CHEMICALS

SUBSTITUTION
NEWSLETTER #15
SEPTEMBER 2019

APEO: OVERVIEW OF butadiene polymer used in tyres), OH

O
THEIR APPLICATIONS vinyl-acrylic and styrene-acrylic n
AND ALTERNATIVES polymers. They are also emulsifiers Figure 2/ Structure of alcohol ethoxylates
and dispersants for the formulation
Ethoxylated alkylphenols (APEOs) of water-based paints and pesticides. There are several hundred alcohol
are nonionic surfactants, among The surfactant properties of ethoxylates with different physical
which the two most commonly OPEOs allow them to integrate the and chemical properties depending
used subgroups are ethoxylated formulation of detergent/cleaning on the length of the alcohol and
nonylphenols (NPEOs) and, to a lesser and anti-foam products. OPEOs ethoxylate chains. Alcohol ethoxylates
extent, ethoxylated octylphenols are part of the synthetic reagents can replace APEOs when the latter
(OPEOs). of octylphenol ether sulfates used are used as emulsifiers for the
in water-based paints for their production of paints and adhesives
NPEOs can be used as emulsifiers1 emulsifying properties. and as dispersing agents for the
for the emulsion production of formulation of paints and inks. A priori,
polymers2, paints, adhesives, additives To date, there are many alternatives to alcohol ethoxylates would generally
or as dispersing agents3, especially NPEO and OPEO when the latter are be more expensive than NPEO
for ink formulation. However, the legal used to form and stabilize an emulsion (20 to 30%), however, it is possible
framework governing the use of NPEOs (emulsifier) or to limit the flocculation that some surfactants (or mixtures
is becoming increasingly stringent. phenomenon (dispersing agent). of surfactants) may require lower
This article is not intended to provide concentrations at equal performance.
an exhaustive list of all alternatives For example, BASF and HUNTSMAN
available on the market, but to list the produce the LUTENSOL® and
main alternatives to APEOs for uses SURFONIC® respectively based on
that are not yet restricted by regulation. alcohol ethoxylates.

To date, alcohol ethoxylates

are the most commonly used Additive for forming and stabilizing
1

products to replace nonylphenol an emulsion

Figure 1/ Structure of APEOs 2
ABS, ESBR (styrene-butadiene rubber),
ethoxylates. Alcohol ethoxylates are ENBR, PVC, PTFE (Polytetrafluoroethylene),
non-ionic surfactants composed PVA (PolyVinyl Acetate), PMMA,
OPEOs are mainly used as emulsifiers of hydrophobic fatty alcohols4 polyacrylates for paints
3
Additive to limit the flocculation
for the production of emulsion combined with a varied number of phenomenon
polymers such as SBR (styrene- ethoxylate groups. 4
long carbon chain

French national institute for industrial environment and risks (Ineris)

Parc technologique Alata • BP 2 • F-60550 Verneuil-en-Halatte
+33 3 44 55 66 77 • ineris@ineris.fr • www.ineris.fr
 can replace APEOs both for the combines high-boiling solvents,
emulsion production of polymers and substances with anti-foaming
for the formulation of pesticides (OPEOs properties and 4-nonylphenol,
can be used as dispersing agents). branched and linear, ethoxylated
(n°CAS 127087-87-0).
Figure 3/ Structure of Alcohol ethoxylate/
propoxylate
Soon, European regulations on the use
Alcohol ethoxylate/propoxylate of chemicals will require authorization
copolymers correspond to a class of for 4-nonylphenol, branched and linear,
chemical substances similar to alcohol Figure 7/ Structure of phosphate ester ethoxylated (CAS No. 127087-87-0).
ethoxylates, with the difference that In this context, BYK (ALTANA group)
one or more propoxylate group(s) is There are also biosourced solutions reformulated the additive BYKETOL-
(are) used instead of a corresponding available to replace APEOs for WS by removing this APEO from its
number of ethoxylated group(s). applications to emulsify polymers: composition, leading to the creation of
these are mainly emulsifiers BYKETOL WA.
These substances replace APEOs as synthesized from glucose. For
dispersants and emulsifiers and have example, SEPPIC has developed the According to BYK, BYKETOL-WA would
applications such as paints and coatings MONTANETM range, which includes have almost identical performance
or inks. For example, DOW markets non-ionic emulsifiers obtained by to its APEO-containing counterpart
the ECOSURFTM range of surfactants esterifying sorbitol with a fatty acid. (BYKETOL WS).
based on 2-((1-((2-ethylhexyl)polyoxy)
poly-propan-2-yl)oxy)ethanol (n°CAS SMA (Styrene Maleic Anhydride Sources :
64366-70-7). n°CAS 9011-13-6) is a copolymer able https://www.byk.com/fr/additifs/additifs-par-
to substitute dispersing agents based nom/byketol-wa.php

Another alternative to APEOs is the use on NPEO or OPEO for pigments, inks,
of sulphur-based anionic emulsifiers and coatings, adhesives...
dispersants such as alkyl or aryl ethoxy
sulfates, sulfonates and alkyl sulfates. There are two major producers of AN ON-LINE TOOL
For example, CLARIANT has developed SMAs on the market, namely: SOLENIS FOR RESEARCHING
various alkyl and aryl ethoxy sulfates (SCRIPSETTM) and POLYSCOPE ALTERNATIVES TO
which, depending on the product POLYMERS (XIRAN®). PHTHALATES
used, promote the emulsion of various
polymers (acrylic, styrene-acrylic, vinyl Sources : In order to simplify your search for
acetate, styrene-butadiene, PVC), these Technical and economic data on octylphenols phthalates alternatives, a table in
products are grouped together in the and ethoxylates (in French) Microsoft® Excel format compiling all
EMULSOGEN® ranges (EMULSOGEN Technical and economic data on nonylphenols the information on this subject and
APS, EPA 073, LA 083, LCA 213, FP...). and ethoxylates (in French) posted on the phthalates substitution
KEMI (2013) ANNEX XV RESTRICTION website has just been published.
REPORT – NONYLPHENOL AND
NONYLPHENOLETOXYLATES IN TEXTILES
Via this table, you can search for
alternative solutions: for PVC or other
SUBSPORT (2013) Specific Substances
Alternatives Assessment – Nonylphenols and
materials; for an application sector
Nonylphenol ethoxylates (for example: medical, construction,
Figure 4/ Structure of alkyl ethoxy sulfates
textiles...) or for a particular application
(floor coverings, PVC foams...). This
table also includes information on
BYK PUT ON THE the alternative material or substance:
MARKET A RELEASE OF examples of the trade name of the
BYKETOL-WS WITHOUT alternative and identification of
Figure 5/ Sulfonate structure APEO developers and/or producers and/or
suppliers. For more information about
BYKETOL-WS is a leveling agent with an alternative solution, the hypertext
anti-foaming properties designed for link associated with it allows you to
water-borne coatings (undercoats directly access the document that
and top coats for the automotive generated the information. In the future,
sector and varnishes for the wood this tool will be updated with each
Figure 6/ Alkyl sulfate structure
and furniture sector). The BYKETOL- major modification of the phthalates
WS is designed to prevent surface substitution website.
Marketed, among others by ADDAPT defects in the coating («pinholes»,
https://substitution-phtalates.ineris.fr/sites/
CHEMICALS BV via its PEXTM range, bubbles, orange peel, craters) and to substitution-phtalates/files/documents/drc-165804-
alkyl phosphates, anionic surfactants, improve its levelling. Its composition 00941a_outil_de_recherche_phtalates_vf_0.xls

INERIS • NEWSLETTER CHEMINALS SUBSTITUTION #15

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COMING SOON FACHPACK 2019 in Nuremberg INPRINT 2019 in Munich
(Germany) from September 24th (Germany) from November 12th
Workshop "The substitution of to 26th, 2019 to 14th, 2019
chemicals in the textile sector", in
La Défense (France) on January 9. This show is an appointment for The INPRINT exhibition is for
professionals in packaging, marking professionals in many printing
This workshop, organized by INERIS and handling, all industrial sectors sectors (ceramics, textiles, packaging,
in collaboration with the Ministry of combined (food, beverage...). Innovative aerospace, automotive ...). It offers
Ecological and Solidarity Transition, aims bisphenol-free solutions are likely to be the opportunity to discuss the
to bring together actors from the textile presented. latest innovations that could replace
sector, as well as civil society stakeholders, https://www.fachpack.de/en alkylphenol ethoxylates.
in order to promote exchanges on the https://www.inprintmunich.com/
challenges, obstacles and drivers of
chemical substitution in this sector.
K 2019 in Düsseldorf (Germany)
It will also be an opportunity to from October 16th to 23th, 2019
communicate on the needs and
availability of alternatives, and to report The triennial K trade fair for the
on the industrial implementation of plastics and rubber industry will
alternative solutions. be organized around four themes
including raw materials and auxiliaries.
The programme will be communicated On this occasion, plasticizer producers
soon. able to replace phthalates will be
For more information, contact: present.
pierre.boucard@ineris.fr https://www.k-tradefair.fr/

If you have any questions,

please contact us:
https://substitution.ineris.fr/en/contact

https://substitution.ineris.fr

INERIS • NEWSLETTER CHEMINALS SUBSTITUTION #15

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