(Received 9 September 2005, Accepted 15 November 2005)

Transcription

1 BUNSEKI KAGAKU Vol. 55, No. 2, pp. 95 _ The Japan Society for Analytical Chemistry R Sample Preparation Method for Simultaneous Determination of the Content and Molecular Weight of Cationic Polymers in Hair Shampoo by Size-Exclusion Chromatography Junichi SUGIYAMA 1, Hiroyuki HANIHARA 1, Kosuke TANAKA 1, Akinori IGARASHI 1 and Masami FUJIWARA 1 1 Analytical Research Center, Research & Technology, LION corporation, , Hirai, Edogawa-ku, Tokyo (Received 9 September 2005, Accepted 15 November 2005) In previous paper, we established an accurate analyzing method by combining a sizeexclusion chromatography (SEC) with multi-angle laser light scattering (MALLS) and a refractive index detector (RI) for determining the amount and absolute molecular weight of the cationic cellulose derivative {cellulose, 2-hydroxyethyl 2-[2-hydroxy-3-(trimethylammonio)propoxy]ethyl 2-hydroxy-3-(trimethylammonio)propylether,chloride} (CC), which is the most popular cationic polymer used in hair shampoo. However, an appropriate sample-preparation method for the analysis has not been established due to the lack of separation and dissolution procedures of the CC from the shampoo. In this work, we investigated a sample-preparation method in which the CC is efficiently separated from the shampoo without its molecular deterioration. We found that the CC is clearly solubilized by the SEC mobile phase (0.3 mol/l NaClO 4 aqueous solution) as long as the CC is separated from the shampoo, because the tetrahydrofuran insoluble matter is immediately diluted by the mobile phase before drying out. In the SEC measurement, the CC from the model shampoo, the recovery rate and the reproducibility were sufficient. Moreover, no deterioration of the CC through the sample preparation was confirmed from a comparison between the molecular weight of the CC separated from the shampoo and that of the standard CC. Keywords : extraction ; preparation ; cationic cellulose derivatives ; determination molecular weight ; polymer ; shampoo ; SEC ; MALLS. 1 1)4) 1 : ) CCFig. 1

2 96 BUNSEKI KAGAKU Vol Fig. 1 Molecular structure of a cationic cellulose Table 1 Cationic cellulose derivatives used in this work Grade Viscosity (mpa s 1, 25) N content, Cationic rate 5 50 (2 aqueous solution) (2 aqueous solution) (2 aqueous solution) (1 aqueous solution) SEC-MALLS-RI EtOH 6)8) Table 2 Component Composition of the model shampoo Concentration, Anionic surfactant (A) 5 Anionic surfactant (B) 5 Amphoteric surfactant 5 Organic acid proper quantity Stabilizer proper quantity Water remainder THF 90 9) ) ph 11) SEC- MALLS-RI 5) CC CC CC Table 1 CC 9) CC 90 IPA 212 CC Table CC NaClO 4 : NaN 3 : IPAEtOH THF D 2O: NMR minimum99.8

3 : SEC 97 MERK SEC MILLI-Q SEC-MALLS-RI model23 DS-4 SSC-2100Wyatt Technology MALLS : nmdawn DSP-F RI-71:D 2 SEC SEC- MALLS-RI MALLS Dell Dimension XPS R350 Wyatt Technology ASTRA ver RI Dell Optiplex GX1 Scientific Software EZChrom Elite Ver.2.5SEC TSKguardcolumn α6.0 mmid.40 mm TSKgel α-m 7.8 mmid. 300 mm 2 TSKgel α mmid.300 mm 12) 222 JEOL JNM-LA300 FT NMR SYSTEMKOKU- SAN H-2000NR SEC SEC 3 mmol/l NaN mol/l NaClO ml/ µl 5) NaClO 4 NaClO g 170 g EtOH EtOH SEC NaClO 4 SEC CC RI MALLS RI Zimm Plot CC dn/dc 5) 232 CC µm HPLCA A 233 CC 10 mg g0.5 2g1 1g 40 ml ml µm HPLC AA SEC SEC EtOH 810 THF 11 CC EtOH THF 211 CC 0.5 g 4ml EtOH THF 100 ml CC CC EtOH 5 THF EtOH THF THF THF 233 THF THF D 2O 1 H-NMR D 2O THF 1 H-NMR Fig ppm CC CH 2CH 2O: 3.5 ppm N-CH 3 : 3 ppm THF ppm 2.5 ppm THF

4 98 BUNSEKI KAGAKU Vol Fig. 2 1 H-NMR spectra of CC (grade ) (a) THF insoluble matter from the model hair shampoo ; (b) the standard sample Fig. 3 1 H-NMR spectrum of CC (grade ) separated from the model hair shampoo by the improved THF treatment D 2O CC D 2O 1)14) CC CC SEC CC THF THF 12 ml THF 40 ml rpm10 2 THF Fig. 3 THF NMR NMR CC THF THF SEC Table 3 Grade Recovery rates from the model hair shampoos Recovery rate, 0.1 added 0.5 added 1.0 added CC CC CC THF THF THF THF SEC-MALLS-RI 5) CC SEC-RI Table 3 CC n 3 CC THF SEC CC CC 500 ppm

5 : SEC 99 Table 4 Grade Determination of the weight averaged molecular weight {Mw (10 4 )} Raw material Mw (10 4 ) Extracts from shampoo SEC C.V. 1.9n 5 CC SEC-MALLS-RI 5) CC SEC-MALLS-RI Table 4 Fig. 4 THF CC 4 RI CC CC CC 4 CC THF 0.3 mol/l NaClO 4 SEC-MALLS-RI CC Fig. 4 Plot of elution volume vs. molecular weight and RI chromatograms for the standard sample (1) and the extracts from the model hair shampoo (2) (a) grade ; (b) grade ; (c) grade ; (d) grade (Concentration : 0.1) 1) K. Ohbu, O. Hiraishi, I. Kashiwa : J. Am. Oil Chem. Soc., 59, 108 (1982). 2),,, : 43 SCCJ, p. 31 (1998). 3) E. D. Goddard, R. B. Hannan : J. Am. Oil Chem. Soc., 54, 561 (1977). 4),,, : 6, p. 153 (2001). 5),,, : (Bunseki Kagaku), 53, 1119 (2004). 6) A. J. Senzel : Newburger s manual of Cosmetic Analysis, 2nd Ed., p. 53 (1977). 7) R. F. Schubert, P. H. Ko : J. Soc. Cosmet. Chem., 23, 887 (1972). 8) D. H. Kirby : Cosmet. Perfum., 90 (8), 19 (1975). 9) :,, (1995), (). 10) : ( 3 ),,

6 100 BUNSEKI KAGAKU Vol , (1995). 11), :, (1984), (). 12) : SEPARATION REPORT, No ) :, 4, (1994), (). 14) :, 1, (2000), (CMC ). CC SEC-MALLS-RI CC CC CC CC CC CC SEC CC CC CC CC CC CC CC