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Multi-purpose surfactants:

low-foaming, fast wetting and


biodegradable
C11 oxo alcohol alkoxylates*

THIS PAPER PRESENTS TWO FAMILIES OF NON-IONIC SURFACTANTS CONSISTING IN ETHOXY- A. POLITO1, A. FOLLI1, B. BREITZKE2
LATES-PROPOXYLATES AND PROPOXYLATES-ETHOXYLATES BOTH BASED ON A MIXTURE OF
PRIMARY LINEAR AND MONOBRANCHED FATTY ALCOHOLS WITH AN ALKYL CHAIN LENGTH OF
ELEVEN CARBON ATOMS. A PHYSICAL-CHEMICAL CHARACTERIZATION (WATER-SURFACTANT
1)
SASOL ITALY S.P.A. - MILANO
PHASE DIAGRAMS, FOAMING PROFILES, WETTING POWER, SURFACE TENSION, DYNAMIC CON- 2)
SASOL GERMANY GMBH
TACT ANGLE AND CRITICAL MICELLAR CONCENTRATION) OF THE NON-IONIC SURFACTANTS HAS
BEEN CARRIED OUT. RESULTS HAVE SHOWN THE COMBINATION OF THE POLY-ETHOXYLIC AND
POLY-PROPOXYLIC CHAINS TOGETHER WITH THE SHORT AND SEMI-BRANCHED HYDROCARBON
CHAIN STRUCTURE OF THESE SURFACTANT FAMILIES ASSURES OUTSTANDING WETTING PRO-
PERTIES AND VERY LOW FOAMING BEHAVIOUR THAN ETHOXYLATES ONLY, MAKING THEM
ABSOLUTELY SUITABLE FOR DETERGENT AND INDUSTRIAL APPLICATIONS WHERE THE HIGH
WETTING POWER AND THE LOW FOAM LEVEL ARE FUNDAMENTAL FOR THE PROCESS OR THE
FORMULATION IN WHICH THEY ARE INVOLVED. THE ALKOXYLATES NON-IONIC SURFACTANTS
HERE PRESENTED ARE BIODEGRADABLE, CLASSIFIED NEITHER N (DANGEROUS FOR THE
ENVIRONMENT) NOR R50 (VERY TOXIC TO AQUATIC ORGANISMS) AND FULFIL THE NEW
EUROPEAN DETERGENT REGULATION 648/2004 EC.
60
TENSIOATTIVI MULTI USO: ALCOL ALCOSSILATI C11 OXO A BASSO PROFILO
SCHIUMOGENO , VELOCE POTERE BAGNANTE , BIODEGRADABILI
QUESTO LAVORO PRESENTA DUE FAMIGLIE DI TENSIOATTIVI NON IONICI CONSISTENTI IN ETOS-
SILATI-PROPOSSILATI E PROPOSSILATI-ETOSSILATI BASATI SU UNA MISCELA DI ALCOLI GRASSI
PRIMARI LINEARI E MONORAMIFICATI CON UNA CATENA ALCHILICA DI UNDICI ATOMI DI CAR-
BONIO. È STATA EFFETTUATA UNA CARATTERIZZAZIONE CHIMICO FISICA DI TALI TENSIOATTIVI
NON IONICI CHE INCLUDE DIAGRAMMI DI FASE ACQUA -TENSIOATTIVO, COMPORTAMENTO
SCHIUMOGENO, POTERE BAGNANTE, TENSIONE SUPERFICIALE, ANGOLO DI CONTATTO DINAMI-
CO E CONCENTRAZIONE MICELLARE CRITICA. I RISULTATI HANNO DIMOSTRATO CHE LA COMBI-
NAZIONE DELLE CATENE POLIOSSIETILENICHE E POLIOSSIPROPILENICHE UNITAMENTE ALLA
STRUTTURA IDROCARBURICA CORTA E SEMI RAMIFICATA DI QUESTE FAMIGLIE DI TENSIOATTIVI
GARANTISCE UN ECCEZIONALE POTERE BAGNANTE E UN COMPORTAMENTO SCHIUMOGENO
MOLTO PIÙ BASSO DI QUELLO DEI DERIVATI ESCLUSIVAMENTE ETOSSILATI. TALI CARATTERISTI-
CHE RENDONO QUESTI TENSIOATTIVI PARTICOLARMENTE ADATTI PER APPLICAZIONI SIA IN
DETERGENZA CHE NEI SETTORI INDUSTRIALI IN CUI UN ELEVATO POTERE BAGNANTE E UN
BASSO PROFILO SCHIUMOGENO SONO FONDAMENTALI PER IL PROCESSO O LE FORMULAZIONI
IN CUI VENGONO IMPIEGATI. I TENSIOATTIVI NON IONICI PRESENTATI SONO BIODEGRADABILI,
NON SONO CLASSIFICATI CON IL SIMBOLO N (NOCIVO PER L’AMBIENTE) NÉ CON LA FRASE
R50 (MOLTO TOSSICI PER GLI ORGANISMI ACQUATICI) E SODDISFANO I REQUISITI DELLA
NUOVA REGOLAMENTAZIONE EUROPEA DELLA DETERGENZA (648/2004 EC).

(*) PAPER PRESENTED AT THE CONGRESS


12° GIORNATE CID, TRIESTE, JUNE 13-15, 2007
CORRESPONDENCE: alessandro.polito@it.sasol.com

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INTRODUCTION • Surface tension
• Critical micellar concentration (c.m.c.)
In the present study we investigated the main phy- • Foaming power
sical-chemical properties of two families of non-ionic • Cotton wetting
surfactants consisting in ethoxylate-propoxylates and • Dynamic contact angle
propoxylates-ethoxylates both based on Lial® 111, • Water–surfactant phase diagram
which is a mixture (50/50) of linear and primary mono-
branched fatty alcohols with an alkyl chain length of Regarding c.m.c. and surface tension evaluation,
eleven carbon atoms. Lial® 111 is obtained starting a Lauda TE 1 C/2 tensiometer was used. The
from an OXO process, which increases by one car- c.m.c. value was calculated by interpolation of the
bon atom the length of a C10 linear internal olefin by surface tension trend related to pre and post-
adduction of a CH2OH functional group. The primary micellar concentration region versus the log of sur-
mono-branched fatty alcohol isomers of which Lial® factant concentration. Measurements were carried
111 is composed are characterised by a statistical out by using deionised water at 25 °C. Foaming
distribution of the CH2OH functional group on the power was evaluated in accordance with Ross-
hydrocarbon chain backbone as it follows: Miles method at 0.5 and 2 g/l surfactant concen-
tration, at 25 and 40°C by using hard water (300
CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH-CH3 ppm CaCO3). According to the test procedure, 50
I ml of pre-heated surfactant solution were poured
CH2-OH
along a glass cylinder walls using gravity. Later on
2-Methyl, 1-Decanol 200ml of solution, contained in a pipette, were spil-
led from the top of the cylinder. Once the solution
CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH-CH2-CH3 ceased to fall, the stopwatch started and the hei-
I ght of the foam generated by fall was measured
CH2-OH
against time. Cotton wetting was evaluated in
2-Ethyl, 1-Nonanol accordance with ISO 8022 (DIN 1772) method by
determining the time between the immersion of a
CH3-CH2-CH2-CH2-CH2-CH2-CH-CH2-CH2-CH3 disc of raw cotton cloth in a surfactant solution at
I 25°C and the instant when the disc begins to sink.
CH2-OH
Each surfactant was tested at 0.25, 0.5, 0.75 and 61
2-Propyl, 1-Octanol 1 g/l. Dynamic contact angle was measured by
placing a drop of 1 g/l surfactant solution on a hard
CH3-CH2-CH2-CH2-CH2-CH-CH2-CH2-CH2-CH3 surface and observing the changing shape of the
I drop with a high speed camera system delivering
CH2-OH
up to 300 frames per second. As temperature and
2-Butyl, 1-Heptanol humidity have a strong influence on the results,
these values were controlled with a climate cham-
We took into account ethoxylate-propoxylates with ber at 25°C and 50% humidity.
same degree of ethoxylation and different degree of Once the measurement finished the contour of
propoxylation (Table I), and propoxylates-ethoxylates the drop was extracted from the video and the
with same degree of propoxylation and different contact angle of the drop to the surface could be
degree of ethoxylation (Table II). calculated. A low contact angle corresponds to
Their physical-chemical properties were evaluated good wetting of the surface and a high contact
in comparison with ethoxylates based on the same angle to a bad wetting. The absolute value of the
fatty alcohol (Lial® 111) (Table III). contact angle alone is not very meaningful, as the
contact angle was not only dependent on the sur-
EXPERIMENTAL PROCEDURE factant but was also related to the surface. The
polarity of the surface depends on the chemical
We focused our attention on the following physical- nature of the material and has influence on the
chemical properties: contact angle.

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Figura 1 - Surface tension vs. surfactant concentration

Table I

Property Unit MARLOX OP1 MARLOX 11027 MARLOX 11009


Cloud point (1% in deionized water) °C 36 26 11
Cloud point (10% in 25 % BDG solution) - 51 44 31
Molecular weight (g/mole) g/mole 667 758 967
HLB (Davies) - 4.8 4.6 4.1

Table II

62 Property Unit MARLOX 40 MARLOX 50 MARLOX 80


Cloud point (1% in deionized water) °C --- 43 56
Cloud point (10% in 25 % BDG solution) - 60 67 76
Molecular weight g/mole 445 550 641
HLB (Davies) - 4.0 4.7 5.4

Table III

Property Unit LIALET 111-5.5 LIALET 111-7 LIALET 111-8


Cloud point (1% in deionized water) °C --- 54 65
Cloud point (10% in 25 % BDG solution) - 70 --- ---
Molecular weight g/mole 402 480 515
HLB (Davies) - 4.8 5.4 5.6

Two different surfaces were selected with rele- important for fast wetting processes. The differen-
vance to the practical application of the surfac- ce between initial and final contact angle showed
tants: stainless steel and glass. The dynamic con- the wetting power of the surfactant and bending of
tact angle curve showed the development of the the curve showed the speed of the surfactant in
contact angle over time. The “initial” contact angle the wetting process. The “initial” contact angle was
right after placing the drop on the surface is very given at t=0.2 s. The final contact angle could not

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Figura 2 - Foaming behaviour at 25°C

63

Figura 3 - Foaming behaviour at 40°C

be determined due to the long spreading times and RESULTS AND DISCUSSION
the evaporation of liquid during the spreading pro-
cess. Thus the contact angle at t=25s was taken Figure 1 shows the surface tension of the water ver-
as a relative indication for the final contact angle sus the surfactant concentration of Lial® 111 alcohol
reached. Water-surfactant phase diagrams were ethoxylates (C11 EO), ethoxylate-propoxylates (C11
obtained for each surfactant by evaluating physical EO PO) and propoxylate-ethoxylates (C11 PO EO). As
appearance of samples of water-surfactant mixtu- it can be seen propoxylation affects micellar aggrega-
res having 10, 20, 25, 30, 35, 40, 60, 70, 75, 80, tion behaviour in opposite directions according to
85, 90 and 95% wt. surfactant concentration. The position of PO groups along the polyalkylene glycol
samples were placed in a cryostat bath and tem- chain. When PO groups were located between
perature was lowered by 5°C every 24 hours star- hydrophobic alkyl chain and hydrophilic polyethylene
ting from 50°C and stopping at –10°C. glycol chain they reduced c.m.c. values from 50-70

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Figura 4 - Cotton wetting at 5°C

64

Figura 5 - Dynamic contact angle on stainless steel

mg/l of Lialet® 111 EO down to 20-40 mg/l of Marlox® the case of Marlox® PO EO (27-28,5 mN/m) compa-
PO EO. On the contrary when PO groups were loca- red to Lialet® 111 EO (25-27 mN/m) and in a drastic
ted at the end of the hydrophilic polyethylene glycol one in the case of Marlox® EO PO (30-34 mN/m).
chain they increased c.m.c. values up to 80-400 mg/l The negative influence of PO groups on the ability to
of Marlox® EO PO. Influence of PO groups on surface reduce water surface tension was clearly evident when
tension was in the same direction either they are befo- foaming power of these three surfactant were compa-
re or after EO groups consisting in a slight increment in red each other, as it can be seen on Figure 2. Marlox®

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Figura 6 - Dynamic contact angle on glass

EO PO foaming profile is very poor and foaming beha- surfactant classes are larger on stainless steel than on
viour of Marlox® PO EO is between the one of Marlox® glass surface. In this case also wetting behaviour
EO PO and Lialet® 111 EO. Lialet® 111-5.5 represent seems to be correlated to molecular weight: lower the
an exception because of its short polyethylene glycol molecular weight better the wetting power. Besides a
chain that makes it not enough hydrophilic. This diffe- correlation with the position of PO groups along the
rent behaviour of the three surfactant families is more polyalkylene glycol chain was evident. The presence
evident passing through 25°C to 40°C where Marlox® of PO groups slightly affected the hard surface wet-
EO PO are not water soluble (Figure 3). ting power if PO groups were located before EO
Figure 4 shows sinking times obtained by using groups. On the contrary PO groups at the end of the 65
LIAL ® 111 alcohol ethoxylates (Lialet ® 111 EO), polyalkylene glycol chain decreased a little the out-
ethoxylate-propoxylates (Marlox® EO PO) and pro- standing wetting performance of the Lialet® 111 EO.
poxylates-ethoxylates (Marlox® PO EO). As it can be Water-surfactant phase diagrams of Marlox® EO PO
seen propoxylation slightly affects cotton wetting effi- and Marlox® PO EO are shown in Figures 7, 8, 9, 10,
ciency (minimum concentration needed to wet the 11 and 12. While Marlox® PO EO forms liquid crystals
cotton disc in a certain time) either PO groups are at medium concentration in water like fatty alcohol
before or after EO groups. Sinking times seem to be ethoxylates generally do, Marlox® EO PO don’t form
correlated more to molecular weight of the polyalkyle- gel at any concentration. In particular Marlox® OP1
ne glycol chain than to position of PO groups along dissolve completely over the entire concentration
the polyalkylene glycol chain. Most of the surfactants range. That is a further confirmation about the strong
tested showed sinking times around 20 seconds for a influence of PO groups on micellar aggregation beha-
surfactant concentration ranging from 0.75 to 1 g/l, viour when they are located at the end of the
whereas the low molecular weight Lialet® 111-5.5 polyalkylene glycol chain.
and the high molecular weight MARLOX® 11009
showed respectively the maximum and the minimum ENVIRONMENTAL BEHAVIOUR
cotton wetting efficiency. Figure 5 and 6 show dyna-
mic contact angle curves of Lialet® 111 EO, Marlox® The impact of Marlox® alkoxylate on the aquatic
EO PO and Marlox® PO EO in the time between 0 environment was investigated. Results from an aero-
and 25 seconds respectively on glass and stainless bic biodegradability campaign, done by using CO2
steel surfaces. Differences between the three different Evolution Biodegradability test (OECD Method 301 B),

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Figura 7 Figura 8

Figura 9 Figura 10

66

Figura 11 Figura 12

showed a biodegradability upper than 60 % after 28 Marlox ® alkoxylate assure additional benefits in
days for all Marlox® alkoxylate. This fully comply with comparison with ethoxylates only making them sui-
the requirements of Detergent Regulation (Reg. table for particular detergent and industrial applica-
648/2004) as specified in the Annex III part A. tions. More in details, the position of PO groups
About ecotoxicology Marlox® alkoxylate have a along the polyalkylene glycol chain affects differently
range of toxicity for aquatic organisms (Fish LC50) the main surfactant physical-chemical properties.
between 1-10 mg/l. On this basis, Marlox® alkoxyla- PO groups at the end of the polyalkylene glycol
tes are not classified dangerous for the environment. chain strongly decrease the surface activity resulting
in a very low foaming and in a non-gelling beha-
CONCLUSION viour. When PO groups were located between
hydrophobic alkyl chain and hydrophilic polyethyle-
The results showed that the combination of the ne glycol chain, they slightly depressed foam main-
EO and PO groups together with the short and taining the fast wetting behaviour typical of the cor-
semi-branched hydrocarbon chain structure of responding ethoxylate derivatives.

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