectroscopy. The FTIR spectra of the derivatives show absorption bands or shoulders for ester groups at - 1741 cm- 1• The v0, (CH2) and v, (CH2) vibrations ofthe fatty acid substituents are present at - 2932 cm-1 and - 2868 cm- 1• r 258 HEC/12 SR- 380 54.67 0.625 0/0 HEC/13 SR- 381 49.96 . 0.625 0/0 Tween 20 - - 0/0 Water 72.80 - -HEC 61.70 1,250 0/0 HEC/MW . 64.80 1.250 0/0 SOS 32.00 1.250 -SOS - Sodium dodecyl sulphate(-)- not detennmg�ce tens1on versus logarithm of polymer concentration70 • - ! I f • • • 'K X -65 )i( )i( X X X 60 X X X X � 55 .<-- X e v , o o Z 50 ■ ◊ o • 45 ■ 40 ■ ■ 35 • ■ 30 -2 -1.5 -1 -0,5 o 0.5 logc 0/0 0/10 ů/0 0/3 0/0 0/11 - -0/0 0/6 0/0 0/5 - -jxsR - 380 oSR- 381 I luSR- 382 [esR- 377 I I' SR- 378 (\ XHEC-MW I ,■sos I Fig. 2: Surface tension ver·sus logarithm of polymer concentration (* - height of oil and cream layers fonned on the surface ofthe emulsion after 5 min (h 1), I h (h2) and 24 h {h3))Performance testing methods The washing power (WP) and antiredeposition efficiency (ARE) some ofthe tested derivatives at concentration 0.5 kg.m-3 (WP) and 5 kg.m-3 (ARE) were detennined by the methods described in more detail in a previous paper [9] using a model soil and cotton fabric (SK- standard 800 101). WP was assesed by detennining the reflectance of an artificially soiled cotton fabric after washing in an alkaline surfactant bath. The washing time for WP was I O mi,n, for ARE 60 min and the washing temperature for WP was 50 °C, 80 °C and for ARE 60 °C. The foarriability (F) of aqueous solutions of the prepared HEC esters at concentration I kg.m-3 was detennined at laboratory temperature using the method described in a previous paper [26]. Tab. 3: Washing power (WP), antiredepositive efficiency (ARE) and foamability (F) of HEC esters ánd controls r: Derivative HEC/I HÉC/2 HEC/3 HEC/4 HEC/5 HEC/6, HEcn•-J HEC/8. a.)b.) WPRll°í (%) -95.0 -96.0 96.2 ---WPs,rr (%) ARE60°, (%) F(¾) - - 78.6 - 84.7 80.7 - - 73.1 - 50,1 65,9 - 86,3 32.1 86,3 - 32.1 82,0 80,5 20.7 82,2 86,0 75.9 260 

Polymeric surfactants prepared by transesterification of hydroxyethylcellulose with methyl ester of rape seed oil and tryacyl glycerides

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Polymeric surfactants prepared by transesterification of hydroxyethylcellulose with methyl ester of rape seed oil and tryacyl glycerides

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