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Abstract: In this paper, polyisobutylene succinic anhydride adduct (PIB-SA) was modi®ed by esteri-
®cation with polyethylene glycol (PEG 600, 1000 and 2000) to obtain mono- and diterminal polyoxy-
alkynated PIB-SA. The monoterminal products were reacted with pentamethylene-hexamine
(PMHA). The structures were con®rmed by FT±IR and 1H NMR analysis. The surface properties,
interfacial tension and the effectiveness in oil dispersion of the synthesized polymeric surfactants are
reported. The maximum ef®ciency of oil spill dispersants was reached when the surfactant molecule
had two moities (polyoxyalkylene and polyamine units).
# 1999 Society of Chemical Industry
Keywords: polymeric surfactants; dispersants; oil spill dispersants; effectiveness of dispersants; water-based
dispersants
* Correspondence to: Ahmed M Al-Sabagh, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
(Received 12 November 1998; accepted 22 May 1999)
product of I with PEG 600 and amide derivatives of product I. The appearance of new peaks at 5 ppm,
PIB-SA45 are presented in Fig 3 (a and b respec- 2.9 ppm and 2.1 ppm in Fig 3(b), which represent
tively). The disappearance of this peak above 10 ppm, amide ÐNH proton, CH2 proton in PMHA and NH2
which relates to hydrogen proton for ÐCOOH in the amine protons respectively, indicates the amidation of
MA group, in the spectra of two compounds indicates I with PMHA. Moreover, the presence of the strong
the complete esteri®cation and amidation of product I. band at 3.5 ppm in both spectra, which represents
The observed peaks at 0.98 ppm and 1.4 ppm, repre- CH2 proton in PEG, indicates the formation of
senting methyl protons and methylene protons in PIB esteri®ed products of I with PEG.15
respectively, can be used to illustrate the structure of The hydrophile±lipophile balance (HLB), surface
Ras Budran
asphaltenic Umbaraka
Speci®cation Method crude waxy crude
Figure 3. 1H NMR spectra of (a) PIB-SA (eo 13) and (b) amide derivatives
of PIB-SA (eo 45).
ef®ciency (70%) at DOR from 1:20 to 1:10 whilst D1 and D4 were 32%, and 63%, respectively at 1:40
exhibits the minimum ef®ciency (50%) at DOR 1:40. DOR.
The dispersion ef®ciencies for D2, D3 and D4 are 58%, The dispersion ef®ciency of D1 to D5 on the waxy
49% and 64% at DOR 1:20, 1:40 and 1:40, re- crude oil is illustrated in Fig 5. The values of WSL
spectively. From the data presented in Fig 4 D1 and D5 percentages at DOR 1:40 are 70%, 63%, 45%, 80%
were selected to investigate the role of interfacial and 90% for D1 to D5, respectively. This observation
tension in its dispersion capability. The interfacial indicates a good dispersion effectiveness of D1 to D5
tension data are plotted for D5 and D1, as shown in Fig on waxy crude. The wide difference in the dispersion
4, against DOR. It was observed that the dispersability capability of D1 to D5 for waxy and asphaltenic crude
for D5 and D1 increases with decreasing interfacial may be due to the large differences in chemical
tension. The effect of polyethylene oxide units (n) on composition between the two crude oils.17 This means
the dispersability of D1, D3 and D5 is observed in Fig that the ethoxylated and aminated PIB are more
4. In this respect, increasing (n) increases dispers- compatible with waxy than asphaltenic crudes.
ability. Moreover, the effect of PMHA on the dis-
persability of D2 is noticed from the increase in WSL Dispersion capability of a blend of two non-ionic
percentage from 54% for D1 to 57% at 1:20 DOR. On surfactants
the other hand, the increasing of (n) in the presence of Hydrophile±lipophile balance, HLB, and the chemical
PMHA increases the dispersion capability of D2 and structure of the surfactants exert a large in¯uence on
D4, as shown in Fig 4. The WSL percentages for D2 the rate of coalescence of emulsions containing blends
of non-ionic surfactants. The best stability is obtained hydrocarbon chains is increased by their proximity.18
by mixing surfactants which vary in HLB values.18±20 The most effective non-ionic surfactant blends, as
In order to estimate the validity of this observation shown in Fig 6, appear to be good with an HLB of
with asphaltenic crude oil dispersions D5 was selected 8±10, these having long hydrophobic chains and long
(HLB = 17.6) due to its good dispersability. The D5 is polyoxyethylene chains. So the maximum dispersion
blended in pairs with sorbitan mono, di- and trioleate power can be arranged in sequence D5 sorbitan
in proportions giving a resultant HLB range from 12 to trioleate > D5 sorbitan dioleate > D5 sorbitan
16. The blends were tested by WSL at ®xed DOR 1:30 monooleate. Under these conditions the interfacial
and the results are shown in Fig 6. tension is generally quite low and the surface viscosity
A real improvement in the percentage of dispersed is high since these long chains add rigidity to the
oil is observed for the blends when compared with the interface, making it more gel-like.18
individual D5 performances. The maximum WSL The screen test, ST, was used as a technique in this
ef®ciency of D5 is 70%, as shown in Fig 4, where the investigation to support the data obtained from WSL.
values reached were from 90 to 100% for blends, as Figure 7 shows the effectiveness from ST against DOR
shown in Fig 6. The interactions between D5 and for D5 and their blends on asphaltenic crude. The data
sorbitan trioleate are favourable to the interface obtained from ST, as shown in Fig 7, agree with those
stabilization and give a quite good dispersion test, as exhibited by using WSL as is shown in Fig 6. In all
shown in Fig 6, since the repulsion between sorbitan cases of blends, interfacial tensions (g) were measured
rings is minimized and the attraction between the and are shown in Fig 8. The lowering of g and the
improved stability of O/W emulsions combining sur- 3 Mackoy D, Chau A, Hossain K and Bobra M, In Oil Spill
factants with high and low HLB have been explained Chemical Dispersants Research Experience and Recommendations,
STP 840, Ed by Allen TE, ASTM, Philadelphia. pp 38±54
on the basis of some speci®c molecular association of
(1984).
surfactants at the interfaces.18,21 The minimum 4 Preston WC, J Phys Colloid Chem, 52:84 (1948).
interfacial tensions of blends against asphaltenic crude 5 Ginn ME and Haris JC, J Am Oil Chemists Soc, 38:605 (1961).
oil (Fig 8) are obtained at the HLB range from 8 to 10. 6 Shinoda K, J Phys. Chem, 58:1136 (1954).
This may give indirect evidence that the HLB and 7 Brochu C, Pelletier E, Caron G and Desnoyers JE, Dispersion of
interfacial tension are linked in the same way by their crude oil in sea water. The role of synthetic surfactants, Oil and
dispersion capability. Chemical Pollut, 3:2567±279 (1986/87).
8 Wells PGS, Abernethy and Mackay D, Acute toxicity of solvents
and surfactants of dispersants to two crustaceans, in 8th Annual
Arctic Marine Oil Spill Program Technical Seminar Ottawa,
CONCLUSIONS
Environment, Canada. pp 228±240 (1985).
The following conclusions are drawn from the present 9 Brit Pat 1 361 179 (1974).
investigation: 10 Belg Pat 886 656 (1975).
11 Fr Pat 2 479 251 (1980).
(1) Polyisobutylene succinic anhydride adduct, PIB-
12 Morris PR and Martinelli F, A speci®cation for oil spill
SA, can be converted to water-soluble polymeric dispersants, Warren Spring Laboratory Report, LR 448 (OP)
surfactants having different HLB by varying the (1983).
relative molar mass of the grafted PEG. 13 Canevari GP, Development of the next generation of chemical
(2) The dispersion ef®ciency of the prepared surfac- dispersants, in Proceed 1973 Conf Prevention Control Oil Spills,
tants on asphaltenic crudes increases with increas- API, Washington, DC. pp 231±240 (1973).
ing relative molar mass of the PEG used for 14 Quirion F and Desnoyers JE, Effects of alcohol and surfactants
on the lowering of the interfacial tension between water and
grafting.
benzene, a correlation with phase diagrams. AOSTRA J Res
(3) The ethoxylated aminated PIB-SA gives good 1:121±126 (1984).
dispersion capability with waxy crude oil. 15 Johansson M, Trollsas M and Hult A, J Polym Sci Part A: Polym
(4) The blending of sorbitan trioleate with the pre- Chem, 30:2203 (1992).
pared surfactants increases dispersion ef®ciency to 16 Youssed AM, Gendy JS, Mohamad AI and Barakat Y, British
about 100%. Polymer Journal 22:339±346 (1990).
17 Ismail M, El-Gamal and Al-Sabagh AM, Fuel 75(6):743±750
(1996).
18 Boyd J, Parkinson C and Sherman PJ, Colloid Interface Sci
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