Surfactants Does hydrophobe branching make a surfactant more or less hydrophilic? Dr Ingegard Johansson of Akzo Nobel Surface Chemistry explains the complex chemistry behind some new products
he hydrophobic-hydrophilic question came up in our
search for new and efficient hydrophobic raw materials 70 Tfor surfactants. It was known that branching with defined BrC broad branches like the Guerbet type gives good environmental prop- 10 65 BrC narr erties, such as lower aquatic toxicity and easy biodegradation, 10 1D broad and one would also expect it to lead to low foaming and good 60 Berol OX cleaning performance. However, a detailed structure-perform- 1D narr ance knowledge was lacking. 55 We carried out an investigation which filled in that gap and, with further fine-tuning, gave rise to a couple of new members 50 of the Akzo Nobel product portfolio. An automatic titration technique was also developed for the characterisation of the 45
surfactants and surfactant blends. Area/hgrp (A2/molecule) 40 Physico-chemical studies A series of non-ionic surfactants was synthesised, based on dif- 35 ferent straight-chain or Guerbet-branched decyl alcohols. The hydrophilic part was ethylene oxide (EO) or glucose. For the EO 30 024681012 derivatives, the total amount of EO varied, as did the distribu- Ethylene oxide units tion, i.e. both broad and narrow. The glucosides were made with only one degree of polymerisation. Many of their physico-chemical properties were determined Figure 2 - Area per molecule at the air/water interface as a function of the average number of ethylene oxide units and some results are given here. More detail was given in a Note: Br C -broad/narrow- broad/narrow range ethoxylates of branched decyl alcohol, 1D broad/narr - ethoxylated straight chain decyl 1 10 paper at CESIO 2004 in Berlin. As shown in Figure 1, the alcohol with broad/narrow distribution, Berol OX91- commercial broad range ethoxylate from a C9-11 straight alcohol Critical Micelle Concentration (CMC) of the surfactants depends both on their branching and the type of distribution. Overall, the branched non-ionics have higher CMCs, intuitive- ly giving them a more hydrophilic nature. The packing of the surfactants at the interface, as reflected in area per molecule and surface tension at CMC, was determined BrC broad 10 from the surface tension versus concentration plot where the BrC narr 7,10E-03 10 break in the curve indicates the onset of the CMC. From the 1D broad 2 same curves the area per molecule (a0) can be deduced and 6,10E-03 1D narr Berol bx 91 the result is shown in Figure 2. The dominating feature is that BrC glucoside larger head groups simply need more space. 5,10E-03 10 1D glucoside Both the branching of the hydrophobe and the broadening of the EO distribution had an influence on adsorption. 4,10E-03 Surfactants with the same type of hydrophobe showed a simi-
3,10E-03 lar area per molecule at the air/water interface for small head groups. Branched hydrophobes are bulkier and need more 2,10E-03 space. Surfactants with the same type of EO distribution
critical micelle concentration (mole/l) showed similar a0 values for bigger head groups; in other 1,10E-03 words, the packing of the hydrophilic part at the interface determines their behaviour. 1,00E-04 Thus the influence of the hydrophobe was dominant for 024681012 smaller head groups and the hetero dispersity of the EO chain degree of polymerization was the dominant factor for larger head groups. This reflects the increase in the size of the head group relative to the Figure 1- CMCs of technical grade alcohol ethoxylates & alkyl polyglucosides as a function hydrophobe with increasing amounts of EO. It is obvious that of degree of polymerisation of the head group broad-range surfactants have smaller areas per molecule than
Note: Temperature = 21±1°C. Br C10 broad/narrow- broad/narrow range ethoxylates of branched decyl alcohol, 1D broad/narr - ethoxylated narrow-range surfactants. Most probably this is a result of the straight chain decyl alcohol with broad/narrow distribution, Berol OX91- commercial broad range ethoxylate from a C9-11 straight alcohol packing advantages of a broader EO distribution.
38 November 2004 Speciality Chemicals Magazine
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tension, contact angle, cloud point and foam. Here the first 38 group of properties would indicate a more hydrophilic nature, while the second group could be described as a more BrC broad 36 10 hydrophobic behaviour. Thus, no straight answer to the ques- BrC narr 10 tion put forward in the title of this paper has been found. 34 1D broad 1D narr Emulsion inversion as a tool 32 Another way of investigating differences between surfactants at 30 air/water or oil/water interfaces is looking at their actual behav- iour in mixtures of oil and water. This was done by mixing equal 28 amounts of oil and water under efficient stirring in the presence of 3% of the surfactant to be investigated, thus producing an
surface tension (mN/m) 26 emulsion. The nature of the emulsifier decides whether the 24 emulsion produced will be oil in water (O/W) or water in oil (O/W). Determining which is which is easy using a conduc- 22 tometer, since an O/W emulsion conducts electricity (is water continuous) while a W/O emulsion does not. 20 024681012 A complementary co-surfactant is titrated into the mixture Ethylene oxide units under continued efficient stirring, using automatic equipment from Scanalys, and the conductivity is measured continuously. The emulsion will then invert when a specific amount of the co- Figure 3 - Surface tension at the CMC as a function of the average number of EO units surfactant has been added. In our case, most of the surfactants were hydrophilic and Span-80, a hydrophobic mono-sorbitane Surface tension at or above CMC increased with increasing oleate, was chosen as co-surfactant. amounts of EO, except for the broad-range Guerbet alcohol- The interesting point comes when the emulsion inverts from based compounds (Figure 3). For the same type of hydrophobe one type to the other. The amount of co-surfactant that has in the surfactant, the smaller the head group the more surfac- been added at that point says something about how far off you tant adsorbs at the interface and the lower the surface tension. were from the start. A very hydrophilic surfactant (high HLB)
However, the special behaviour of the branched C10 broad- would need a more hydrophobic co-surfactant in order to invert range compounds is found also in the area/molecule graph. than a less hydrophilic one. Measuring and comparing the rel- The most striking feature is that the Guerbet alcohol-based ative co-surfactant part at the inversion point gives a scale of surfactants showed lower surface tension values, despite their hydrophilicity that can be compared to other characterisation relatively low adsorption compared to the straight-chain surfac- measures like HLB, phase inversion temperature (PIT)3 and sur- tants. Apparently, the branched surfactants form a more factant affinity difference (SAD)4. hydrophobic surfactant layer at the air/water interface. The rea- A typical run is shown in Figure 5, where the specific con- son for this might be found in the fact that the branch may be ductivity is found on the y-axes and the amounts of added co- positioned planar to the interface, while the rest of the surfac- surfactant on the x-axis. The inversion points were decided tant tails are positioned laterally to the interface. Therefore, the according to the procedure described in Figure 5. IPupper is branch reduces the contact between water and the air, result- determined as the breakpoint of a horizontal line through the ing in lower surface tensions for branched surfactants. maximum in the conductivity curve and a linear fit to the first
The change of the contact angle of a droplet of 0.25% sur- portion of the steep drop in conductivity. IPlower is the amount factant solution on Parafilm as a hydrophobic model surface of added surfactant in millilitres at the breakpoint of a horizon- was followed over time with a high-speed video camera. The values after 60 seconds are shown in Figure 4, measured against amounts of EO. 65 BrC broad Contact angles as a measure of wetting capacity are impor- 10 BrC10 narr tant in many practical uses for surfactants, such as cleaning hard 60 1D broad water 1D narr surfaces, spreading formulations on hydrophobic surfaces like 55 Berol OX 91 )
leaves and so forth. Surfactants with a higher amount of EO ° show higher contact angles, which is intuitively natural, since 50 they are more hydrophilic and thus less prone to adsorb at the hydrophobic surface. 45
Narrow range 1-decanol-based surfactants showed a larger contact angle ( 1-decanol 40 contact angle than similar Guerbet C10 alcohol-based surfac- tants. This observation corresponds well with the observed 35 trend in the surface tension at the CMC. It is also in line with 30 the fact that the contact angle of neat C10 Guerbet alcohol on Parafilm is smaller than the contact angle of neat 1-decanol. 25 Broad range surfactants with
Speciality Chemicals Magazine November 2004 39
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alent HLB (EHLB) from the results for the isomerically pure
C10 E5, C10 E7 and C10 E8 for which the HLBs can be calculated lp upper according to Griffin.The equation obtained in this manner pro- vides a way to determine the EHLB number of any (mixture of) surfactant(s) once its inversion point in the same system (i.e. the 1. 6 same temperature, pressure and type of oil) is established.
Conclusions Technical ethoxylates from Guerbet alcohols contain higher amounts of unreacted alcohol and show hydrophilic shifts like 0.8 higher CMCs and larger areas per molecule at the air/water inter- face, but also hydrophobic shifts like lower surface tension, lower conductivity (mS/cm) cloud points, less foam, lower contact angles against hydrophobic lp lower surfaces and lower inversion points in emulsion systems. 0.0 Technical grade C10 E
References 1. I. Johansson & I. Voets, About Characterisation of Surfactants 1D gluc 50% pure C10 Outside the HLB-system, Proceedings of the 6th World Surfactants 45% 1D broad Congress, CESIO 2004, Berlin pure C10 2. B.Jonsson, B.Lindman, K.Holmberg & B.Kronberg, Surfactants & 40% BrC10 broad BrC10 narr Polymers in Aqueous Solution, Wiley & Sons, Chichester 1998, chap- 35% pure C10 ter 12 30% BrC10 broad 1D narr 3. K. Shinoda & S. Friberg, Emulsions & Solubilisation, Wiley, New York 25% 1986 20% BrC10 gluc 4. M. Pérez, N. Zambrano, M. Ramirez, E. Tyrode, & J. Salager, J. BrC10 narr Dispersion Science & Technology 2002, 23(1-3), 55-63 15 % 1D broad 10 % dp 5% ratio Span-80 to total surfactant (w%) BrC10 narr For more information, please contact: 0% Dr Ingegard Johansson 02468Akzo Nobel Surface Chemistry AB S-44485 Stenungsund Sweden Figure 6 - Inversion points for the whole group of surfactants as a function of the degree of Tel: +46 303 85108 polymerisationFinally, the average (amount of the of EOtwo or inversion glucose) point values can be E-mail: [email protected] taken as the inversion point and used to extrapolate an equiv-
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