Accepted Manuscript

Title: Adsorption behavior of branched polyoxyethylene ether

carboxylate surfactants

Authors: Qinghong Zhang, Yunling Li, Yongbo Song, Jun Li,

Zhifei Wang

PII: S0927-7757(17)30879-8
DOI: https://doi.org/10.1016/j.colsurfa.2017.09.050
Reference: COLSUA 21953

To appear in: Colloids and Surfaces A: Physicochem. Eng. Aspects

Received date: 21-8-2017

Revised date: 26-9-2017
Accepted date: 26-9-2017

Please cite this article as: Qinghong Zhang, Yunling Li, Yongbo Song,
Jun Li, Zhifei Wang, Adsorption behavior of branched polyoxyethylene ether
carboxylate surfactants, Colloids and Surfaces A: Physicochemical and Engineering
Aspects https://doi.org/10.1016/j.colsurfa.2017.09.050

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Adsorption behavior of branched polyoxyethylene ether carboxylate
surfactants

Qinghong Zhang, Yunling Li*, Yongbo Song, Jun Li and Zhifei Wang

China Research Institute of Daily Chemical Industry, Taiyuan 030001, P. R. China

Graphical abstract
air

Branched chain
Hydrogen
Hydrophilic head bond
with -COOH water
COOH HOOC 1s

air

Branched chain
Electrostatic
Hydrophilic head repulsion
with -COONa
COO- COO- 1s water


Author to whom correspondence should be addressed, E-mail: lyunl0068@sina.com.

Tel: +86-351-4046827. Fax: +86-351-4040802.

Address: 34# Wenyuan Str. Taiyuan, Shanxi Province P. R. China: 030001

Abstract: In our work, branched anionic surfactant (3, 5, 7-trimethyl decanol

polyoxyethylene ether carboxylate (A13EC5-Na)) has been successfully synthesized

and characterized by fourier transform infrared (FT-IR) spectra. Static equilibrium

surface tension, contact angle and dynamic surface tension of alcohol ether carboxylic

acid (A13EC5-H), alcohol ether carboxylate (A13EC5-Na) and linear chain carboxylate

(A12EC5-Na, as comparison) were investigated to study their spreading and adsorption

behaviors. Electrolyte tolerance of anionic surfactants (A13EC5-Na and A12EC5-Na)

was also studied to explore the application in enhanced oil recovery. The results
indicated that critical micelle concentration (CMC) and minimum area per molecule

(A0) are the lowest and the surface excess concentration (m) is the highest for

nonionic surfactants (A13EC5-H). A13EC5-Na can decrease the surface tension of

water to 27.43 mN/m. Due to the introduction of branched chains, m of A13EC5-Na

is smaller than that of A12EC5-Na. And the adsorption efficiency and the efficiency of

forming micelles of A13EC5-Na molecules are superior to that of A12EC5-Na. By

contact angle and dynamic surface tension measurements, we can know that for

branched products, the wetting ability is stronger, diffusion rate to the interface is faster

and the time of surface tension reaching equilibrium is shorter. The adsorption process

of A13EC5-Na is diffusion controlled, while the adsorption process of A12EC5-Na is

mixed diffusion-kinetic adsorption mechanism. CaCl2 tolerance of A13EC5-Na is

stronger than that of A12EC5-Na but NaCl tolerance of A12EC5-Na is stronger.

Key words: branched anionic surfactants; spreading; adsorption behaviors; diffusion.

1. Introduction

Surfactants are indispensable components in laundry, cosmetics and household

cleaning products, accounting for 15%-40% in total detergent formulation [1].

Anionic surfactants are especially important which have the ration of 60% in the

world production [2]. Exploring low surface energy surfactants has attracted much

attention due to their applications in printing, painting, emulsification/suspension used

in cosmetics and medicines and washing etc. [3-5]. It is reported that chain branching

can lead to lower surface tensions (γcmc) in comparison with linear analogues [6-9].

Mohamed et al. [10] studied short branched hydrocarbon surfactants like the trichain

(TC14) can obtain surface energy of 27 mN/m which is said to be low for

hydrocarbon surfactants and comparable to a fluorocarbon surfactant DiHCF4 (γcmc =

26.8 mN/m) [11,12]. Zhang et al. [13] synthesized a series of polyoxyethylene alkyl

ether carboxylates then investigated their properties, and they raised that the
introduction of branching in the hydrocarbon chain contributes to higher surface

activity and higher foam volume than linear chain surfactants. Alexander et al. [14]

also concluded that branched hydrophobic chain anionic surfactants can decrease the

surface tension of water to 24-27 mN/m. These values can match by a certain

fluorocarbon surfactant with serious environmental issues. So the study of branched

chain surfactants is of great significance.

Wetting ability on low energy solid surface is crucial in our daily life and some

industrial applications [15-17]. As is known to us all, wetting on the solid surface of

water is difficult, so surfactants are generally used to improve the wettability of water

on solid surface by changing the surface tension of water. There are many literatures

about the study of various wetting. Liu et al. [18] studied wetting behavior on paraffin

film of anionic-nonionic surfactants with different ionic headgroups (carboxylate,

sulfonate and sulfate) and they concluded the surface activity and spreading ability of

the three surfactants decrease in the order AE3C > AE3S > AE3SO. Chang et al. [19]

proposed the adsorption on solid surface polytetrafluoroethylene (PTFE) would rely

on hydrophobic interaction and the van der Waals force. But Paraffin is a

petroleum-based alkane mixture, which makes its surface hydrophobic. Nascimento

[20] investigated five nonionic surfactants with different oxyethene (EO) number to

evaluate their wettability and they found with the increasing of EO number, their

wettability on paraffin showed a drop. It is quite interesting to study wetting behavior

of surfactants.

Now anionic surfactants have attracted considerable interest due to their

excellent performance at water-solubility, low Krafft point, high salinity and

temperature tolerance. They generally contain two hydrophilic groups: nonionic

hydrophilic groups (polyethylene oxides groups) and anionic hydrophilic groups

(carboxylate group, sulfonic group and sulfate group) which make them possess

characteristics of both anionic and nonionic surfactants. And there are a great deal of

studies on fat alcohol ether sulfates (AES) [21-23]. Alkyl polyoxyethylene ether
carboxylates are also a kind of anionic-nonionic surfactant whose terminal group is -

COOH. They show high surface activity, excellent biodegradability and salt resistance

[24]. Many papers were mainly focused on the application performances and surface

properties of alcohol ether carboxylates [25-27].

In the present work, branched alkyl polyoxyethylene ether carboxylates (3, 5,

7-trimethyl decanol polyoxyethylene ether carboxylates (A13EC5-Na)) have been

synthesized by one step oxidation. The structures of raw material A13EO5 and

synthesized product A13EC5-Na are displayed in Scheme 1. The static surface tension,

dynamic surface tension, dynamic wetting ability on the parafilm of different

concentration A13EC5-H, A13EC5-Na and A12EC5-Na solutions (A12EC5-Na as

comparison) were investigated to explore the spreading and adsorption of surfactant

solutions at air/water interface. What’s more, their electrolyte tolerance was also

tested in the paper.

O OH A13EO5
O
4

O ONa
A13EC5-Na
O
4 O

Scheme 1. The structures of raw material (A13EO5) and synthesized product

(A13EC5-Na).

2. Experimental section

2.1. Chemicals and materials

Branched alcohol polyoxyethylene ether (A13EO5, hydroxyl value = 128.86,

averaged molecular weight = 435.37) with purity higher than 99% was obtained from

Sinolight Surfactants Technology Co., Ltd. Straight chain alcohol ether with twelve

carbon (A12EO5) was natural fatty alcohol ether obtained from Sinolight Surfactants

Technology Co., Ltd. This nonionic surfactant was thought as raw material of

oxidation reaction. Oxygen was purchased from Taiyuan Iron & Steel Co., Ltd of

China. Catalyst was multi-component palladium carbon catalyst made by ourselves.

2.2 Experimental techniques

The structure of synthesized products was characterized by Fourier transform

infrared (FT-IR) spectrometer (Bruker Vertex 70, Germany) by KBr plate method.

Equilibrium surface tension of surfactant aqueous solutions was operated on a

Krüss K12 Processor Tension meter (Wilhelmy plate method) at the temperature of 25

± 0.2 ºC. Before measurement, surface tension of triply water was measured to reach

72.5 ± 0.5 mN/m to adjust the instrument. Every surfactant solution was stabilized

for 5 min in the thermostatic bath before measurement.

The dynamic surface tension of surfactant aqueous solutions was measured at 25

± 0.1ºC using a Krüss bubble pressure tensionmeter BP100 method, which involves

measuring the maximum pressure necessary to blow a bubble in a liquid from the tip

of a capillary. Effective surface ages of the measurements range from 0.01 s to 250 s.

The contact angle measurements of surfactant solutions were performed on a

Drop Shape Analyzer DSA255 (Krüss Company, Germany) at 25ºC to measure the

wetting ability on parafilm of surfactant solutions. A piece of parafilm was placed on

glass pane in front of microscope connected to a horizontal CCD camera which

displays dynamic spreading process of drop. The contact angle was obtained by

software calculation. Each experiment was repeated at least three times to ensure the

accuracy of results.

The electrolyte tolerance experiment was carried out by the transmittance

measurement of surfactant solutions at different concentrations using a UV-1601

spectrophotometer (Beijing Beifen-Ruili Analytical Instrument Company, China) at

300 nm. The temperature was kept at 25 ± 0.1ºC. Each measurement was repeated at

least three times to reduce errors.

2.3. Preparation of sample

Branched alcohol polyoxyethylene ether carboxylate (A13EC5-Na) and straight

chain alcohol ether carboxylate (A12EC5-Na) were synthesized by oxidation process

[26, 27]. Synthesized products (A12EC5-Na) were directly evaporated and dried to
remove water to make comparison. A certain amount of products were taken out to

prepare branched alcohol polyoxyethylene ether carboxylic acids (A13EC5-H). Firstly,

they were adjusted to the pH of 3 to ensure full conversion of alcohol ether carboxylic

acids. Secondly, they were placed into water bath with the temperature of 90ºC to

make organic phase stratified. After stratifying completely, the yellow organic phase

(alcohol ether carboxylic acid) was rapidly extracted by separating funnel. Then,

deionized water of 90ºC was added into organic phase and repeat above operation for

two times. Our aim was to remove sodium chloride, hydrochloric acid and a part of

fatty alcohol ether adequately. Finally the products was evaporated and dried to

anhydrate. So A13EC5-H was obtained for a series of research and A13EC5-Na can be

obtained by the reaction of A13EC5-H with 20% sodium hydroxide solution. The

reaction equation was as follows:

Pd/C
R(OCH2CH2)nOH + O2 R(OCH2CH2)n-1OCH2COONa
NaOH

3. Results and Discussion

3.1. Characterization of sample

The significant changes in structure of synthesized products have been confirmed

by FT-IR spectra.

The FT-IR spectra of acid products (A13EC5-H) and raw material (A13EO5) were

shown in Fig. 1. The peak of 2855 cm-1 was corresponding to stretching vibration of

-C-H both in A13EC5-H and A13EO5. The absorption band of -C-O-C- appeared at

1117 cm-1 both in the spectra of A13EC5-H and A13EO5, which was due to the

existence of polyoxyethylene ether groups in the structure of A13EC5-H and A13EO5.

An obvious absorption peak at 1740 cm-1 was regarded as the stretching vibration of

-C=O. The reason why the strong absorption band appeared at 3410 cm-1 of A13EO5 is

the existence of -OH group in A13EO5. We can see the broad peak of 3410 cm-1,

which is for the influence of carboxyl group in A13EC5-H. These characteristic peaks

implied that A13EC5-H was obtained from the reaction of A13EO5.

 Fig. 1. FTIR spectra of A13EO5 and A13EC5-H

3.2. Equilibrium surface tension

Surface activity is the most basic property of surfactants. Surface tensions of

A13EC5-H and A13EC5-Na aqueous solutions were measured to evaluate their surface

abilities and that of linear dodecyl fatty alcohol polyoxyethylene ether carboxylates

(A12EC5-Na) was also measured to make comparison. Static surface tensions of

different concentration of A13EC5-H, A13EC5-Na and A12EC5-Na aqueous solutions

were investigated at 25°C (seen as Fig. 2). Critical micelle concentration (CMC) and

surface tension at this concentration (γcmc) can be shown in surface tension curves.

From Fig. 2, we can know surface tension of water declines sharply once surfactant

solutions are added and it remains relatively constant above the CMC. The curve is

different from that of single-tailed anionic surfactant sodium 3, 6, 9, 12,

15-pentaoxaheptacosanoate (AEC4-Na) and monoalkyl phosphate (MAP) salts

reported by Takaya Sakai [28, 29]. Their curves have two break points, that is, surface

tension firstly decreases and then increases and finally keeps balance. Takaya Sakai

thought vesicles formed in the first break point and transition of vesicle-to-micelle

occured in the second break point. The results were listed in the table 1, γcmc of

A13EC5-Na is 27.43 mN/m, which is in accord with that of A12EC5-Na (27.14 mN/m)

and lower than that of A13EC5-H (28.13 mN/m). The value is lower than γcmc of

AEC9-Na (29 mN/m). It can be concluded that surface activity of A13EC5-Na is

excellent, that is, the effect of decreasing surface tension of water is great. So our

branched anionic surfactants show more excellent properties than their acid products.

Considering CMC, A13EC5-H is lowest and the value is 0.175 mM. The CMC of

A13EC5-Na is 0.201 mM, which is basically the same with that of A12EC5-Na (0.193

mM). As is known to all, CMC can also be used as an indicator of surfactant surface

activity and the smaller CMC, the lower the concentration of forming micelles for

surfactants and the lower the concentration of the surface saturated adsorption. So the

concentration of forming micelles for non-ionic surfactants (A13EC5-H) is the lowest

which is very valuable and the concentration of forming micelles of A13EC5-Na and

A12EC5-Na is comparative. In a word, the surface properties of branched surfactants

A13EC5-Na are excellent.

Fig. 2. Static surface tension versus concentration of A13EC5-H, A13EC5-Na and

A12EC5-Na aqueous solutions.

We also calculated the maximum surface excess concentration (Γm) and the

surface areas (A0) at the air-water interface of surfactants to further study their

properties. They were calculated according to Gibbs adsorption equation [30]:

1 d
Γm   ( )T (1)
2.303nRT d log C

1
A0  (2)
Γm N A
 Where R is the gas constant (8.314 J/mol·K), T is the absolute temperature

(298.15 K), NA is Avogadro’s constant and (dγ/dlogC)T is the slope of the surface

tension γ versus logC below the CMC. The parameter n is the number of solute

species. So n is taken as 1 for non-ionic surfactants and 2 for anionic surfactants by

ionization of ionic surfactants without other electrolyte. All the results are listed in

Table 1. From the table, we can know that the maximum surface excess concentration

of non-ionic surfactant (A13EC5-H) is higher than anionic surfactants. This is because

repulsive force between ion head groups with the same charge in ionic surfactants

makes ionic surfactant molecules arrange loosely on the surface adsorption layer, so

the value Γm is smaller than that of non-ionic surfactants. After all, the smaller the

surface area, the higher the maximum surface excess concentration. We also observed

Γm of A13EC5-Na is smaller than that of A12EC5-Na. The reason is that the steric
hindrance between branched chains in A13EC5-Na molecules leads to loose

arrangement on the air-water interface compared with linear surfactants A12EC5-Na.

Thus the surface area of A13EC5-Na is bigger than that of A12EC5-Na. What’s more,

we studied the adsorption efficiency of surfactants at air/water interface pC20 (the

negative logarithm of surfactant molar concentration required to decrease the surface

tension of water by 20 mN/m) and the efficiency of surfactant molecules’ adsorption

to the air/water interface then forming micelles CMC/C20. The larger the pC20, the

greater the adsorption efficiency of the surfactant at the air/water interface. And the

larger the CMC/C20, the more efficiency of forming micelles. From Table 1, we can

know pC20 and CMC/C20 value of A13EC5-H are largest, which indicates that its

adsorption to the air/water interface is fastest and forming micelles is fastest. For

A12EC5-Na, the pC20 and CMC/C20 value is smallest, which shows the adsorption

efficiency and the efficiency of forming micelles of A12EC5-Na molecules are inferior

to that of our synthesized products. In short, the adsorption efficiency of branched

A13EC5-H at the air/water interface is the fastest and the formation of micelles is the

easiest, correspondingly, its CMC is also the smallest. The adsorption behaviors were
illustrated in scheme 2.

Table 1 Surface properties of three surfactant solutions.

CMC γ cmc Γm A0
sample pC20 CMC/C20
(mM) (mN/m) (μmol/m2) (nm2)

A13EC5-H 0.175 28.13 2.67 0.622 5.27 32.59

A13EC5-Na 0.201 27.43 1.53 1.09 5.13 27.31

A12EC5-Na 0.193 27.14 1.81 0.918 4.91 15.56

air

Branched chain
Hydrogen
Hydrophilic head bond
with -COOH water
COOH HOOC 1s

air

Branched chain
Electrostatic
Hydrophilic head repulsion
with -COONa
COO- COO- 1s water

Scheme 2. Schematic representation of adsorption behavior for A13EC5-H and

A13EC5-Na molecules at air/water interface.

3.3. Wetting ability

Wetting is an important process in human production and life. It is of great value

to study the spreading of surfactant solutions on the solid surface due to its wide

application in coating, herbicide and painting [31,32]. The wetting ability of

surfactants was measured by contact angle measurement at 25°C. Fig. 3 showed the

dynamic contact angles of different concentrations of A13EC5-H, A13EC5-Na and

A12EC5-Na aqueous solutions on parafilm. From Fig. 3a, b, c, we can know contact

angle is 100ºat the lower concentration with increasing of time. With the increasing
of time, contact angle is firstly decreased and then kept changeless at higher

concentrations. We also found when the concentration is 0.05 mM, contact angle of

A13EC5-H aqueous solutions begins to decrease to about 80º. But contact angle of

A12EC5-Na aqueous solutions can decrease to 90ºwhen the concentration is 0.5 mM.

Fig. 3d showed that dynamic contact angle curves versus different concentrations for

different samples at the same time of 120 s from which we intuitively see contact

angles of the three samples decrease first and then keep almost constant. Contact

angle of A13EC5-H aqueous solutions is smallest (30º) and that of A12EC5-Na aqueous

solutions is the largest (60º), so wetting ability of A13EC5-H aqueous solutions is

more excellent than that of anionic surfactants. Young's equation was usually used to

explain the wetting behavior:

 sg   lg cos    sl (3)

Where θ is the contact angle of surfactants, γsg is gas-solid interface free energy,

γlg is liquid surface free energy, and γsl is solid-liquid interface free energy. γsg and γlg

can be regarded as constant because in the experiment water is the liquid media and

parafilm is the solid media, whose γ is their inherent quality. γsl will decrease when

surfactants are added into water, that is, γsl would decrease all the way, so in the

equation, cosθ must increase and this promotes the spreading of surfactant drop on

solid surface.

Considering the correlation between wetting ability and diffusion of surfactant

molecules, we conducted the study of dynamic surface tension of different

concentration surfactant solutions.

 130 Concentration/mmol/L 130 Concentration/mmol/L
a 120 0.01 0.02 0.05 0.1 0.2 b 120 0.01 0.02 0.05 0.1 0.2
0.5 1 2 5 0.5 1 2 5
110
Contact angle/degree 110

Contact angle/degree
100
100
90
90
80
70 80

60 70
50 60
40 50
30 40
0 20 40 60 80 100 120
0 20 40 60 80 100 120
Time/s Time/s
130 110
Concentration/mmol/L A13EC5-H
c 120 0.01 0.02 0.05 0.1 0.2 d 100 A13EC5-Na
0.5 1 2 5 A12EC5-Na
90
110
Contact angle/degree

Contact angle/degree
80
100
70
90
60
80
50
70
40
60 30
0 20 40 60 80 100 120 0 1 2 3 4 5
Time/s Concentration/mM

Fig. 3. Dynamic contact angle curves as a function of time for different concentrations

of a) A13EC5-H b) A13EC5-Na c) A12EC5-Na. d) Dynamic contact angle curves versus

different concentration for different samples at the same time of 120 s.

3.4. Dynamic surface tension

The dynamic surface tension method by a maximum bubble pressure technique

can be used to measure the change of surface tension with the increase of time and

investigate the kinetics of surfactant adsorption. Fig. 4 showed dynamic surface

tension curves with surface age for A13EC5-H, A13EC5-Na and A12EC5-Na solutions of

various concentrations at 25ºC. From Fig. 4, we can know that dynamic surface

tension curves of the three surfactant solutions all decrease rapidly first and then keep

equilibrium slowly. From Fig. 4b and c, we can surmise for surfactant system with

similar structure, branched surfactants (A13EC5-Na) make the time of their surface

tension reaching equilibrium shorter and make the rate faster. What’s more, the higher

the concentration of surfactant solutions, the faster the rate of surface tensions

reaching equilibrium (Fig. 4a, b, c). We also conclude that when the concentration is

above the CMC, the rate of surface tensions reaching equilibrium is affected
minimally by the concentration. This is because that monomer concentration is

approximately constant after the micelle formation. We can infer that A13EC5-H

molecules diffuse fastest to the interface, and A12EC5-Na is the slowest, which is

consistent with the wetting process in Fig. 3.

80
a A13EC5-H
0.01mM
b 70
A13EC5-Na
0.01 mM
70 0.05 mM 0.05 mM
0.1 mM 0.1 mM
Surface tension/mN/m

0.2mM 60 0.2 mM

Surface tension/mN/m
60 1mM 1 mM
5mM 5 mM

50 50

40 40

30
30

0 50 100 150 200 250 0 50 100 150 200 250

surface age/s Surface age/s

c 90
A12EC5-Na
0.01mM
0.05mM
80 0.1 mM
Surface tension/mN/m

0.2mM
70 1 mM
5 mM
60

50

40

30

0 50 100 150 200 250

surface age/s

Fig. 4. Dynamic surface tension versus surface age (s) for (a) A13EC5-H (b)

A13EC5-Na (c) A12EC5-Na solutions of different concentrations at 25ºC.

Rosen [33] divided the DST curve into four stages when he studied changes of

the dynamic surface tension with time, which were respectively induction region,

rapid fall region, meso-equilibrium region and equilibrium region. The dynamic

surface tension data of the first three regions fit the following equation.

 0  t t
 (  )n (4)
t   m t

Where γ0 is surface tension of solvent, γt is surface tension of surfactant solutions

at surface age t and γm is meso-equilibrium surface tension. n and t* are constant, n is

dimensionless quantity and t* is a unit of time the same as t.

Taking the logarithm on both sides of equation (4):

 lg( 0  t ) /(t   m )  n lg t  n lg t  (5)

We got three figures about A13EC5-H, A13EC5-Na and A12EC5-Na solutions

using the above model (seen as Fig. 5). We can calculate the n and t* value from the

fitting straight line. The time parameters ti and tm also can be obtained from the

equations.

lg ti  lg t   1 (6)
n

lg t m  lg t   1 (7)
n
Where ti is time for induction region to end. tm is time of the meso-equilibrium

region to begin.

The fall rate in surface tension rapid decline region at t*, that is R1/2, is defined

by the following equation:

0  m
R1  (8)
2 2t 
The dynamic surface tension characteristic parameters are all listed in Table 2.

For pure surfactant, with the increase of concentration, n value increases first, then

decreases, which indicates that the diffusion rate of surfactants becomes faster in the
3
3.0 A13EC5-Na
a A13EC5-H
0.01 mM
b 2.5 0.01 mM
2 0.05 mM 2.0 0.05 mM
0.1 mM 0.1 mM
1.5
0.2 mM 0.2 mM
lg0-t)/(t-m)]

1.0
lg0-t)/(t-m)]

1 1 mM 1 mM
5 mM 0.5 5 mM

0 0.0
-0.5
-1.0
-1
-1.5
-2.0
-2
-2.5
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 -3.0
-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5
lgt lgt
3
A12EC5-Na
c 2
0.01 mM
0.05 mM
0.1 mM
0.2 mM
1
1 mM
lg0-t)/(t-m)]

5 mM
0

-1

-2

-3
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5
lgt
Fig. 5. lg[(γ0-γt)/(γt-γm)] versus lgt for (a) A13EC5-H (b) A13EC5-Na (c) A12EC5-Na

solutions of different concentrations.

high concentration region. Because n is a measure of inherent tendency of surfactant

molecules to absorb at the air/water interface. Thus when the concentration increases,

more surfactant molecules will diffuse to the interface layer, which contributes to

larger diffusion rate. t* value is smaller and smaller and R1/2 value is larger and larger

with increasing concentration of surfactant. The decrease of t* is the result of

increasing adsorption barrier. Because when the concentration increases, more

surfactant molecules are absorbed onto the surface of the solution, but in the later

stage of adsorption, a significant number of surfactant molecules occupied on the

surface hinder the adsorption of new surfactant molecules due to the increasing of

repulsive interaction of molecules. So adsorption barrier increases. The increase of

R1/2 value shows the rate of surface tension decreasing increases, that is, dynamic

surface activity enhances with the increase of concentration. For surfactants with the

same concentration, n value of A12EC5-Na is smaller than that of branched products

(A13EC5-H and A13EC5-Na) and n value of A13EC5-Na is smaller than A13EC5-H. It

reveals the diffusion rate of A12EC5-Na is the largest, and A13EC5-H is the slowest.

We can know t* of A13EC5-Na is smaller than that of A12EC5-Na, which indicates

more energy is needed to absorb to surface for A13EC5-Na. tm is the time of the

meso-equilibrium region beginning. The tm of A12EC5-Na is larger than that of

A13EC5-Na because surface excess value of A12EC5-Na is larger and adsorption

efficiency (pC20) is smaller compared with A13EC5-Na (seen as Table 1), which needs

more time to reach the meso-equilibrium region. ti is the time for the induction region

to end and is related to the surface coverage of the air/water interface and to the

apparent diffusion coefficient of the surfactant at short times Dap. ti of A12EC5-Na is

the largest.

3.5. Diffusion Coefficient

In order to test the adsorption rate at air/water interface of surfactant, we usually

use the diffusion-controlled adsorption model by Ward and Tordai [34] to analyze the

dynamic surface tension.

Dt D t
Γt  2C 0

2
t 0
C sd( t   ) (9)

Where Γt is the surface excess concentration at time t, t is time, D is the apparent

diffusion coefficient, C0 is the bulk concentration, Cs is the concentration in the

subsurface and  is a dummy time delay variable. Because experimental data can’t fit

the equation, the short and long-time adsorption behaviors could be obtained by the

following asymptotic equations.

Dt
Short time: (t )t 0   0  2nRTC 0 (10)

2
nRTΓeq 
Long time: (t )t     eq  (11)
C0 4Dt

Where γ(t) is surface tension at time t, γ0 is surface tension of solvent water, γeq

is the equilibrium surface tension, Γeq is the equilibrium surface excess concentration

and n is 1 for nonionic surfactants and 2 for ionic surfactants.

Fig. 6 shows the plots of the DST versus short-time (t1/2) and long-time (t-1/2) for

A13EC5-H, A13EC5-Na and A12EC5-Na solutions at different concentrations.

Table 2 Dynamic surface tension parameters of A13EC5-H, A13EC5-Na and

A12EC5-Na with different concentrations.

C(mM)
A13EC5-H
Parameter
0.01 0.05 0.1 0.2 1 5

n 0.53 0.80 0.75 0.82 0.82 0.80

t*(s) 802.93 18.89 5.32 1.76 0.26 0.07

ti (s) 10.43 1.06 0.25 0.11 0.02 3.84×10-3

tm(s) 6.18×104 335.93 112.34 29.02 4.31 1.22

R1/2 (mN/m·s) 0.028 1.17 4.16 12.58 84.48 320.80

C(mM) A13EC5-Na

Parameter
0.01 0.05 0.1 0.2 1 5

n 0.54 0.69 0.72 0.76 0.70 0.34

t*(s) 873.48 44.72 13.50 3.23 0.16 4.14×10-3

ti (s) 12.05 1.58 0.55 0.16 5.83×10-3 4.93×10-6

tm(s) 6.30×104 1264.77 329.11 66.56 4.39 3.48

R1/2 (mN/m·s) 0.03 0.50 1.67 6.96 140.53 5431.20

C(mM) A12EC5-Na

Parameter
0.01 0.05 0.1 0.2 1 5

n 0.51 0.56 0.55 0.54 0.48 0.31

t*(s) 6148.90 329.60 110.50 30.11 2.05 0.06

ti (s) 65.62 5.20 1.64 0.42 0.02 3.38×10-5

tm(s) 5.77×105 2.09×104 7435.70 2169.80 259.78 116.24

R1/2 (mN/m·s) 3.68×10-3 0.07 0.21 0.75 11.06 359.21

 70
a 70 b
60
60
Surface tension/mN/m

Surface tension/mN/m
50
50
40
40
30 A13EC5-Na
A13EC5-H
0.01 mM
0.01 mM
30 0.05 mM
0.05 mM 20
0.1 mM
0.1 mM
20 0.2 mM
0.2 mM 10
1 mM
1 mM
5 mM
5 mM 0
10
0.0 1.2 2.4 3.6 0.0 1.2 2.4 3.6
1/2 1/2 1/2 1/2
t (s ) t (s )

70
c d 70

60 60
Surface tension/mN/m

Surface tension/mN/m
50 50

40 A12EC5-Na 40 A13EC5-H
0.01 mM 0.01 mM
0.05 mM 0.05 mM
30 30 0.1 mM
0.1 mM
0.2 mM 0.2 mM
20 1 mM 20 1 mM
5 mM 5 mM
0.0 1.2 2.4 3.6 0.0 1.2 2.4 3.6
1/2 1/2 -1/2 -1/2
t (s ) t (s )

70
e f 70
60
60
Surface tension/mN/m

Surface tension/mN/m

50

40 50

A13EC5-Na A12EC5-Na
30
0.01 mM 40 0.01 mM
0.05 mM 0.05 mM
20
0.1 mM 0.1 mM
0.2 mM 30 0.2 mM
10 1 mM
1 mM
5 mM 5 mM
0 20
0.0 1.2 2.4 3.6 0.0 1.2 2.4 3.6
-1/2 -1/2 -1/2 -1/2
t (s ) t (s )

Fig. 6. Dynamic surface tension as a function of a short-time (t1/2) at various

concentration of surfactant solutions: (a) A13EC5-H (b) A13EC5-Na (c) A12EC5-Na and

a long-time (t-1/2) at various concentrate of surfactant solutions: (d) A13EC5-H (e)

A13EC5-Na (f) A12EC5-Na.

The apparent diffusion coefficient can be calculated from the slope of the DST

plots versus t1/2 (short time) and t-1/2 (long time) as shown in Fig. 6 based on equation

(10) and (11). The calculated results are listed in Table 3, from which we can know

Dshort value of A13EC5-H increases first then decreases, but Dlong value decreases all the

way with the increase of concentration. Overall, both Dshort and Dlong value of

A13EC5-Na and A12EC5-Na decrease when their concentrations increase. This may be
because for ionic surfactants, electrostatic repulsion between intermolecular

headgroups is enhanced when their concentrations increase, which slows down the

adsorption kinetics of surfactant molecules at the air/water surface. What’s more, at

the same concentration, Dshort and Dlong values of A13EC5-H are the largest which is due

to the lack of effect of electrostatic repulsion and Dshort value of A13EC5-Na is larger

than that of A12EC5-Na. While for Dlong, when C<CMC, A12EC5-Na>A13EC5-Na;

when C>CMC, A12EC5-Na<A13EC5-Na. A possible explanation is the effect of steric

hindrance between branched chains of A13EC5-Na molecules at the stage of diffusion.

We choose 1mM which is larger than CMC of three surfactants to calculate Dlong/Dshort.

For A13EC5-H and A12EC5-Na, the ratio of Dlong and Dshort is less than one, which

indicates that the adsorption process is mixed diffusion-kinetic adsorption mechanism;

while the ratio of A13EC5-Na is close to one, which suggests the process is diffusion

controlled [35,36].

Table 3 Calculated apparent diffusion coefficients of A13EC5-H, A13EC5-Na and

A12EC5-Na surfactant solutions.

A13EC5-H A13EC5-Na A12EC5-Na

C (mM) Dshort Dlong Dshort Dlong Dshort Dlong

(m2/s) (m2/s) (m2/s) (m2/s) (m2/s) (m2/s)

0.01 6.12×10-12 3.07×10-10 2.22×10-12 6.88×10-11 6.78×10-13 8.09×10-10

0.05 1.52×10-11 1.80×10-11 1.90×10-12 5.45×10-12 4.91×10-13 2.74×10-11

0.1 1.55×10-11 8.96×10-12 1.19×10-12 1.72×10-12 3.56×10-12 5.45×10-12

0.2 1.32×10-11 7.95×10-12 1.11×10-12 1.18×10-12 1.75×10-13 6.77×10-13

1 2.82×10-12 2.39×10-12 5.15×10-13 7.49×10-13 2.34×10-13 4.23×10-14

5 2.17×10-13 2.56×10-13 3.07×10-14 4.83×10-13 2.43×10-14 1.30×10-14

3.6. Electrolyte Tolerance

The test of electrolyte tolerance is of significance for its application in industry,

detergency and surfactant enhanced oil recovery [37]. Generally, Na+, Mg2+ and Ca2+

are used to study surfactant tolerance. We chose the surfactant concentration as 6 mM,
which is close to 3 g/L. The curves of salt tolerance of A13EC5-Na and A12EC5-Na

solutions against transmissivity of solutions are shown in Fig. 7. As shown in Fig. 7a,

the turbidity decreased critical concentration of NaCl for A13EC5-Na is 130 g/L and

for MgCl2, it is around 80 g/L. NaCl and MgCl2 tolerance of A12EC5-Na are excellent.

Although added NaCl reaches saturation and MgCl2 reaches 180 g/L, A12EC5-Na

solution is still clarified. NaCl tolerance of A13EC5-Na is also preferable than alky

carboxylates [38] although it cannot compare with that of A12EC5-Na. For A13EC5-Na,

transmissivity declined but salting-out didn’t occur when larger concentration NaCl

and MgCl2 were added. NaCl tolerance was stronger than MgCl2 tolerance. From Fig.

7b, we can conclude that the turbidity decreased critical concentration of CaCl2 of

A13EC5-Na is 0.4 g/L, which is stronger than that of A12EC5-Na (0.2 g/L). In summary,

the order of influence of inorganic counter ions on surfactants was Na+ < Mg2+ < Ca2+.

It is due to the fact that the binding of surfactant ions to monovalent counterions is

dominated by regional binding, while the binding of surfactant ions to divalent

counterions is mainly localized binding. When the charge of inorganic counterions is

the same, it may be the effect of radius of inorganic counterions.

Interestingly, after 3 months, we found that there were precipitation occuring in

all the A12EC5-Na solutions with CaCl2. However, A13EC5-Na solutions were still

homogeneous. This is because the existence of EO chain strengthens hydrophily of

alcohol ether surfactants, so their salt tolerance is great. What’s more, the existence of

branched chain in branched surfactant molecules may make themselves possess

dendritic three-dimensional structure, which is chelation for metal ions. Under such

circumstances, branched surfactants were not easily precipitate. Considering practical

application, the salt tolerance of branched A13EC5-Na is better.

 110 110
A13EC5-Na A13EC5-Na
a b 100 A12EC5-Na
100 90

80
90 70
T/%

T/%
60
80
50

40
70
30

20
60
60 70 80 90 100 110 120 130 140 150 160 0.1 1 10 100
NaCl/ g/L CaCl2/ g/L
100
c A13EC5-Na
A12EC5-Na
T/%

80

0 20 40 60 80 100 120 140 160 180

MgCl2/ g/L

Fig. 7. Transmittance curves at 300 nm for 6 mM A13EC5-Na and A12EC5-Na

solutions against (a) NaCl concentration (b) CaCl2 concentration (c) MgCl2

concentration.

4. Conclusions

A kind of branched polyoxyethylene ether carboxylates (A13EC5-Na) have been

successfully synthesized by one step oxidation. Alcohol ether carboxylic acid

(A13EC5-H) shows the lowest CMC and A0 and the highest Γm. And the adsorption

efficiency of branched A13EC5-H at the air/water interface is the fastest and the

formation of micelles is the easiest. The surface energy of A13EC5-Na is great, of

which CMC is 0.201 mM and γcmc is 27.43 mN/m. These values are excellent for

anionic surfactants and can comparable with linear chain A12EC5-Na. From contact

angle and dynamic surface tension measurements, we can know the wetting ability is

stronger, diffusion rate to the interface is faster and the time of surface tension

reaching equilibrium is shorter for branched products. For A12EC5-Na, the adsorption

process is mixed diffusion-kinetic adsorption mechanism; for A13EC5-Na, the

adsorption process is diffusion controlled. The electrolyte tolerance of A13EC5-Na and

A12EC5-Na is superior. The order of influence of inorganic counter ions on surfactants

was Na+ < Mg2+ < Ca2+. CaCl2 tolerance of branched A13EC5-Na is better than that of

A12EC5-Na.

Acknowledgment

The project is funded by the Science and Technology Innovation Foundation of

China SinoLight Corporation (2016) and the National Key Research and

Development Program of China (No. 2017YFB0308804) and JALA Research Fund

(Jala 2015). We would like to express our great gratitude to these foundations.

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