POLY(GLYCERYL) ALKYL ETHER SURFACTANTS 423 Glycidol {y)used in fhe synfhesis 12 0 2 4 6 8 I0 I I I I I 0 Ri2TxGy {Ri23yTGy} [] RisTxGy (Ri83yTGy} -30 -24 -18 -12 -6 0 I I I I I 0 2 4 6 8 I0 12 Glyceryl group {y)in RnTxGy Figure 3. Average moles of x and y in poly(oxytetramethylene) (x) poly(glyceryl) (y) alkyl ether (RnTxOy Rn3yTGy) synthesized from fatty alcohol (1 mol), THF (3y mol), and glycidol (y mol). or Rt2TxGy/H2 ¸ system. This mesomorphic characteristic may be due to the branching of the hydrophilic group. Values of HLB, cloud point, and critical micellization concentration (cmc) of Tt2T3.204. o are listed in Table I. Cmc was taken as the concentration at the point of intersection of the two linear lines of the •/-1og C plots. For comparison, the values of R12EO 6 from the literature are listed (21-23). Since the HLB-value and cloud point of R•2T3.204. o are higher than those of R•2EO6, it is evident that R•2T2.3G4. o is more hydrophilic than Rt2EO 6. However, the cmc of R•2T3.204. o is lower than that of R•2EO 6. Cmc values show an increase with an increase in the hydrophilicity (24). The cmc value of R•2T3.204. o indicates that RnTxGy has a sufficient aggregation ability in aqueous media.

424 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS IOO 80 • 40 oe0 i i i I -.o-o---o w+s 0 I I I 0 0.2 0.4 0.6 Wafer wt. fraction I 0.8 .0 RmTh2G2.1 'W + D'• • LC,• W+LC•j I I I I 0.2 0.4 O.G 0.8 0 1.0 Water wt. fraction R•2EO 4 Figure 4. Phase diagrams of (a) R•2Tz,2G 2 z/H20 and (b) Rz2EO4/H20 (16) systems. HLB VALUES OF RnTxGy The HLB-values of R•2TxGy, R•8TxGy , Rt2EOx, and R•8EO X are shown in Figure 7. The HLB-values of the R•2TxGy and the Rt8TxGy series increase from 7 to 30 with increasing numbers of glycerol groups (y). On the other hand, the HLB values of the R•2EOx and the R•8EO x series change from 8 to 21. The HLB value of the POE-type nonionic surfactant cannot exceed 20, according to Griffin's equation (21). The fact that the HLB-value of R,EOx was under about 20 was confirmed by phase inversion emulsi- fication. R,TxGy may be the first nonionic surfactant with an HLB value exceeding 20. We believe that the high HLB value of R,TxGy results from the large number of hy- droxyl groups present. IOO 80 • 6o o 40 t_ E • 20 i i i ! •c ic c t.c o o w+s o-.... w +1 s•-O--•)•.•_c• • 0 0.2 0.4 0.6 0.8 I.O 0.2 0.4 0.6 0.8 Water wt. fraction Ri2T2.2G3j (bJ Water wt. fraction RizT3.264.0 Figure 5. Phase diagrams of (a) R•2T2.2G3.z/H20 and (b) Rz2T3.2G4.o/H20 systems.