REVIEW ARTICLE
y Pinklesh Arora, Rakhi Singh, Geetha Seshadri and Ajay Kumar Tyagi
Synthesis, Properties and Applications
of Anionic Phosphate Ester Surfactants:
A Review
This paper reviews the various technologies involved in the syn-
thesis of anionic phosphate ester surfactants. Use of base mate-
rial such as alcohol ethoxylates, alkyl phenol ethoxylates, fatty
acid ethoxylates and phosphating reagents plays a key role on
Tenside Surfactants Detergents downloaded from www.hanser-elibrary.com by Hanser - Library on July 31, 2018
the applications and properties of phosphate ester surfactants.
Also roles are played by the reaction conditions maintained
and charging conditions on the mono-diester ratio. In this paper
attempt has been made to review the base materials used for
the synthesis of phosphate esters, synthesis processes and their
effect on the properties of phosphate esters, applications and
global scenario of phosphate ester surfactants.
Key words: Phosphate esters, surfactants, alcohol ethoxylates,
phosphation
For personal use only.
Synthese, Eigenschaften und Anwendungen von anioni-
schen Phosphatestertensiden: Ein Übersichtsbeitrag. In
diesem Artikel werden die verschiedenen Technologien, die bei
der Synthese anionischer Phosphatester-Tenside eine Rolle spie-
len, dargestellt. Die Verwendung der Ausgangsmaterialien wie
Alkoholethoxylate, Alkylphenolethoxylate, Fettsäureethoxylate
und Phosphatierungsreagenzien spielt eine Schlüsselrolle bei
den Anwendungen und Eigenschaften von Phosphatestertensi-
den. Auch spielen die beibehaltenen Reaktionsbedingungen
und Aufladungsbedingungen auf das Mono-Diester-Verhältnis
eine Rolle. In dieser Arbeit wurde versucht, die für die Synthese
von Phosphatestern verwendeten Ausgangsmaterialien, Synthe-
seprozesse und ihre Wirkung auf die Eigenschaften von Phos-
phatestern, Anwendungen und das globale Szenario von Phos-
phatestertensiden zu überprüfen.
Stichwörter: Phosphatester, Tenside, Alkoholethoxylate, Phos-
phatierung
1 Introduction
Phosphate esters are highly versatile anionic surfactants
with a useful combination of multifunctional properties.
Compared to other anionic surfactants, phosphate esters of-
fer specific advantages including stability over a broad pH
range, good solubility and corrosion inhibiting properties.
Phosphate esters are highly suitable for use as emulsifying
agents, wetting agents, anti-static agents, corrosion inhibi-
tors, lubricants, fire retardants, hydraulic fluids, paints and
coatings, emulsifiers, plasticizers and hydrotropes in clean-
ing formulations [1].
Phosphate esters are known for exhibiting mild and non-
irritating properties [2]. Phosphate esters are widely used as
lubricants and hydraulic fluids because of high performance
and safety advantage over others due to their high thermal
stability [3]. The properties of phosphate esters depend on
266 ª Carl Hanser Publisher, Munich
several factors such as the type of alcohols used as raw ma-
terial, phosphating agents, degree of ethoxylation of alco-
hols, synthesis process and mono/diester ratio. In this pa-
per, the effect of base materials (alcohols), phosphating
agents, and synthesis procedure on the properties of phos-
phate esters and their applications has been discussed and
correlations are established.
2 Base Materials
Phosphate esters are anionic surfactants which are produced
by phosphation of aliphatic or aromatic (ethoxylated) alco-
hols [4]. The reaction of alcohols with phosphating agents
is depicted in Fig. 1. The properties of phosphate esters can
be altered by the type of alcohol used as raw material and
degree of ethoxylation of the alcohol [5].
The most common base materials, which are used for
synthesizing phosphate esters, include fatty alcohol ethoxy-
lates, alkyl phenol ethoxylates, sorbitan ester ethoxylates,
fatty amine ethoxylates and ethylene oxide-propylene oxide
copolymers [3]. The hydroxy functional hydrophobe typically
consists of from 1 to 30 carbons of linear or branched, ali-
phatic, olefinic, or aromatic hydrocarbon. They are ethoxy-
lated with the degree of ethoxylation ranging from 0 to 50
ethylene oxide units [6] responsible for hydrophilicity.
2.1 Alcohol Ethoxylates
Alcohol ethoxylates are based on either synthetic or natural
fatty alcohols. Synthetic alcohol ethoxylates are produced by
direct ethoxylation of alcohols, whereas natural fatty alcohols
are first reduced to make them saturated before going for
ethoxylation. Both synthetic and natural alcohol ethoxylates
are used as nonionic surfactants in many industries [7]. Al-
cohol ethoxylates having a degree of ethoxylation or ethylene
oxide moles (EO moles) of 6 – 10 are used as surfactants in
detergents, ethoxylation greater than 10 is used in lime soap
as dispersants, wetting agents and emulsifiers. The fatty al-
cohol ethoxylates are non-ionic surfactants which are widely
used in washing detergents both domestic and industrial.
These are used as wetting and cleaning agents in cosmetics,
agriculture, textile, paper, oil and various other process in-
dustries. The examples of fatty alcohol ethoxylates are lauryl
Figure 1 Reaction scheme of alcohol with phosphating agent
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 Pinklesh Arora et al.: Synthesis, Properties and applications of anionic phosphate ester surfactants: a review
alcohol ethoxylate, stearyl alcohol ethoxylate, behenyl alcohol
ethoxylate etc. All of these ethoxylated products vary in phys-
ical appearance and have different properties like pour
point, cloud point, density, viscosity, and flash point depend-
ing on the level of ethoxylation process from which they are
formed [8]. The chemical structures of alcohol ethoxylates
present in household cleaning products are presented in
Fig. 2.
2.2 Fatty Acid Ethoxylates
Fatty acid ethoxylates are synthesized through ethoxylation
of fatty acids. These are extensively used in formulations of
emulsifying softeners, wetting agents, cleansing agents and
dispersants. The most popular application of acid ethoxy-
lates is in textile industry. The ethoxylates based on stearic
acid are applied in cosmetic industrial sectors as emulsifiers
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in oil-in-water type creams and lotions. Some other exam-
ples of fatty acid ethoxylates are coconut fatty acid ethoxy-
late, lauric acid ethoxylate, oleic acid ethoxylate and myristic
acid ethoxylates [9]. The chemical structure of fatty acid
ethoxylate is shown in Fig. 3.
2.3 Alkyl Phenol Ethoxylates
Alkyl phenol ethoxylates are prepared by the reaction of
ethylene oxide with the appropriate alkyl phenol. The most
common phosphate esters are based on nonyl phenol
ethoxylate. Owing to their properties of solubility in aqueous
For personal use only.
and non-aqueous media, good emulsification and dispersion
properties play an important role in making number of in-
dustrial products such as pulp and paper, textiles, coatings,
agricultural pesticides, lubricating oils and fuels, metals and
plastics. Alkyl phenol ethoxylates are most effectively used
in commercial cleaning products. [4]. Most common com-
mercially used products are octyl, nonyl, and dodecylphenol
with a degree of ethoxylation ranging from 4 to 40. Octyl
and nonylphenols with 8 – 12 ethylene oxide moles are used
in detergents. Compounds having ethylene oxide moles < 5
are applied in antifoaming agents or detergent in non-aque-
ous media. Ethoxylates with ethylene oxide moles ranging
from 12 to 20, are wetting agents and O/W emulsifiers.
More than 20 ethylene oxide moles exhibit detergents prop-
erties at high temperature and high salinity. The chemical
structure of alkyl phenol ethoxylates is given as Fig. 4.
3 Phosphating Agents
Phosphating agent is one important reactant for the synthe-
sis of the phosphate ester. The structure of phosphating
agent affects its reactivity and selectivity, resulting in vari-
ation in the monoester, diester, and triester product dis-
tribution [10]. The main phosphating agents used for the
Tenside Surf. Det. 55 (2018) 4
synthesis of phosphate esters are phosphoric anhydride
(P2O5), polyphosphoric acid (H4P2O7), phosphorus oxychlor-
ide [P(O)Cl3], orthophosphoric acid (H3POˇ4) and pyrophos-
phoric acid which are summarized in Table 1.
3.1 Phosphoric Anhydride
Phosphoric anhydride is a thermally stable, white, free-flow-
ing powder. It is very hygroscopic, acting as powerful desic-
cating agent. Addition of phosphorus anhydride to alcohol
can results in a vigorous, potentially uncontrollable and ha-
zardous reaction. With primary alcohols, phosphoric anhy-
dride reacts preferentially. Secondary alcohols are prone to
undergo undesirable side reactions such as dehydration.
When using P2O5 as the phosphating agent, the reaction
yields equimolar amounts of di and monoesters with no
phosphoric acid [11]. It is possible to obtain a desirable inter-
mediate product mixture by certain multi staged reaction se-
quences [12, 13]. The reaction of alcohol and phosphorus an-
hydride is given in Fig. 5.
3.2 Polyphosphoric Acid
Polyphosphoric acid is the concentrated grade of phosphoric
acid (H3PO4) above 95 %. It is a highly viscous colorless li-
quid. Polyphosphoric acid consists of a mixture of linear, oli-
gomeric chains having alternating phosphorus and oxygen
atoms [14]. The strength of polyphosphoric acid is com-
monly expressed as a percentage of phosphoric anhydride
(P2O5). As the corresponding percentage of phosphoric acid
increases, the material becomes progressively more viscous.
Most frequently, polyphosphoric acid of about 83 – 84 %
P2O5 is used. The linear polymeric structure of poly-
phosphoric acid makes it less reactive than the phosphoric
anhydride. Polyphosphoric acid reacts with alcohols to pro-
Figure 3 Chemical structure of fatty acid ethoxylates
Figure 4 Chemical structure of alkyl phenol ethoxylates
Figure 2 Chemical structure of alcohol ethoxy-
lates
267
 Pinklesh Arora et al.: Synthesis, Properties and applications of anionic phosphate ester surfactants: a review
Sample No. Name
1 Phosphoric anhydride
2 Polyphosphoric acid
3 Phosphorus Oxychloride
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4 Orthophosphoric acid
5 Pyrophosphoric acid
For personal use only.
Table 1 Phosphating agents for synthesis of phosphate esters
Figure 5 Reaction of phosphoric anhydride with alcohol for synthesis of
phosphate esters
duce a mixture of high monoalkyl phosphate, low dialkyl
phosphate and high residual phosphoric acid [15]. Reaction
of polyphosphoric acid (Fig. 6) with an alcohol results in the
cleavage of the polyphosphoric acid chain. In this reaction a
large amount of residual phosphoric acid is formed because
each chain produces one mole of phosphoric acid. One mole
of phosphoric acid would theoretically be produced from the
tail end of each chain, or alternatively, the amount of phos-
phorus remaining, as H3PO4 would be equal to 1/n where n
equals the average polymer chain length. The monoalkyl to
dialkyl ratio increases with increasing reaction temperature
and decreasing strength of the polyphosphoric acid [16].
3.3 Phosphorus Oxychloride
Phosphorus oxychloride is a highly reactive, colorless, low-
viscosity liquid and hydrolyses in moist air to phosphoric
acid to release fumes of hydrogen chloride. Phosphorus oxy-
chloride is tetrahedral in shape, featuring three P–Cl bonds
and one very strong P=O double bond. The reaction of phos-
phorous oxychloride with alcohol gives phosphate ester en-
rich in triester (Fig. 7). Phosphorus oxychloride is the only
phosphating agent, which gives a high content of triesters
[17]. It produces three moles of HCl that makes it highly cor-
268
Molecular Formula Structure
P2O5
(H)n+2 · (P)n · (O)3n+1
POCl3
H3PO4
H4P2O7
rosive. It also produces undesirable alkyl chloride, so that it
is difficult to enhance the phosphoric monoester content of
the reaction product [18].
3.4 Orthophosphoric Acid
Pure orthophosphoric acid corresponds theoretically to a
mixture of H2O and P2O5 in the ratio of 3 moles of water to
1 mole of P2O5 and is expressed as phosphoric acid contain-
ing 72.4 % P2O5 [19]. It is a white solid that melts at 42.35 8C
to form a colorless, viscous liquid. Phosphoric acid is a very
polar molecule; therefore it is highly soluble in water. Phos-
phoric acid molecule can form a monoalkyl, a dialkyl, or a
trialkyl ester by reaction with one, two, or three molecules
of an alcohol.
3.5 Pyrophosphoric Acid
Pyrophosphoric acid is colorless, odorless, hygroscopic and
soluble in water, diethyl ether, and ethyl alcohol. It is pro-
duced from phosphoric acid by dehydration. Pyrophosphoric
acid and phosphoric anhydride (P2O5) are generally two dif-
ferent types of commercially used phosphating agents. The
selection of the phosphating reagent has an effect on the ra-
tio of the components and on the functional properties of
the final product [20].
4 Synthesis of Phosphate Esters
Phosphate esters are the reaction products of phosphating
agent and alcohol. Typically, phosphate ester surfactants are
produced by the reaction of alcohols with an activated phos-
phorous derivative. Phosphate ester products are a mixture
Tenside Surf. Det. 55 (2018) 4
 Pinklesh Arora et al.: Synthesis, Properties and applications of anionic phosphate ester surfactants: a review
Tenside Surfactants Detergents downloaded from www.hanser-elibrary.com by Hanser - Library on July 31, 2018
of monoalkyl phosphate (monoester), dialkyl phosphate (die-
For personal use only.
ster), residual alcohol and residual phosphoric acid [21].
There can be a range of phosphate esters depending upon
the base material used. For example, if the base material is
ethoxylated tridecyl alcohol, several products can be of vary-
ing the number of moles of ethylene oxide attached to the
alcohol. A series of products with a wide range of properties
can be obtained. The quality and properties of phosphate es-
ters can be altered by selection of base materials, phosphat-
ing agents and reaction conditions [22].
There are various patented methods available for the syn-
thesis of phosphate ester surfactants. Mostly, application
based methodology has been followed to develop the product
mixture of the targeted ratio of the monoester, diester, residu-
al phosphoric acid and ethoxylates i. e. the base materials can
be adjusted to get the desired applicability of the final pro-
duct.
For personal care applications, high content of monoalkyl
ester, low level of residual phosphoric acid and residual alco-
hol formulations are most preferred. Monesters are also pre-
ferred over diesters due to their excellent detergency, foam
formation, stability, low surface tension and skin irritation
[4]. The presence of high content of diesters causes poor de-
tergency, low water solubility and foaming. Many mono-
esters with relatively high percentage diesters, display in-
creased surface tension in aqueous solution and reduces
their cleansing effectiveness [23]. Furthermore, a large
amount of residual alcohol causes low solubility, skin irrita-
tion and haziness to formulation, while the presence of re-
sidual phosphoric acid increases the viscosity of solution
making it unmanageable for formulations. Hence, it is ne-
cessary to remove the excess alcohol and phosphoric acid
from the product [24]. A composition containing a high con-
tent of monoester of at least 95 % is so effective in solubiliz-
ing that they do not require the presence of additional
hydrotropes to prevent precipitation of other active ingredi-
ents and have high chemical stability. The desired ester is
obtained by mixing stoichiometric equivalents of a mixture
Tenside Surf. Det. 55 (2018) 4
Figure 6 Reaction of polyphosphoric acid with
alcohol for synthesis of phosphate esters
Figure 7 Reaction of phosphorus oxychloride
with alcohol for synthesis of phosphate esters
Figure 8 Reaction of orthophosphoric acid with
alcohol for synthesis of phosphate esters
of ethoxylated alcohols with 115 % to 116 % polyphosphoric
acid at ambient temperature [25].
The phosphate esters with high monoalkyl content are
generally made by reacting the base alcohol or alcohol ethox-
ylates with polyphosphoric acid [19]. In this method the pro-
duct has a higher amount of residual phosphoric acid which
is undesirable in the use of personal care applications [18].
The presence of high level of residual phosphoric acid may
cause the phase separation problem in formulation [12].
Phosphate ester with a high amount of monoester can be
prepared by the esterification of the alcohol with a two-step
reaction. In the first step, the organic hydroxy compound is
esterified in the presence of an excess amount of one or
more phosphating agents selected from the group consist-
ing of phosphorus pentoxide, phosphoric acid and poly-
phosphoric acids. In the second step, a further portion of
the same organic hydroxy compound is added to the reac-
tion mixture of the first step. The reaction product on the
analysis shows the 80.5 % monoalkyl phosphate, 7.8 % of
dialkyl phosphate and 11.7 % of orthophosphoric acid [21].
In an industrial process of phosphate ester preparation
using the P2O5 method, a reaction product has an enriched
amount of monoalkyl phosphate and a reduced amount of
orthophosphoric acid depending on product. In this method
the base material (alcohol ethoxylate) is added in two steps,
so that the reaction product has an enhanced ratio of
monoester to the diester. The phosphating agent, P2O5 is
added to one mole of alcohol and the reaction was carried
out at 80 8C for one hour [19].
The typical phosphation processes do not produce pro-
ducts with the high monoalkyl phosphate together with the
low dialkyl phosphate, low phosphoric acid and residual al-
cohol contents. In the reaction process a phosphating agent
is selected to use in a single step, solventless process having
compositions with high level of monoalkyl phosphate, low
levels of free phosphoric acid and residual alcohol. The
phosphating reagent is prepared by blending of phosphoric
anhydride with phosphoric acid to form a slurry or paste. It
269
 Pinklesh Arora et al.: Synthesis, Properties and applications of anionic phosphate ester surfactants: a review
dissolves more easily than phosphoric anhydride and can be
added to alcohol to reduce the exothermic reaction problems
and black chunks, which are formed during the addition of
phosphorus anhydride [18]. This phosphating agent when
reacted with alcohols under optimized reaction conditions
yields a product having monoalkyl phosphate to diakyl phos-
phate ratio greater than 80:20 with low level of residual
phosphoric acid and alcohol [26 – 28].
A process was developed for the preparation of a phospho-
ric monoester with high purity and a lower residual ortho-
phosphoric acid content, which does not give any product
of high-viscosity gel and has good odor. In this process, reac-
tion was carried out in two steps. In the first step an organic
hydroxyl compound was reacted with polyphosphoric acid at
60 8C to 100 8C for 5 h. In the second step phosphorus pen-
taoxide is added and the reaction was kept at 60 8C to 100 8C
for 5 – 15 h. The reaction product contains a compound hav-
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ing a pyrophosphate bond, if in a large amount it increases
the viscosity of the product. In order to hydrolyze the pyro-
phosphates, water is added. The unreacted organic hydroxyl
compound is removed by steam distillation [29].
A mixture of monoalkyl phosphate and dialkyl phosphate
esters was synthesized and the structure of hexadecyl phos-
phate ester with a low mono/dimole ratio was confirmed by
FTIR and NMR. The surface tensions of these alkyl phos-
phate esters were analyzed using a surface tensiometer. The
results showed that the critical micelle concentration (CMC)
and critical surface tension of phosphate esters with a high
mono/di ratio decreases with the increase of alkyl chain
length [30]. During the synthesis of phosphate esters, diox-
For personal use only.
anes are formed. 1,4-dioxane is carcinogenic and has a low
rate of biodegradability, hence it is desirable to reduce the
formation of this material during phosphation. 1,4-Dioxane
is produced as a by-product in the processes in which poly-
ethylene glycol chains are in contact with even catalytic
amounts of strong acid. To control the formation of 1,4-diox-
ane, the phosphation reaction was carried out in two steps.
In the first step the phosphoric anhydride was blended with
polyphosphoric acid to form a slurry or paste under mild
conditions. In the second step this phosphating reagent was
mixed with alcohol ethoxylate and the reaction mixture was
kept at 100 8C for 5 h to conduct the reaction. The 1,4-diox-
ane level was found to be reduced to less than 15 ppm based
on the total weight of the active ingredient [31, 32].
An amphoteric phosphate ester surfactant was synthe-
sized by using polyphosphoric acid as phosphorylation re-
agent at 80 8C and 5.5 hour reaction time. The monoalkyl
phosphate content and the conversion rate was found to be
89.3 % and 97.2 % respectively [33].
5 Applications of Phosphate Esters
Phosphate esters have industrial applications due to their
overall stability, especially in the presence of oxygen [34].
Phosphate esters are distinguished within their class of sur-
factants because of the additional unique characteristic of
the phosphate group. They have the broad range of applica-
tions because of the versatility in structure and properties.
They are excellent hydrotropes and effective coupling agents,
which give outstanding wetting, emulsification and deter-
gency. They are widely used in emulsion polymerization,
textile auxiliaries, maintenance chemicals, metal finishing
and many other applications. Phosphate esters of organic
hydroxyl compounds are used in a wide field as detergent,
textile treating agent, emulsifying agent, rust preventive
and liquid ion exchanger [19]. In addition to the surfactant
properties, a significant benefit provided by the phosphate
270
group is adhesion enhancement. Phosphate esters are used
as anti-wear, anti-corrosion and adhesion promoting addi-
tives in metal lubricants and coatings and as anti-stripping
agents for the aggregates in asphalt. Higher MAP content
contributes to higher performance in these applications [6].
These high monoalkyl phosphate surfactants exhibit a un-
ique combination of good detergency and low skin irritancy,
especially in comparison to alkyl sulphate or alkyl sulpho-
nate surfactant [35].
Phosphate esters have an unique range of properties,
which are exploited in the production of specialized chemi-
cal processing aids for industry [36]. They are especially use-
ful in household and maintenance cleaning products. Phos-
phate esters are extremely soluble in alkaline solutions and
have excellent heat and chemical stability. They are very effi-
cient emulsifiers and provide excellent wetting properties at
temperature above 50 8C. Phosphate esters have a greater
solubility and compatibility than the nonionic surfactants
from which they are derived. Applications include uses as
cleansing agents, emulsifiers, wetting agents and disper-
sants. The choice of a phosphate ester for a specific applica-
tion is highly dependent upon the monoalkyl to dialkyl
phosphate ratio. Other important performance parameters
include the amount of residual alcohol and phosphoric acid
present in the surfactant [37, 38].
Phosphate esters have been used as fire resistant hydrau-
lic fluids in a wide variety of industrial processes and they
have made a significant contribution to a safe working envi-
ronment for operating personnel [39]. Phosphate esters are
used as lubricants due to good thermal stability, high film
strength, lack of flammability, non-corrosiveness, excellent
boundary lubrication properties, low volatility and fair hy-
drolytic stability [28].
Phosphate ester surfactants are also applied as surface ac-
tive agents [40, 41], flame retarding agents [42 – 45], anti-
freeze liquids [46], emulsifiers [47, 48], special fertilizers
[49 – 52] and in emulsion polymerization [53]. The important
application of aryl phosphates is in the field of hydraulic
fluid and lubricants [54 – 56]. The aryl phosphates are also
used as rust and corrosion inhibitors [57, 58]. The use of
phosphate ester surfactants is also reported in pigment ink
for jet printing [59, 60], water based ink compositions con-
taining water-soluble and water insoluble resins [61]. Other
significant applications are as environmentally degradable
pesticides due to their toxicity to a wide range of insects
and their relatively short residence time in the environment
[62].
6 Global Market and Manufacturers of Phosphate Esters
The global phosphate ester market was valued at USD 843.9
Million in 2017 and is expected at USD 1,179.8 Million by
2022, at a CAGR (Compound Annual Growth Rate) of
6.9 % from 2017 to 2022. The market will grow due to high
demand for phosphate esters from the Asia-Pacific region
and technological advancements in lubricants, surfactants,
pesticides, fire retardants, hydraulic fluids, plasticizers, and
paints and coatings for application-based end-use industries
[63]. Phosphate esters have been manufacturing worldwide
with different carbon chain length and ethylene oxide mo-
les. Asia pacific is the major manufacture of the phosphate
ester. North America and Europe have stringent regulations
regarding manufacturing as well as usage of phosphate es-
ter. Thus owing to the presence of few manufacturers in
North American and Europe, there is low production in this
region [64]. The major manufacturers of phosphate esters
are summarized in Table 2.
Tenside Surf. Det. 55 (2018) 4
 Pinklesh Arora et al.: Synthesis, Properties and applications of anionic phosphate ester surfactants: a review

S. No. Manufactur- Location Trade Name HPTLC and GC has to be explored for the structure activity
er correlation.
1 Rhodia France Rhodafac
References
2 Akzo Nobel USA Phospholan
1. http://www.elementisspecialties.com/esweb/esweb.nsf/pages/
3 Cognis Korea Agnique surfactants-anionicsurfactants
2. Williamson, S. C.: Cleansing compositions comprising ethoxylated alcohol
4 Ashland USA Dextrol, Strodex, Zenix monoesters of phosphoric acid, U.S. Patent 4493782 (1985).
3. Report on \North America Phosphate Esters Market: By Type (Tri Aryl/Alkyl Aryl
5 Clariant Germany Hordaphos Phosphate Esters, Tri Alkyl Phosphate Ester and Bisphosphates); By Application
(Lubricants, Surfactants, Pesticides, Fire Retardants, Hydraulic Fluids, Plastici-
6 Dow Midland-USA Triton zers, Paints & Coatings, and Others); By Geography (U.S., Canada, and Mexico)
– Forecasts till 2020", 2016, Report Code-PH1001.
7 Ethox USA Ethfac 4. Derian, P. J., Tao, G., Herve, P. J. C. and Reierson, R. L.: High solids, pumpable
aqueous compositions of high monoalkyl phosphate ester salt content, U.S.
8 Chemcor USA Phoschem Patent 6262130 (2001).
5. http://www.elementisspecialties.com/esweb/esweb.nsf/pages/surfactants-
9 BASF USA Maphos anionicsurfactants.
6. Reierson, R. L., Crooks, R., Gabbianelli, A. and Warburton, S.: Phosphate Esters:
10 Librachem USA Libraphos
A natural for personal care and cosmetic applications, Cosmetic Science Tech-
11 Croda USA Crodaphos nology, T4 International, Hertfordshire (2006) 267 – 274.
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7. https://biokhimact.com.ua/images/catalogs/Surfactants.pdf.
12 De-forest USA Dephos 8. http://www.rimpro-india.com/articles1/surfactants-widely-used-in-industrial-
processes-fatty-alcohol-ethoxylate,-fatty-acid-ethoxylate.html.
13 Stepan USA Stepfac 9. https://sites.google.com/site/demulsifiers/home/fatty-alcohol-ethoxylate-
fatty-acid-ethoxylate-surfactants-for-industries.
14 Uniqema USA Monafax 10. Tracy, D. J. and Reierson, R. L.: Phosphate ester surfactants, Handbook of De-
tergents Part F: Production, Surfactant Science Series, edited by U. Zoller and
15 Lubrizol USA Lubrizol P. Sosis, CRC Press, Boca Raton, Florida, USA, 142 (2009) 183 – 199.
DOI:10.1201/9781420014655
16 Ilcochem Germany Ilcophos 11. Tadashi, H., Method for producing copolymerizable compound containing
functional group of phosphoric acid, US 3686371 A, 1972.
17 Lankem UK Lanphos 12. Reierson, R. L.: Phosphation reagent, US 6136221 A, 2000.
13. Thilo, V. E. and Sauer, R.: On the chemistry of condensed phosphates and ar-
18 MFG Chemicals USA Ultaphos senates. XVII. The course and products of dehydration of monophosphoric acid
H3PO4, J. Prakl. Chem. 4 (1957) 324 – 348. DOI:10.1002/prac.19570040512
19 Lakeland UK Lakeland PA 14. Clarke, F. and Lyons, J.: The alcoholysis of polyphosphoric acid, J. Am. Chem.
Soc., 88 (1966) 4401 – 4405. DOI:10.1021/ja00971a018
For personal use only.

Table 2 Main manufacturers of phosphate esters
7 Conclusions
Phosphate esters are highly versatile, multifunctional anion-
ic surfactants with a useful combination of multifunctional
properties. The properties of phosphate esters depend on
several factors such as the type of alcohols used as raw ma-
terial, phosphating agents, degree of ethoxylation of alco-
hols, synthesis process and mono/diester ratio of phosphate
esters. Using different phosphating materials and alcohols,
a range of phosphate esters can be synthesized. Phosphate
esters are distinguished within their surfactant class because
of the additional, unique properties of the phosphate group.
They have the broad range of applications because of the
versatility in structure and properties. High content of
monoalkyl ester, low level of residual phosphoric acid and
residual alcohol, the formulations are preferred in personal
care applications. The monoesters have excellent detergency,
foam formation, stability, low surface tension and skin irrita-
tion. The presence of high content of diesters causes poor
detergency, low water solubility and foaming. Large amount
of residual alcohol causes low solubility, skin irritation and
haziness during formulation, while the presence of residual
phosphoric acid increases the viscosity of solution making it
unmanageable for formulations. Phosphate esters have been
manufactured worldwide with different carbon chain length
and EO moles as per their respective applications. Asia paci-
fic is the major manufacturer of the phosphate ester.
Although phosphate ester surfactants are the most pre-
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Tenside Surf. Det.
55 (2018) 4; page 266 – 272
ª Carl Hanser Verlag GmbH & Co. KG
ISSN 0932-3414
y Correspondence address
Dr. Pinklesh Arora
Shriram Institute for Industrial Research,
19 University Road
Delhi – 110007
India
Tel.: +91112766 7267
Fax: +91112766 76 76
E-Mail: pinklesh@shriraminstitute.org
The authors of this paper
Dr. Pinklesh Arora, has done her Ph. D. in 2009 from C.C.S. University, Meerut, In-
dia. She has 11 years experience in Shriram Institute for Industrial Research, Delhi,
India in the field of surfactants, polymers, polymer nanocomposites and adhesives.
She has been worked on various national and international R & D projects. She has
authored one book, five research papers and five conference papers in her credit.
Dr. Rakhi Singh has done her Ph. D. from B.R. Ambedkar University, Agra, India in
2007. She has got 11 years experience in Shriram Institute for Industrial Research,
Delhi, India as Scientist in the field of development and modification of surfactants,
optical polymers, perm-selective membranes and analytical chemistry. She has also
research experience on method development and validations of various national
and international R & D projects. She has authored two chapters in book, two re-
search papers and four conference papers in her credit.
Dr. Geetha Seshadri, Assistant Director & Chief, has done her Ph. D. from Dr. B. R.
Ambedkar University, Agra, India in 2001. She has 22 years research experience in
the areas of fluoropolymers, surfactants, optical polymers, polymer nanocompo-
sites, block co-polymers & tetrazole, perm-selective membranes and lubricants etc.
She has authored one book, more than 30 research and conference papers and 13
patents. She has headed various research projects from national and international
agencies.
Dr. Ajay Kumar Tyagi, Senior Assistant Director & Chief and Head of the Depart-
ment, Material Science Division has 33 years of research experience. He has com-
pleted his Ph.D in 1998 from Kanpur University, Kanpur, India. His research experi-
ence is exclusively in the fields of polymer synthesis and their modifications such as
polylactide, polyglycolide, glycolide-caprolactone copolymers, styrene – butadiene
– styrene triblock copolymer, perfluorinated lubricating oil from hexafluoro propy-
lene as radiation resistant materials, polyurethane based perm selective mem-
branes, dry lubricants, adhesives and derivatization of natural polymers etc. He has
executed various national and international research projects. He has published
more than 35 research papers in national and international journals and five pa-
tents. He is a member of Association of Carbohydrate Chemists and Technologists
(India).
Tenside Surf. Det. 55 (2018) 4