Synthesis and Surface Activity of Cashew-Based Anion-Nonionic Surfactants

doi:10.4236/ojapps.2012.22012

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Open Journal of Applied Sciences, 2012, 2, 93-97

doi:10.4236/ojapps.2012.22012 Published Online June 2012 (http://www.SciRP.org/journal/ojapps)

Synthesis and Surface Activity of Cashew-Based

Anion-Nonionic Surfactants

Haiyan Li1, Jun Wang1*, Cha ng h ua n Li u1, Jun Han2, Cuiqin Li1, Mengmeng Ning1

1College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing, China

2Jinzhou Engineering Technology Department of Liaohe Oilfield Company, Jinzhou, China

Email: *[email protected]

Received April 13, 2012; revised May 14, 2012; accepted May 23, 2012

ABSTRACT

Four novel anion-nonionic surfactants were synthesized using cashew phenol as raw material. The four structures were

characterized by IR and elemental analysis. Their surface activities were investigated. Their critical micelle concentra-

tions (CMC) are 9.30 × 10–3 mol/L, 8.50 × 10–3 mol/L, 8.10 × 10–3 mol/L and 7.71 × 10–3 mol/L respectively, and the

corresponding surface tensions at CMC are 28.38 mN/m, 28.60 mN/m, 30.40 mN/m and 30.00 mN/m respectively. The

contact angles of the solutions on sheet galsses were measured to observe their surface wettabilities. The effects of their

concentrations, the concentrations of NaCl and temperature on their foaming capacity and foam stability were studied.

Keywords: Cashew Phenol; Anion-Nonionic Surfactant; Surface Activity; CMC

1. Introduction

Anionic surfactants are easy to generate precipitation so

as to lose surface activity in high salinity formation water,

and nonionic surfactants are difficult to dissolve when

temperature exceeds the cloud point. But anion-nonionic

surfactants can overcome the weaknesses of the single

anionic or nonionic surfactants and apply to the reservoir

conditions of high salinity and high temperature [1,2].

Cashew phenol is cheap, green and easy to get in na-

ture, so the surfactants synthesized by cashew phenol

have better ecological performance and accord with the

demand of “green raw materials” of green surfactants.

There are no reports on anion-nonionic surfactants with

cashew phenol as starting material till now.

In the present study, we prepared a series of novel

surfactants-cashew phenol polyoxyethylene-carboxylates

modified anion-nonionic surfactants containing nonionic

and anionic hydrophilic moieties and investigated their

properties. In this paper, we report the surface activities

of theses surfactants, including their surface tension,

wetting and foaming properties, and they exhibit surface

activities similar to those of traditional surfactants [3].

2. Materials and Methods

2.1. Materials

Cashew phenol was supplied by Shanghai Meidong Bio-

logical Material Co., Ltd. in commercial grade. Ethylene

oxide was supplied Liaoyang Petrochemical Company in

commercial grade. Chloroacetic acid, sodium hydroxide,

potassium hydroxide and acetone, purchased from Tian-

jin Damao chemical reagent factory, were of analysis

grade.

2.2. Preparation of Cashew Phenol

Polyoxyethylene-Carboxylates Modified

Anion-Nonionic Surfactants

We obtained novel surfactants possessing anion-nonionic

structures through a three-step process (shown in Scheme

1) [4]. In the first step, a series of polyoxyethylene ethers

presenting hydrophilic ethylene oxide chain segments at

phenolic hydroxyl were obtained through ring-opening

polymerizations of cashew phenol with ethylene oxide in

the presence of potassium hydroxide as a catalyst. In the

second step, these polyoxyethylene ethers and chloroace-

tic acid were reacted with sodium hydroxide. The third

step was nucleophilic substitution reaction. The following

description is typical of the procedures used to prepare

the anion-nonionic surfactants: cashew phenol (0.5 mol),

ethylene oxide (4 mol, 5 mol, 6 mol, 7 mol respectively),

and potassium hydroxide (catalyst, 1g) was stirred me-

chanically and heated to 120˚C - 140˚C under the pressure

of 0.25 ± 0.05 MPa. Polyoxyethylene ether (0.02 mol,

13.04 g, 14.8 g, 16.56 g, 18.32 g), chloroacetic acid (3.78 g),

and sodium hydroxide (6.4 g) was stirred magnetically

and heated 30˚C for 1h, and then heated 60˚C for 4.5 h

under the pressure of 5.32 ± 0.05 KPa. The sodium salts

of the products were washed with acetone. Compounds A,

*Corresponding author.

H. Y. LI ET AL.

B, C and D possess 8, 10, 12 and 14 ethylene oxide units,

respectively (as depicted in Scheme 1).

Step.1: ring-opening polymerization

Step.2: alkalization reaction

Step.3: nucleophilic substitution reaction

Scheme 1. Synthesis of anion-nonionic surfactants A, B, C

and D.

2.3. Analysis

The structures of the final products were confirmed

through infrared (IR) and elemental analysis. IR spectra

recorded in the range 4000 - 600 cm–1 were obtained us-

ing a Japan Spectroscopic FT/IR–3 spectrometer. The ma-

terials were ground with KBr and smeared onto pellets.

Elemental analysis datas were obtained using a Germany

Heraeus Elemental Analyzer.

2.4. Measurements

Surface tensions were determined by Hanging Drop

Method using a JC2002CI surface tensiometer. and the

temperature was maintained precisely at 25˚C. Contact

angles were measured using a JC2002CI intravenous drip

contact angle meter. The foaming properties were deter-

mined using the Ross-Miles method and the temperature

was maintained precisely at 45˚C except the temperature

effect. The foaming capacity was measured in terms of

the height of the foam produced initially; the foam stabil-

ity was measured in terms of the height after 5 min.

3. Results and Discussion

3.1. Preparation of Cashew Phenol

Polyoxyethylene-Carboxylates Modified

Anion-Nonionic Surfactants

The four structures were confirmed through IR and ele-

mental analysis (the results are shown in Table 1). The

IR spectra display bands at 3000-3010 (ph-H),

1715-1760(C=O),1680-1620(-CH=CH-),1340-1380(CH3),

1210-1275(-O -),110 -1225(-CH 2CH2O-),750-810(p h-H),7

25-780(CH2) [5].

3.2. Surface Tension

Figure 1 shows plots of the surface tensions vs molar

concentrations of anion-nonionic surfactants A, B, C and

D. CMC values of each surfactant given according to the

intersection points of the extension of the straight part of

both sides of turning point in Figure 1 are shown in Ta-

ble 2 [6,7]. An increase in the length of the polyoxye-

thylene chain of the nonionic portion resulted in a de-

crease in the surface activity. This phenomenon is related

to the increased hydrophilicity decreasing the concentra-

tion of the surfactants at the surface [8].

3.3. Wetting Power

Surface tension of water is larger in the common liquid

and it can not be wetting and spreading on the glass sur-

face, after adding surfactant the surface tension of water

Table 1. Elemental analysis of cashew phenol polyoxyethylene-

carboxylates modified anion-nonionic surfactants (F:Found

C: Calculated).

Elemental analysis

C (%) H (%) O (%)

CompoundsUnits of EO

F C F C F C

A 8 63.9364.36 8.88 9.33 24.0424.39

B 10 62.3960.15 8.90 8.72 25.3727.69

C 12 62.1160.79 8.92 8.89 26.4328.15

D 14 61.4560.84 8.94 9.02 27.3128.69

H. Y. LI ET AL. 95

Figure 1. Surface tensions of A, B, C and D in aqueous so-

lution at 25˚C.

Table 2. CMC values and surface te nsions of anion-nonionic

surfactants at 25˚C.

R A B C D

CMC (mmol/L) 9.30 8.50 8.10 7.71

γCMC (mN/m) 28.38 28.60 30.40 30.00

can significantly reduce, but also may reduce the solid-

liquid interfacial tension, so that it can be spontaneous

re-spread on the glass surface [9]. Usually strong hydro-

philic surfactant has good wetting, and therefore the

contact angle can be measured in aqueous solution of

surfactant on the glass slide to respond to its wettability.

Figure 2 shows the contact angles formed beween

surfactant solutions and glass slide vs concentrations of

the four surfactants. The smaller contact angles observed

for the solutions containing the surfactants, compared

with that of water alone, indicate that these compounds

possess wetting power on the glass slide. With their con-

centrations increased, the contact angles decreased. When

their concentrations exceeded 5000 mg/L, they almost

kept the values and behaved the most effective wet ability.

3.4. Foaming Properties

Tables 3-6 lists the foam properties of four anion-non-

ionic surfactants. Table 3 indicated that with the concen-

trations of the four products increased, the foaming ca-

pacity (measured in terms of the height of foam initially

produced) and foam stability (measured in terms of the

height after 5 min) of them increased. After reaching a

certain degree, they kept the value all long [10-12].

When adsorbing in the gas-liquid interface, the hydration

of the hydrophilic EO chain in molecules makes the hy-

drophilic groups of the surface form the inter-molecular

hydrogen bonding or cross-cut in order to wind each

other so that surface film has a certain strength, so the

products have a foaming ability and foam stability. With

the increase of their concentrations, the concentration of

hydrophilic EO groups increased, the foaming capacity

and foam stability gradually increased, but when the

concentration reached a certain degree, the hydrophobic

of EO chain started to pick up, so foaming capacity and

foam stability were almost no change.

Table 4 indicated that with temperature increased, the

foaming capacity and foam stability decreased. This was

mainly due to the increase of temperature, liquid viscos-

ity and surface viscosity dropped and the foam evapora-

tion rate and inter-bubble gas diffusion rate increased,

and therefore the decay process of foam accelerated, so

the foaming capacity and foam stability decreased.

Figure 2. Contact angles of A, B, C and D in aqueous solution

at 25˚C.

Table 3. The effect of the concentrations of the four surfactants

on their foaming properties.

C/gL–1 3 4 5 6 7 8

H0min/cm10.5 10.6 10.8 11.0 11.3 11.3

H5min/cm8.0 8.3 8.5 9.0 9.0 9.0

H0min/cm12.5 12.8 13.0 13.8 14.0 13.8

H5min/cm11.0 11.5 11.8 12.0 12.0 12.1

H0min/cm13.0 13.3 13.5 13.8 14.0 14.0

H5min/cm12.0 12.3 12.8 12.9 13.0 13.0

H0min/cm12.0 13.8 14.3 14.3 14.3 14.3

H5min/cm10.3 11.8 12.5 12.8 12.5 12.5

H. Y. LI ET AL.

Table 5 indicated that with the concentrations of NaCl

increased, the foaming capacity and foam stability in-

creased at first and then decreased. This was mainly be-

cause on the one hand, after adding electrolyte, ionic

atmosphere and the thickness of diffuse double layer of

the surfactant ionomers were compressed, and therefore

decreased the repulsion between them, so that surfactant

ions more quickly adsorbed on the surface to form mi-

celles; and with the Na+ concentration increased, more

Na+ into the ionic fog, micelles and adsorption layers, the

formation of the surface micelles speeded up, so that γ,

cmc decreased. In general, the lower γ and the smaller

cmc, the more easily bubble and the more stable foam.

On the other hand, NaCl reached a certain concentration,

diffuse double layer of the membrane was compressed,

and reduced repulsion between the membrane and accel-

erated the discharge fluid process. Therefore, NaCl addi-

tion of a small amount, will help improve the foam per-

formance of the products.

Table 6 indicated that with the concentrations of Ca2+,

Mg2+ increased, the foaming capacity and foam stability

Table 4. The effect of temperature on foaming properties of

the four surfactants.

Temperature/˚C 25 35 45 55 65

A H0min/cm 11 10.7 10.6 10.1 10

5min/cm 8.6 8.5 8.3 7.5 6.4

B H0min/cm 12.8 12.6 12.5 12 11.8

5min/cm 11.3 11.1 11.0 9.8 7.6

C H0min/cm 13.3 13.4 13.0 12 11.1

5min/cm 12.5 12.5 12.0 9.9 8.3

D H0min/cm 14.3 13.9 13.8 13.3 12.7

5min/cm 11.9 11.8 11.3 10.7 8.1

Table 5. The effect of the concentrations of NaCl on foaming

properties of the four surfactants.

W(NaCl)/% 0 0.5 1.0 2.0 3.0 4.0 5.0

A H0min/cm 10.6 11.5 12.312.3 11.9 10.35.9

5min/cm 8.3 9.0 10.09.6 9.5 7.0 3.0

B H0min/cm 12.5 12.5 13.5 13.2 13.0 12.3 12.0

5min/cm 11.0 11.0 11.411.3 11.0 10.39.5

C H0min/cm 13.0 13.5 12.3 11.9 11.9 11.8 11.3

5min/cm 12.0 12.2 8.88.8 8.7 8.57.8

D H0min/cm 13.8 14.0 11.811.5 11.3 10.8 10.6

5min/cm 11.3 11.5 5.55.5 5.5 4.54.3

Table 6. The effect of the concentrations of Ca2+, Mg2+ on

foaming properties of the four surfactants.

w(Ca2+, Mg2+)/10–6 0 0.51.0 2.0 3.0 4.05.0

0min/cm 10.610.610.5 10.4 10.1 9.89.5

5min/cm 8.38.38.1 8.0 7.9 7.97.8

0min/cm 12.5 12.5 12.3 12.3 12.2 12.0 11.5

5min/cm 11.011.010.3 9.5 9.5 9.59.0

0min/cm 13.0 12.3 12.2 11.9 11.8 11.6 10.9

5min/cm 12.010.910.7 10.7 10.4 108.8

0min/cm 13.8 12.9 12.5 12.2 11.5 11.2 10.8

5min/cm 11.3 10.7 10.7 10.6 10.5 10.39.3

decreased. This was because, from the molecular struc-

ture -CH2COO- possessed poor resistance to hard water,

when encountering Ca2+, Mg2+, easily generated curd-

like material, and therefore affected the foam properties.

4. Conclusion

We prepared a series of novel cashew phenol polyoxye-

thylene-carboxylates modified anion-nonionic surfactants

through ring-opening polymerization, alkalizetion reac-

tion and nucleophilic substitution reaction. Because of

the unique structural features resulting from the presence

of ethylene oxide and carboxylic hydrophilic groups in a

single molecule, the auxiliaries exhibit good surface ac-

tivities, including low-surface tension, well-foaming and

wetting.

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