21st CENTURY

SURFACTANTS
RESEARCH & INNOVATION

White paper with studies on surfactants for PU foams

developed at CONCENTROL R+D laboratories
INDEX
Introduction ............................................................................................................................2

Testing the effect of the reactivity of silicone surfactants in

polyurethane rigid foams................................................................................................3

New silicone surfactants for low emission HR foams presented at PSE

Europe 2017 ............................................................................................................................5

Study on stabilizers for rigid foam and identification of the most

appropriate surfactant .....................................................................................................7

Silicone surfactants for low content of aldehyde and aromatic

emissions PU Foam ............................................................................................................11

Acoustic insulation for the automotive industry ..............................................20

Evolution of silicone surfactants for high resilience (HR) flexible

polyurethane foam...........................................................................................................23

The sector of polyurethane panels and blocks .................................................25

Silicone surfactants for polyurethane systems in footwear - Part 1 ......29

Silicone surfactants for polyurethane systems in footwear - Part 2 ......31

Surfactants for HFO, the blowing agent of tomorrow in the

polyurethane industry ....................................................................................................33

1
Introduction
Polyurethane foams have a great presence in the industry and in the domestic environment. It
is a very versatile material, since depending on the additives it contains and the
manufacturing systems used, its characteristics and properties can be very different. Its use
can range from the manufacturing of protective foams, mattresses, automotive accessories
and construction materials, to refrigerators and freezers.

In some of its applications it will suit that they are rigid and have good thermal insulation
properties, in others flexibility will be sought and the load (compression characteristics) will
be expected to afford good cushioning. The formulation of each foam will vary according to
the desired properties. However, the production of polyurethane foams, whatever their
application, requires essential additives that stabilise the foam during its production:
surfactants.

Silicone surfactants for polyurethane foams allow improving the emulsification of

polyurethane foam components offering the desired stabilization in the foam expansion
process, as well as good control of the size and distribution of the cells. This provides regular
foam in the blocks and with specific characteristics. Silicone surfactants can also be
formulated to improve some properties of polyurethane foams, such as thermal insulation or
flammability.
Concentrol has a long experience in silicone production for the chemical sector and has the
infrastructure and expert team for bottom-up control of its synthesis.
This enables the possibility that the technical team can design different structures of silicone
surfactants according to the desired characteristics of PU foam.

Research is an essential tool to provide the best possible solutions to our clients. At Concentrol
laboratories we carry out detailed technical studies in order to develop innovative and
effective products that can meet market needs. In addition, we use research to analyse in
depth the new demands and market trends.

At Concentrol we understand that research and development are key to offering high quality
and efficient products and solutions. Therefore, we strive to maintain a high level of
innovation and continuous improvement in all our processes, and share our knowledge in
documents such as this.

2
Testing the effect of the reactivity of silicone
surfactants in polyurethane rigid foams
CONCENTROL has conducted a study on 15 new surfactants used in formulations of rigid
polyurethane foams to analyze the effect of the reactivity of the surfactant on their
properties. CONCENTROL has conducted this study with the aim of providing surfactants with
the best performance and minimum cost to produce polyurethane.

The study was carried out in CONCENTROL's labs and was led by Mr. Josep Nadal, doctor of
chemical sciences and technical director in PU additives.

Rigid polyurethane foams have different applications in industry, construction and the
domestic sphere: refrigerators, freezers, refrigeration chambers, wall coverings and roofs…
Polyurethane in these applications must meet specific properties to obtain good results in
terms of thermal isolation, consistency, flammability and adhesion. Silicone surfactants are
essential components for the production of polyurethane foams because they allow to
stabilize foaming while also improving other properties.

From a chemical perspective, silicone surfactants are formed by a polyether and a

polysiloxane. The study carried out by CONCENTROL focuses on the synthesis of different
groups of surfactants where the only difference is the terminal group of the polyether,
thereby modifying its reactivity.

CONCENTROL, thanks to their synthesizing capabilities, can produce surfactants with

different terminal groups, reactive and non-reactiv, in order to obtain specific properties in
rigid polyurethane foams, such as improving adhesion or to produce one-component foams
(for use with spray guns). In this study, three different situations altering the reactivity were
analyzed:
› Non-capped (-OH)
› Methoxy capped (-OCH3)
› Acetoxy capped (-OCOCH3)

Each of the 3 types of resulting surfactants have different

applications depending on the type of polyurethane desired. The
preparation of polyurethane panels is where most often one of
these 3 types of surfactants is used. For this reason, and in order to
obtain comparable results between 3 variations of surfactants,
CONCENTROL focused this study on analyzing the effects of
reactivity in PUR / PIR formulations in particular.

The study is divided into two parts. In the first, 15

samples of new experimental surfactants using
different types of polysiloxane (based on molecular
weight and ramification) and different types of
polyethers (based on molecular weight and on the
percentage of ethylene oxide EO) are synthesized,
where the only difference is the reactivity. This part of
the study observed the synthesis and characterization
of these surfactants using different technologies to
analyze:

› Polarity (cloud point analysis)

› Infrared spectrum
› Molecular weight

The second part consisted in the physical analysis of

the foams prepared with the surfactants resulting
from the first part of the study, in order to link the
chemical structure with the resulting physical

3
Fig. 1: Surfactants reactivity
parameters. To do so, the following characteristics were taken into account:

› Lambda values (thermal conductivity)

› Flammability
› Measurement of dimensional stability
› General appearance

The results provided by the different analysis show us that, in the chosen formulations for
polyurethane panels, the most important changes in the foam come from the different
combinations of chemical components of the surfactants (EO, PO, Siloxane %) while altering
the reactivity of the terminal group of silicone surfactants does not show an effect on the
quality and performance of polyurethane panel foams.

Therefore we can conclude that in the 3 silicone surfactants synthesis technologies developed
by CONCENTROL's lab for this study (non-capped -OH, -OCH3 capped and -OCOCH3 capped)
no negative effects were detected in the properties (thermal conductivity, flammability,
dimensional stability and overall appearance) of the resulting polyurethane panels.

Capping the reactivity of a surfactant is a synthesis process that makes the resulting product
more expensive. This study demonstrates that this process is not necessary to improve the
properties of the different formulations of PUR / PIR panels studied.

To continue this study, we plan to evaluate the effect of different surfactants in the resulting
foam by analyzing parameters such as adhesion of the foam on the metal sides of the panel
and the effect on the flowability of the foam.

This study was presented to the public last April 2016 at a conference by Mr. Josep Nadal
during the bi-annual CONCENTROL UTECH North America event.

Fig. 2: Visual appearence results of tested surfactants

4
New silicone surfactants for low emission HR foams
presented at PSE Europe 2017
From June 27th to 29th, Concentrol attended PSE Europe (International Polyurethane
Solutions Exhibition) presenting a seminar titled "New silicon surfactants with low emissions
HR foams" by Dr. Josep Nadal and Mr. Adrià López from the technical department.

The presentation was divided into three sections: a general introduction on flexible
polyurethane foams, an experimental section with the results and conclusions. The aim of the
study was to find efficient surfactants which in turn presented the minimum volatile emissions
and to achieve good results in both stability and cellular regulation.

Introduction
At the beginning of the lecture, Dr. Nadal made an introduction about flexible polyurethane
foams and its evolutions throughout the history. Their origin is in the 1950s and suffered
important changes in the 80s with growing demands to reduce the volatile emissions. In the
90s the commercialization of surfactants made with MDI formulations began. The most recent
change was in 2000, when it became possible to analyze precisely the value of the volatile
emissions thanks to the introduction of analysis methods based in thermal desorption.

Dr. Nadal also presented the experiments carried out in Concentrol’s labs, divided into two
parts. The first was the synthesis and characterization of 24 new surfactants designed
specifically for low emissions. This part presented the results of the maximum volatile
emissions of each one of the surfactants from the analysis by gas chromatography (GC)*. The
second part related to the preparation of TDI and MDI foams using the surfactants previously
synthesized. On these foams physical analyzes have been performed and the results have
been related to the theoretical emissions calculated by each of the surfactants.

The 24 new surfactants have been synthesized from the combination of 6 polyethers and 4
polysiloxanes. The analytics include turbidity point analysis to classify surfactants based on
their polarity, molecular weight analysis (by GPC chromatography) and analysis of volatile
components by gas chromatography (GC- FID).

These new surfactants have been tested in two different formulations, representative of those
currently used in the manufacture of polyurethane foam for car seats. A TDI-type formulation
and an MDI-type formulation.

TDI Formulation
The foams with free growth were developed with each of the 24 new surfactants, with the
dosage of 1% (parts per 100 parts of polyol, pphp). A lower density of the foam, good general
appearance and good cell regulation have been the qualitative parameters used to
discriminate 12 of the 24 surfactants as the most appropriate.

Then, these 12 surfactants were tested at 0.5% pphp, 6 of those 12 surfactants even better
results. It could be verified that the density with free growth had dropped significantly,
decreasing from 51 Kg / m3 (foam without surfactant) and from 33 Kg / m3 (foam with
benchmark surfactant CONCENTROL STB PU-1259 PF), to 31 kg / m3 on average and showing
a better stability and general appearance of the foam. Among the 6 surfactants, the MX-11,
MX-12 and MX-13 surfactants were highlighted with the best results.

MDI Formulation
Once the first selection in the TDI foams was made, in this case, only the 12 best surfactants
were tested. The first tested dosage was 0.5% pphp. Coinciding with the previous results, 6
surfactants have been those that have produced the best foams in terms of lower densities,
good appearance and good cellular regulation in general.

5
Regarding free growth density, the foams achieve values in the range of 44-47 Kg / m3, while
the density value without surfactant is 50 Kg / m3 and the density value with the benchmark
surfactant CONCENTROL STB PU-1259 PF is 48 Kg / m3.
After these tests, molded foams were prepared, with a density of 67 Kg / m3, to measure the
values of breaking strength (FTC). A low FTC value is associated with an open cell structure
foam and a high FTC value, to a more closed cell foam. Flexible foams with open cellular
structures are desirable, so usually, a low FTC value with low dependency on the
concentration of surfactant is the most suitable solution. All 6 surfactants show low FTC
values, slightly lower than those obtained using the CONCENTROL STB PU-1259 PF benchmark
surfactant, and therefore an open cell structure.

Emissions of volatile components

Employing the gas chromatography technique by choosing the appropriate patterns, the
present volatile components in each of the surfactants can be quantified. This technique is a
useful, accurate and fast tool for the calculation of the maximum volatile emissions of any
silicone surfactant and is an ideal complement in the use of direct thermal desorption
methods such as the VDA-278.

Through the experiments, the new surfactants MX-01, MX-02 and MX-03 emit less volatile
components than the standard surfactant (CONCENTROL STB PU-1259-PF). This standard
surfactant has been previously evaluated and can be considered to be very low in emissions,
so at least 3 of the new surfactants offer even better results in terms of volatile emissions.

Conclusions
The choice of a correct chemical composition and a proper molecular weight of the
surfactant is the key to reducing the emissions of volatile components (VDA-278) so that
almost any free emission foam can be achieved or related with the surfactant.

6
Study on stabilizers for rigid foam and identification of
the most appropriate surfactant
The term polyurethane is attributed to the wide range of polymers obtained by the
polymerization reaction between the polyol compounds with hydroxyl groups and the
compounds with isocyanate groups. By varying the chemical nature of these two compounds
and the relationship between them, different products can be obtained to cover a wide range
of applications in different industrial sectors, such as flexible foam for the automotive sector
or for the manufacture of sofas and mattresses, rigid foam for insulating sandwich panels,
integral foam for shoe soles or even in applications such as adhesives or elastomers.

At Concentrol we have a wide range of silicone stabilizers that cover the particular needs of
each manufacturer of polyurethane systems. In the following study we evaluated different
silicone stabilizers in a rigid polyurethane system used in the manufacture of continuous
panels. In this case we will focus on two of the most important characteristics of this type of
foam, its low thermal conductivity (lambda value) and its dimensional stability, calculated as
the ratio between the compression forces in the vertical and horizontal directions of
expansion of the foam.

The foaming method consists of a manual mixture of polyol formulation with isocyanate, the
most important parameters being:

• Preparation of the mixture of polyol, a silicone stabilizer, catalysts and a foaming agent
with a special agitator for 15 seconds at 2500 rpm.
• The different reactants are kept at a temperature of 25ºC.
• Addition of MDI and mix for 8 seconds at 2500 rpm.
• Pouring the reaction mixture into a mold of dimensions 30x30x20 cm, where the foam
freely expands. The foaming starts at 25 °C.

First test: density of the foam

The foam density was measured 24 hours after foaming. The result is as follows:

Second test: thermal conductivity

The thermal conductivity was analyzed using a system of heat flow meter NETZSCH model
HFM 436 Lambda. The sample size is 300 mm X 300 mm base length and 30 mm thickness.

7
The system operates according to ASTM C 518, ISO 8301, DIN EN 12667, DIN EN 13163 and JIS
A1412.

Third test: dimensional stability

In this process, the effect of compressing the foam 10% is measured vertically and
horizontally.

8
Fourth test: affectation of aging in conductivity

The foams have been re-analyzed after an aging process. The foams were kept for one
month, tempered at 20 °C, stored without the contact of natural light, and the value of the
thermal conductivity (lambda) was analyzed again.

Fifth test: Fluidity of the foam

Once the foams with the best thermal conductivity values have been selected, they have also
been evaluated in a model test that simulates the flowability of the molten polyurethane.
Silicone stabilizers affect this property, and this test enables us to analyze this effect. In this
case, the free expansion of the foam develops inside a plastic tube 125 mm in diameter. The
height reached by the foam is directly related to fluidity.

9
Conclusions

In the first series of experiments, 3 stabilizers were identified, CONCENTROL STB PU-2242,
STB PU-2285 and STB PU-2245B whose lambda values are the lowest of all the candidates.

In terms of dimensional stability, CONCENTROL STB PU-2242 obtains the best value. All the
candidates are far from the ideal coefficient (1) due to the large differences between the
vertical and horizontal compression forces.

Regarding the value of lambda aged, the best result is obtained with the stabilizer
CONCENTROL STB PU-2285. In all cases the aged values are worse than the initial values,
which coincides with the usual behaviour in the sector.

We conclude that 3 of our silicone stabilizers, CONCENTROL STB PU-2242, STB PU-2285 and
STB PU-2245B are the best candidates.

At Concentrol we consider that this type of studies and tests are key to know in depth the
products we offer and to be able to inform our clients as best as possible about the
possibilities of our products and help them to choose the most suitable ones in each case.

To review Concentrol’s STB PU range of polyurethane stabilizers and all its possibilities
consult here.

10
Silicone surfactants for low content of aldehyde and
aromatic emissions PU Foam
Polyurethanes were invented in 1937 by Otto Bayer and his co-workers. Flexible PU foams
were developed and used in car seats in the early 1950s. In the 1990s, the first low-emission
foams were developed and, due to emanations control, were extended to subsurface
materials used, such as seat cushions. Raw material suppliers were asked to explore the
sources of the emanations and work with OEMs to reduce their overall quantity. At that time,
silicone surfactants played a key role in low emissions. A general overview on the emissions
and the analytical methods used to analyze PU foam emissions was published in 2018, but it
focused mainly on emissions under well-established methods such as VDA 278, which is one of
the standard European methods. As other markets such as the Asia-Pacific economic zone
may have different requirements and quality standards when emissions are considered, we
summarize in this paper the main volatile components currently monitored in this region and
how they are analyzed. We also discuss analytical data regarding the contribution of silicone
surfactants to emissions and how they can be improved to meet customer requirements.

1. Introduction

Automotive market leading OEMs are pursuing a reduction in emission from their plastic
components following the trend of customers worldwide looking for less emission-intensive
environmental conditions. Low volatile organic components (VOC) are thus a requirement of
the industry and different methods have been used worldwide for the material testing. Some
requirements are generally recognized in some countries or economic areas, like the VDA
(Verband der Automobilindustrie) methods in Europe, while other methods are specific for
each car producer and they have some differences that make it difficult to obtain
standardized methods and comparable values.

In the Asia Pacific economic zone, the control of the emissions of very volatile compounds,
specifically a group of aldehydes and aromatic substances, besides the odor control on plastic
components has taken a major importance in the last years.

The main concern is a list of very volatile substances, being the most analyzed ones
summarized in table 1.

Table 1: Properties of volatile substances

(considered as VOC) analyzed in Asia-
Pacific economic zone. (*) LD50 orally in
rats.

11
The list of volatile substances includes a variety of aromatic structures, three aldehydes and
acrolein. They are characterized by a low boiling point (below 150 °C), and regarding its
toxicity (based on LD50 (lethal dose to kill 50% of test population) data), the values are quite
variable, ranging from dangerous substances like acrolein and formaldehyde to substances
with less toxicity like toluene.

Some of the above substances cause also odor. This is a general complaint of consumers
when they get in close contact with goods that contain plastic parts, especially when they are
recently produced. Odor is a very sensitive feeling and it has been regarded as extremely
difficult to quantitatively ascertain odors through equipment analysis. Many chemicals have
odor, and so generally speaking, odor components are said to be substances with a molecular
weight of around 20 – 400 g/mol.

As an example, the following chemicals analyzed as odor substances under the specifications
of some methods (according to Hyundai-Kia MS 300-55):

• Butyl acetate
• Acetaldehyde
• Propionaldehyde
• Butylaldehyde
• Valeraldehyde
• Nonyladehyde
• Decylaldehyde
• Methyl ethyl ketone
• Methyl iso-butyl ketone
• Trimethylamine

2. VOC emissions – Study background

The range of additives for HR molded and slabstock foam, Concentrol STB PU-12XX
PF was released more than ten years ago to introduce phthalate free versions of the
well stabilized Concentrol STB PU-12XX range of surfactants, maintaining their performance
and recognized technical capabilities.

With this new range of additives, the emissions under methods like VDA278 were very low,
especially in some of the last references introduced into the market. But the emissions of
certain aldehydes were found to be not as low as some customers require.

More recently and considering the needs found in the Asia-Pacific economic zone regarding
emissions and odor, a new family of additives has been developed under the tradename
Concentrol STB PU-12XX PFJ.

The new references had shown excellent emissions results, under well-established methods
like VDA-278 and also regarding aldehydes, aromatic substances and odor, compared with
existing surfactants. The materials had been evaluated in different countries and using
different methods, showing in all cases improved values compared with materials made with
Concentrol STB PU-12XX PF. It also showed, in most cases, improved values of emissions
compared with other well-established references available on the market.

3. VOC methods

Gaseous VOC constituents emitted from test samples are captured and identified depending
on the chosen method. Some of the most used methods for the analysis of aldehydes and
aromatic substances are summarized in table 2.

12
 Specification Test Method VOC Test Description

Hyundai-Kia MS300-55 3L bag – DNPH & VOC analysis

Various size bag – DNPH & VOC analysis – 1

Toyota TSM 0508G
part & 1 background

Method #2 – 10L bag – DNPH & VOC

Nissan NES M0402
analysis – 1 part & 1 background

Method #1 – 2000L bag – DNPH & VOC

Nissan NES M0402
analysis – 1 part & 1 background

Honda DWG 0094Z SNA 0000 3-day bag prep – DNPH & VOC analysis

20L pot – DNPH & VOC analysis – blank &

Mazda MES CF 080 B
test part

Table 2: List of methods for the analysis of aromatic substances and aldehydes.

4. VOC analysis of silicone surfactant. Results

The first analysis was conducted directly on the sample of each silicone surfactant. So the
substances analyzed were part of the stabilizer, were byproducts of the reaction or were non-
intentionally added substances (NIAS), coming from the process or the raw materials used.

Regarding the aldehydes, it is believed that they are degradation products (mainly from
oxidation processes), most of them coming from the polyether part of the surfactant. The
siloxane backbone is not believed to be a major constituent of aldehyde emissions, nor of
aromatic ones. Usually, the VOC emissions of the siloxane backbone are low molecular weight
linear siloxanes and cyclic structures (Dx), that are usually well analyzed by thermo
desorption methods like VDA278.

The aromatic substances can be present because of the chemical process (residues of the
solvents used in the reaction) or they can be NIAS. The chemical process depends on each
producer, and the preparation of the surfactants without the use of any aromatic component
is thus a clear advantage. At Concentrol, the preparation of the stabilizers is always done in a
free of aromatic components synthesis.

4.1 Emissions of silicone surfactants. Comparison between PF and new PFJ

families

13
The method used was TSM 0508G (Toyota). The emissions of PF and PFJ surfactants were
directly measured from the sample. The results of seven VOC components are summarized
and illustrated in Figure 2 and Table 3.

Fig. 1 : Comparison of VOC values between PF and PFJ families

(concentration in μg/piece).

STB PU-1259
Substance STB PU-1234 PF STB PU-1254 PFJ STB PU-1259 PFJ
PF

Toluene 0,74 1,86 0,13 0

Ethylbenzene 5,25 0 0 0

Xylene 2,12 3,34 0,21 0,71

Styrene 0 0 0 0

Formaldehyde 4,8 6,21 0.98 0,06

Acetaldehyde 38,8 94,7 0.98 0,05

Propionaldehyde 1726 628 2,58 8,64

The new PFJ family highly improves the emissions of aldehydes compared with the values
obtained with PF family of 3:
Table surfactants.
Comparison ofRegarding the aromatic
VOC values between emissions,
PF and PFJ families all references gave
comparable results. (concentration in μg/piece).

14
4.2 Emissions of silicone surfactants: Comparison between new PFJ family
and comparative silicone surfactants

The method used was TSM 0508G (Toyota). The emissions of PFJ families as well as silicone
surfactants A-F were directly measured from the samples. The results of the seven VOC
components are summarized and illustrated in Figure 2 and Table 4.

Fig. 2: Comparison of VOC emissions from foam samples made with

PFJ references and a standard stabilizer (concentration in μg/m3).

S T B
STB PU-1254
Substance PU-1259 A B C D E F
PFJ
PFJ

Toluene 0,13 0 2,45 1,1 0,71 1,83 7,23 10,8

Ethylbenzene 0 0 2,15 2,18 1,38 1,79 6,34 0

Xylene 0,21 0,71 2,54 2,48 12,8 0,62 10,81 0,54

Styrene 0 0 1,18 1,06 1,91 2,24 1,92 0,36

Formaldehyde 0.98 0,06 0,23 4,43 41,2 26,5 0,96 1,92

Acetaldehyde 0.98 0,05 1,22 9,62 915 3,56 26 5

Propionaldehyde 2,58 8,64 244 4465 2301 4263 3122 164

Table 4: Comparison of VOC emissions from foam samples made with PFJ references and a
standard stabilizer (concentration in μg/m3).

15
The new PFJ family offers very low emissions in all substances analyzed. Especially regarding
the aldehydes, the obtained values are clearly better compared with comparative silicone
surfactants. In all cases, propionaldehyde is the main source of aldehyde-type emissions.

5. VOC and odor analysis of polyurethane foams

Besides the results of emissions directly measured from the silicone surfactant seen in the
previous analysis, the values of the emissions of PU foam samples were also investigated. In
the first experiment (5.1) three PFJ references were compared with each other, and also with
a reference surfactant (sample G), analyzing both the VOC emissions and a list of ten
substances that are known to be odor sources. The second experiment (5.2) compares the
emissions of silicone STB PU-1259 PFJ (two dosages) with those found using two standard
stabilizers.

5.1 Comparison between three PFJ references and one standard surfactant

Four foams were prepared using three PFJ stabilizers and a reference foam using a standard
surfactant. The foams were analyzed for the VOC emissions (eight components) and for the
odor emissions (ten components). Figure 3 and Table 5 illustrate the results of the eight VOC
components, and Figure 4 and Table 6 illustrate the results of ten odor components.

The method used was MS 300-55 (Hyundai-Kia). For the sample preparation 1 g of foam
sample was introduced in a plastic bag with a volume of 3L, nitrogen was introduced filling
the complete 3L volume. The sample bag was heated to 65 °C for 2 h. A DPNH cartridge and
Tenax tube was used for the adsorption of VOC. The analysis was conducted on
chromatographic equipment, HPLC and MS/GC.

Results of 8 VOC components:

Fig. 3: Foam emissions (VOC). Comparative values between PFJ

references and a reference stabilizer.

16
Substance STB PU-1234 PFJ STB PU-1235 PFJ STB PU-1259 PFJ reference G

Benzene 0 0 0 0

Toluene 43 43 55 67

Ethylbenzene 14 15 17 18

Xylene 46 55 58 72

Styrene 16 17 7 16

Formaldehyde 188 204 247 328

Acetaldehyde 121 112 162 1218

Acrolein 7 6 18 9

Results of 10 odor components:

Fig. 4: Foam emissions (odor). Comparative values between PFJ

references and a reference stabilizer (nd=not detected).

17
 Substance STB PU-1234 PFJ STB PU-1235 PFJ STB PU-1259 PFJ reference G

Butyl acetate nd nd nd 4
Acetaldehyde 121 112 162 1218
Propionaldehyde 48 40 287 315
Butylaldehyde 31 34 32 239
Valeraldehyde 22 21 22 24
Nonyladehyde nd nd nd nd
Decylaldehyde 22 5 15 13
Methyl ethyl ketone 160 161 147 168

Methyl iso-butyl ketone nd nd nd nd

trimethylamine nd nd nd nd
Table 6: Foam emissions (odor). Comparative values between PFJ
references and a reference stabilizer (nd=not detected).

5.1 Comparison between STB PU-1259 PFJ (2 dosages) and 2 reference

surfactants

Two foam samples were prepared using STB PU-1259 PFJ, at dosages 0.90 pphp and 1.20
pphp and two other foams were prepared using standard surfactants at a dosage of 1.20
pphp. The first objective was to analyze if the VOC emissions have a direct relation with the
surfactant dosage. The second objective was to carry out a comparison between STB PU-1259
PFJ, a recommended stabilizer for TDI based foams and two well known standard stabilizers
from the market. The foams were analyzed for the VOC emissions
(seven components). The method used was TSM 0508 G (Toyota) and the results are
summarized and illustrated in Figure 5 and Table 7.

Regarding the first objective, the results show that increasing the dosage of the surfactant
also increases the VOC emissions, although the increase is not very high. This can be
explained due to a low VOC contribution of STB PU-1259 PFJ. Although the substance is used
at higher amounts, the final contribution to the total VOC emissions is low.

Fig. 5: Foam emissions (VOC). Comparative values between STB

PU-1259 PFJ (2 dosages) and 2 reference surfactants.

18
 The comparison of STB PU-1259 PFJ with the two standard stabilizers shows that the
emissions are similar, except for propionaldehyde, were STB PU-1259 PFJ and reference H
offer the best result compared to reference I.

Substance STB PU-1259 PFJ STB PU-1259 PFJ Reference H Reference I

Dosage 0,90 pphp 1,20 pphp

Toluene 0,51 0,57 0,62 0,52

Ethylbenzene 1,16 1,38 1,39 1,3

Xylene 1,21 1,56 1,49 1,28

Styrene 0,57 0,59 0,64 0,58

Formaldehyde 0,61 0,65 0,58 0,75

Acetaldehyde 1,19 1,28 1,08 1,43

Propionaldehyde 1,84 2,4 2,35 5,01

Table 7: Foam emissions (VOC). Comparative values between STB

PU-1259 PFJ (2 dosages) and 2 reference surfactats.

6. Conclusions

Strong efforts had been taken in the last years to reduce the emissions of volatile substances
of plastic components, being flexible PU foams one of them. The automotive industry has
been focused in the reduction of VOC and odor from the interior parts of the cars.
Considering this, the request for new additives with lower volatile components is still a major
need.

While some existing references fulfill the requirement of phthalate free, low VOC stabilizers
(under thermal desorption methods like VDA278), the need for low aldehyde, aromatic and
odor foams was not fully resolved with the existing range of references.

New stabilizers had been designed and they had been tested in commercial PU foams in
order to fulfill the requirements found in some countries from the Asia-Pacific area, regarding
aldehyde, aromatics and odor components. Some of the new references of Concentrol STB
PU-12xx PFJ offer an excellent overall performance and very low emission profile.

Research published in PU Magazine

19
Acoustic insulation for the automotive industry
Research and specialization are key processes in the development of effective, safe products
that meet market needs. After over 80 years developing solutions and working side by side
with our customers and suppliers, Concentrol has become one of the benchmarks in the
chemical sector worldwide.

At the Perfomance Materials division, Concentrol manufactures solutions for the automotive
sector, such as mold release agents for polyurethane foams, stabilizers or silicone surfactants
for polyurethane foams and mold cleaners, among others.

Next we will see the most used materials and the manufacturing process for acoustic
insulation for the automotive industry, also called ‘soundproofing’, or ‘soundproofing systems’.
In addition, there will be a brief explanation on the release agents, an essential product for
the manufacture of these parts, and the rest of the solutions for this sector.

The main materials used to make acoustic insulation for the automotive industry are
composite materials and polyurethane.
Regarding polyurethane, the parts are made entirely from only polyurethane foam, or
combined with other materials such as rubber, phenolic and polyspan, among others. The
most widely used type of PU foam is high resilience (HR) flexible foam, but we can also find
densified flexible foam, viscoelastic and R.I.M process.

Insulation is achieved thanks to “acoustic barriers”, which are molded parts used in the
automotive sector basically with the purpose of acoustically insulating the passenger
compartment as much as possible.

PU foam exhibits excellent behaviour because

noise enters through the pores and dissipates
inside the foam. The ability to regulate the pore
allows absorbing noise in a precise and measurable
way.

These parts, or soundproofing systems, are

incorporated into the vehicle interior, the boot and
the engine. The most common is to find them under
the dashboard, on the entire surface between the
engine and the passenger compartment, to avoid
the noise that the engine produces when operating.
On the floors and the boot they are also
strategically present, avoiding the transmission of Acoustic insulation with polyurethane
noise to the passenger compartment.

Types of materials

There are different types of materials that can be used as soundproofing. Composite
materials such as phenolic resins and rubber agglomerates, as well as polyspan inserts, non-
woven or other materials within molded polyurethane (PU) parts, among others.

Phenolic Composite materials

20
Because of its quality and performance, PU is the most suitable, and that is why in many cases
we come across a part totally made of injected polyurethane on an EPDM blanket,
carpet or R.I.M. polyurethane.

Another type of cold curing foam that we can find on the market is the “densified flexible”. As
its name indicates, it is flexible foam with a higher density, so that it is clearly harder, with a
smaller internal pore and almost closed on the surface. Small filler and / or acoustic protection
parts are typically manufactured in the automotive industry. Some examples are: padding in
the gear shifter area, padding in the clutch and accelerator pedal areas, specific bodywork
soundproofing, etc.

Due to its higher density, the part tends to swell inside the mold, and at the time of demolding
it can pose problems if the release agent does not provide extra slip. Greasy water-based
mold release agents are usually used, despite the fact that they are usually used at low
temperatures and in quite deep molds, since they meet the lubrication requirement of the
parts, facilitating their extraction. Unlike large parts, the small ones do not have any type of
material other than the densified flexible one.

Manufacturing process

For the manufacturing process we focus on the PU that interests us. It is always done through
a cold molding process, and for them there are two distinctions:

• Full PU part
It is the typical process of molding, application of the release agent, injection of the
components in the mold and after curing, extraction of the part.

• Mixed part
Normally a rubber sheet is deposited in the mold (it is usual to preheat it first to increase its
surface adhesion) and the PU is injected on top. When removing the part, one side is made of
rubber (barrier) and the other made of PU (adsorption). This “barrier” part can also be made
of other materials besides rubber, such as PU R.I.M. In this case, the R.I.M. sheet is previously
molded and then it is deposited in another mold, where the flexible PU is injected on top.

As we have mentioned before, inserts can be used in the PU parts to improve their properties
or facilitate assembly inside the vehicle.

Requirements:

The fundamental thing is to obtain the acoustic function. It is considered that the ideal thing is
that the area where the part receives noise is absorbent, and the end face, which is in contact
with the passenger compartment, is a barrier. It is not totally clear however, so sometimes it
is like that and sometimes the other way around, always having to work according to the
indications of the clients.

Concentrol solutions

Concentrol offers a wide range of solvent-based (class I, II, III), water-based, co-solvent and
hybrid release agents for this application. In addition, we have an extensive range of silicone
surfactants, specifically designed for flexible HR polyurethane foam, and other auxiliary
products such as reinforcing pastes, contact glues, mold cleaners, among others.

Release agents for polyurethane:

All mold release agents for the cold curing process are suitable:
• Solvent release agents (class I, II, III according to flash point).

21
 • Co-solvent water-based (5 – 20% water) and water-based (<5% solvent) release agents.
• Hybrid release agents (50 – 70% water).

Concentrol’s know-how consists of, once the problems and specific requirements of
polyurethane soundproofing manufacturers have been detected, finding the best solution,
which involves designing the most suitable skin for each need.

Other specialities of ours at Concentrol are silicone surfactants for all those manufacturers of
these acoustic systems that are self-formulating. We also have complementary products such
as reinforcement pastes (solvent-based or water-based), contact adhesives (for repairing
foams), among others.

At Concentrol we are specialists and a global reference in solutions adapted to the client from
custom manufacturing to the support we provide to industries in their different processes. In
addition, at the Performance Materials division we have developed an extensive catalogue of
solutions for the automotive sector.

22
Evolution of silicone surfactants for high resilience (HR)
flexible polyurethane foam
Silicone surfactants are copolymers formed by a silicone base (apolar part) and polyethers
(polar part), usually polyethylene oxide (OE) chains and polypropylene oxide (OP) chains. OE,
OP and silicone content significantly affect the function of surfactants. Also the substituent at
the terminal position of the polyether (R) can influence the properties of the surfactant.
Therefore, you can also influence the final properties of PU foam by playing only with the
surfactant, thus meeting the different needs for different applications that we can find on the
market, such as flexible foams, HR foams, rigid foams, among others.

Purpose of these additives

Surfactants act as surface tension depressants by reducing the pressure differences between
bubbles of different sizes formed and therefore a better stability of the bubbles and a small
average cell size are obtained. Therefore, surfactants condition the formation of fine cells,
thick cells, closed cells, and open cells, and these cellular structures influence the final
properties of PU foam.

Types of surfactants

Thus, two main groups of surfactants can be distinguished, foam stabilizers and cell
regulators.

Foam stabilizers are surfactants used in critical PU formulations, i.e. formulations that due to
the type of chemical nature of the components of polyols and / or isocyanates or due to the
amounts of catalysts or water, have very little stability. In these cases a surfactant with
stabilizing capacity is required, which helps in the foaming process in the expansion of the
gases. We find this type of surfactant in formulations where only TDI or TDI / MDI mixtures are
used, but with a high percentage of TDI.

Secondly, there are cell regulators. These surfactants are primarily designed to regulate and
unify the size and distribution of cells. These surfactants are aimed at PU formulations that by
themselves already have a high stability, able to grow with a solid and consistent structure
without collapsing, without the need for the help of a surfactant. We find this type of
surfactant in formulations where only MDI or TDI / MDI mixtures are used, but with a high
percentage of MDI. Cell openers are often requested on the market, which are cell regulatory
surfactants that increase the size of the cell to prevent shrinkage problems.

Flexible HR PU foam

Concentrol surfactants in the STB PU-12XX range are driven by high resilience PU foam, HR.
HR formulations have different needs for cell stabilization and regulatory efficiency, as we find
TDI, MDI systems or mixtures of these. Therefore, a wide range of additives must be offered to
meet all possible requirements. However, these systems are usually quite stable and a well-
balanced foam opening is usually sought.

One of the most common requirements is low compressive strength. The optimal level of
compression can be achieved with the proper selection of surfactant.
At the same time, due to the increasingly stringent legislation requirements of the automotive
and mattress industry, the minimum contribution to volatile component emissions is sought.

Emissions are classified into VOC (volatile organic compounds) and FOG (fogging organic
compounds). VOCs, which include VVOC (very volatile organic compounds) and VOCs, are
easily released from PU foam in a closed car in the summer, when internal temperatures
between 25 °C and 90 °C can be reached. FOGs are the sum of VOCs and SVOCs (semi-
volatile organic compounds) that evaporate at temperatures above 90 °C.

23
Evolution of Concentrol’s range

Given the casuistry of the sector, in Concentrol the lines of surfactants have evolved in the
following direction:

• STB PU-12XX PF: Second line designed, free of phthalates but high in aldehydes, more
directed to the European market.
For the determination of VOCs and FOGs in car interior materials, the most widely used
methodology in Europe is VDA278. The VDA (Verband der Automobilindustrie in German) is
the German quality management system (QMS) for the automotive industry. Within these
results, we must look for those volatile components that are produced by the surfactant.

• STB PU-12XX PFJ: Third line designed, free of phthalates with low content of aldehydes
and aromatics, aimed more at the Asian market, especially China and Japan.

It should be noted that in other markets such as Asia, other methodologies are used for the
analysis of VOCs. In addition, in this same market also seeks the minimum contribution of
aldehyde and aromatic compounds. Thus, in recent years it has been investigated how to
reduce the VOCs of silicone surfactants with a new generation of products that allow the
obtaining of PU foams with emission values related to the stabilizer lower than 20ppm (for a
dose of 1pphp).

For all these reasons, there are currently 3 types of products within the STB PU-12XX line,
although there are no differences in performance between the PU foam.

24
The sector of polyurethane panels and blocks
At present we can find multiple applications of polyurethane in many areas, due to its great
versatility and its insulating efficiency. At Concentrol we currently offer an extensive range of
chemical specialties that includes release agents and silicone surfactants specially designed
for the manufacture of polyurethane foam insulating panels.

In the sector of polyurethane panels and blocks, we can differentiate two main types of
applications that are used in the technical insulation and construction industries: insulating
sandwich panels (continuous or discontinuous) and box mold blocks made from rigid
polyurethane foam. Their increasingly widespread use is due to the fact that they not only
provide thermal and acoustic insulation, but also work as a waterproofing and enclosing
agent, with solutions that are light as well as resistant.

Polyurethane

A polyurethane system is made up of two types of liquid components that, through the
chemical reaction that is generated between them, give rise to polyurethane foam:

a) Firstly, polyols to which other chemical additives are added (such as catalysts, silicones,
blowing agents, etc.)
b) Secondly, isocyanates, such as TDI, MDI, MMDI, PMDI, or pre-polymers.

Currently, the sector that generates the highest consumption and demand for polyurethane
panels and blocks is industrial and residential construction and building. The main application
in this market is formulated and semi-formulated polyurethane systems that allow closed or
open cell rigid foams to be obtained.

One of the most interesting solutions in this sector is sandwich panels formed by an insulating
core of rigid polyurethane (PUR) or poly-isocyanurate (PIR) foam adhered to two steel or
aluminium metal profiles.

The PIR (polyisocyanurate foam) variety looks almost like polyurethane (PUR) foam, but has
different thermal and mechanical properties. The main difference is the reaction of PIR foam
to fire, forming a carbonated surface layer that protects and prevents the fire from
penetrating the internal layers of the panel. This greater resistance to fire allows these
solutions to obtain the BS2D0 or BS1D0 certification. The UNE-EN 13501 standard is detailed
below, with the different possibilities in the results:

This table summarizes some main technical differences between a PUR and PIR panel:

PUR PIR

Components line 4-5 5

Density 35-40 kg/m3 41-43 kg/m3

Press temperature 35-42ºC 50-60ºC

Sheet temperature 30-35ºC 40-45ºC

Adherence promoter NO SÍ

25
 Source:: https://www.une.org/

Applications of polyurethane systems

PUR and PIR sandwich panels with continuous technology are used both with metallic and
flexible coatings, in enclosures (for facades and roofs), in cold rooms and in general as
insulation in construction. PUR and PIR sandwich panels with discontinuous technology are
used for their thermal properties in the cold industry. Finally, rigid foam blocks are also a
polyurethane application that is used in different sectors.

Requirements of polyurethane foams

The main requirements of rigid polyurethane foam are:

– Thermal insulation properties (closed cell structure and low conductivity)
– Good adhesion to different substrates
– Dimensional stability
– Flame retardant properties
– No surface defects
– Good fluidity (refrigerated and discontinuous)

Coefficient of thermal conductivity (λ)

The thermal conductivity of a material is the property that it has to transmit heat, allowing
the passage of kinetic energy from its molecules to adjacent substances. Thermal conductivity
is calculated from a coefficient (λ ‘lambda’) and will differ depending on the molecular nature
of each material, measuring how well a material conducts heat in units of watts over meters
Kelvin (W / m·K).

26
The calculation is carried out with the following formula, where q is the heat flux per unit of
time and area, and grad. T is the temperature gradient:
λ = q/grad. T

For insulation, the lower the lambda value, the better the thermal performance. Polyurethane
sandwich panels are one of the materials on the market that currently has the lowest
coefficient of thermal conductivity, which is why its use as a constructive element for thermal
insulation has spread. The λ value is usually less than 0.025 (W / m · K), always measured at a
temperature of 10ºC. For this reason, the required thickness is also usually lower compared to
other types of insulating materials.

Source: https://www.camarasfrigorificas.es/blog/comportamiento-del-panel-sandwich/
Source: https://concepto.de/conductividad-termica/#ixzz6zNJr4ZVM

Concentrol’s range
Silicone stabilizers

In choosing the optimal stabilizer (or surfactant) for each polyurethane system, both chemical
requirements and those related to the manufacturing process must be considered.

The chemical requirements are related to the type of polyol, isocyanate and blowing agent
used. The influence of other components such as catalysts must also be considered. The most
important points to consider regarding the process include effective mixing, curing
conditions, and the flow demands of the casting. Our stabilizers are developed for each
specific application, considering the foaming agent, which plays a critical role in each
formulation.

Advantages of Concentrol’s range of stabilizers -STB PU-22XX-

Concentrol surfactants meet the main needs and requirements of rigid polyurethane
producers:

• A wide selection of additives that allows to offer a different stabilizing power for the
MDI, TDI / MDI and TDI systems, also providing different proportions in cell regulation.
• Cell regulation and internal stabilization can be adjusted to obtain good quality foams
with improved processability.
• Lambda optimization
• Optimization of flowability
• Optimization of B2 test results (PUR / PIR)
• Options for different blowing agents
• Possibility to choose options free from SHVC (following market trend)
• Options of partially or fully coated surfactants
• Adhesion regulation option
• Custom developed products
• Flexible R&D
• Flexible production conditions (batches from 200 kg to 10 t)

Release agents

Within the three detailed applications, it is necessary to differentiate in each case when
release agents are used or not:

• With regard to continuous sandwich panels, silicone paper is usually used on the sides
of the panels, so in many cases it is not necessary to use a release agent. Now, in those
processes in which one of the sides is used a continuous carousel of side-blocks (high-
density PE pieces), in that case a solvent-based release agent is applied by spraying it
on top of these pieces using an airbrush gun.

27
 • Likewise, in the case of discontinuous sandwich panels, we distinguish those in which the
panels are completely closed on all four sides, in which a release agent would not be
used, except in areas where foam overflows, an area in which release agent could be
applied on top of the panel to facilitate the removal of the rigid PU more easily. Now the
productions in which the discontinuous lateral panels are opened in the longitudinal
zone on both sides, solvent-based release agents are generally used, but also,
depending on the case, a water-based release agent can be used. In general, release
agents are generally applied by spray gun, but they can also be applied by brush.
• In the case of box molds, release agents are applied in a simple and rudimentary way,
sometimes using brooms that wet the entire surface of the mold. We have noticed in
some cases that some clients also use semi-permanent release agents, so that the
release agent does not transfer from the mold to the piece and allows not having to
apply release agent in each injection.

Main product lines

Some solvent-based products that we have at Concentrol are: CONCENTROL LP RD-8-6 (*)
which has a dry finish, easy to degrease, for rigid foam imitation wood and automobiles.
CONCENTROL LP RD-07 BT has a slightly greasy finish and is especially suitable for
discontinuous sandwich panels. CONCENTROL LP RD-5 ASA (*) and CONCENTROL LP RD-5
ASC laminated leather finish, discontinuous insulating panel, concentrated to dilute with
CONCENTROL LP RD-5 ASA (*), with a laminated leather finish and applied to discontinuous
insulating panels.

* These products do not contain silicone

Concentrol offers an extensive range of chemical specialties, such as silicone release agents
and surfactants, essential in the manufacture of these polyurethane foam insulating panels for
different applications. In addition, by providing personalized attention, we are able to adapt
the products to the requirements and needs of each client.

28
Silicone surfactants for polyurethane systems in
footwear - Part 1
Concentrol is a leading company in the chemical solutions sector that works by structuring its
product lines in four divisions: Performance Materials, Food Processing Aids, Additives and
Adhesives. Footwear is one of the sectors with the most product lines by Concentrol for the
manufacturing process of monodensity and bidensity soles and shoes. In addition, we have
products for the different manufacturing processes: direct injection or subsequent assembly.

Silicone surfactants are copolymers made up of a silicone base and polyethers and
polyethylene and polypropylene oxide chains. The different types of compositions that can be
made combining all these elements will lead to differences in the function of the final
surfactant.

Polyurethane foams designed exclusively for footwear or integral polyurethane foam have a
very similar composition, which is why there are surfactants that can work with both systems
equally. However, it should also be borne in mind that there are different types of surfactants:
those that are designed for polyester-based PU systems (in integral PU and footwear) and
those that are for polyester-based systems (only in PU for footwear). Additionally, there are
silicone stabilizers that can also be used in combination with other surfactants, so they act as
co-surfactants, offering improvements to the surface appearance and cell structure of the
foam.

This type of PU foam, with very similar characteristics to rubber, usually has elastic properties
and abrasion resistance. In the case of shoe soles, the use of this foam is very suitable, as it
provides a point of resistance to the wear and tear of everyday use.

When evaluating polyurethane foam, once the system has been formulated with the
appropriate surfactants, four factors must be taken into account that are key to determining
its quality:

• Its Ross-Flex properties, i.e. resistance to

flexibility. A machine calculates the ability of the
material to withstand cracking due to continuous
and rapid bending. In tests of this parameter, a
device is used that makes the same movement
about 100 times repeatedly.
• Degree of hardness. The natural hardness of
materials is usually calculated with devices called
durometers, in which a series of plastics and
rubbers are used. However, it is not possible to
establish a simple relationship between the
hardness of the material and its fundamental
property.
• Tensile strength, i.e. the natural resistance of a
plastic material to breaking due to an elongation
force. This parameter is usually measured with a
dynamometer, and the exercise consists of
cutting a piece of material in the shape of a loop In this image you can see the technical
and calculating how much force it needs to break. device used to analyze the Ross-Flex
properties at the beginning of the test and
in the bending phase of the studied
material.

29
 • Cell regulation. It is important to analyse in detail the
components of the material to try to find a cell structure as
small and uniform as possible, also minimizing surface
defects such as “pinholes”, i.e. those small craters that may
appear on the surface of the products and which
compromise their strength and tightness. Finally, it should
also be noted that it is preferable to look for a cell opening
that is completely or partially open, since a closed cell
structure leads to shrinkage defects.

The device used to measure the

tensile strength of a material, in a
test.

The first image shows the detailed composition of

an open cell. The second shows a closed cell.

These aspects of the foam can be regulated with the use of surfactants, as they are additives
that allow the formulation of thin, thick, closed and open cells, and these cellular
structures influence the final properties of integral PU foam and for footwear.

Concentrol is a diversified company that works to bring its chemical solutions to all sectors,
and researches to make them as sustainable as possible. End customers are one of the most
important parts for Concentrol, which is why we always try to find the best possible service
and product customization.

30
Silicone surfactants for polyurethane systems in
footwear - Part 2
Concentrol is a company devoted to the manufacture of chemical solutions designed to
intervene in various processes of the production chain. The company’s R&D team always
works to achieve the best degree of efficiency in the manufacturing process of the solutions,
as well as to seek the maximum degree of sustainability in terms of emissions. Concentrol’s
products focus on the international industrial market, in which we always try to satisfy
customers with solutions designed exclusively for their needs.

In this article, which is the continuation of: Silicone surfactants for polyurethane systems in
footwear – Part 1, we will delve into the characteristics and properties of Concentrol’s product
lines with respect to silicone surfactants for PU systems for shoe soles and integral type foam.
Each of the options offered by Concentrol has certain characteristics thanks to their accurate
composition. The most prominent lines are:

CONCENTROL STB PU-2248.

It is designed for the formulation of integral polyurethane foam and for footwear, and is
suitable for both polyester and polyether systems. It has a high stabilizing power and can be
used in medium density PU systems.
This product allows obtaining a fine and uniform cell structure, closed cell, and it should be
noted that it has good emulsifying characteristics thanks to its high polarity.

CONCENTROL STB PU-2246 and STB PU-2253.

They are designed for footwear and integral systems of polyether type. They have a high
stabilizing power and can be used in medium-high density PU systems.

These two lines behave as powerful cell regulators, achieving a high percentage of cells and
allow obtaining foam with a uniform and fine final cell structure. One of their main features is
that they increase the tensile strength and therefore have good Ross-flex properties.
CONCENTROL STB PU-2103 and STB PU-2104.

Two products designed for shoe systems and integral foam based on polyether and polyester
base with low-medium density. They have a medium stabilizing power, and also provide a
medium degree of cell opening. They allow obtaining PU foam with a good surface
appearance, and both surfactants are considered low-emissions.

These used as co-surfactants offer improvements in the area of surface appearance of the
foam and also offer a degree of cell opening that is appropriate when formulating low-density
PU systems.

CONCENTROL STB PU-1231 PFJ and STB PU-1234 PFJ.

They are suitable to be used in integral PU systems of polyether type. They have a low
stabilizing power, a medium cell opening and achieve a good surface appearance. They are
stabilizers suitable for low-density systems and have a very low volatile emission profile.

These two products act as cell regulators, and their use reduces the appearance of pinholes
and improves the surface appearance of the final foam. It should be noted that they help to
obtain a very good cellular structure of the skin.

CONCENTROL STB PU-2160.

31
Suitable for PU systems for footwear. It has a medium stabilizing power and allows obtaining
foams with a certain degree of cell opening. It is suitable for low-medium density systems.
With its use, foams with an excellent surface appearance are obtained.
This product line is mostly used as a co-surfactant, offering extraordinary skin formation, as it
minimizes the peeling effect and other defects such as flow marks or craters.

CONCENTROL STB PU-3160, STB PU-2290 C and STB PU-2291.

These three are designed for footwear and integral systems of polyether type. They have a
high stabilizing power and offer a medium degree of cell opening. They are surfactants
suitable for low-medium density PU foams and, with their use, the surface appearance of the
foam is very good.

These medium-regulating silicone stabilizers have the ability to improve the surface
appearance and reduce imperfections such as pinholes.

CONCENTROL STB PU-4001.

It is designed for polyester type shoe systems. This product is used as a cell-opening additive
and does not provide a stabilizing effect on the system. It is suitable for low-medium density
systems. It provides an excellent surface appearance of the PU garment and has a very low
amount of volatile emissions.

It is a regulating and cell-opening additive. It is formulated with organic polymers and is

silicone free. The peculiarity of this product is that it improves the formation of the skin as
more homogeneous foams are obtained, the pigments are better distributed and fewer
defects by flow lines are observed.

CONCENTROL STB PU-4002.

Formulated for PU systems for polyester type shoe soles. It has a low stabilizing power and
provides a medium degree of cell opening. The product is suitable for low-medium density
foams, and their use provides an excellent surface appearance.

It is a regulating and cell-opening additive. This fluid has very low polarity and, therefore, it
provides characteristics of flexibility, lubricity and hydrophobicity in polyurethane coatings. It
is often used in high-density formulations such as filters.

CONCENTROL STB PU-4052.

It is made for PU systems for shoe soles. It has a low stabilizing power and offers a medium
degree of cell opening. Suitable for low-medium density PU foams. It provides an unsurpassed
surface appearance of foam.

The use of this product provides good skin formation and little flaking. In addition, it also
reduces pore formation and improves mechanical properties.

For Concentrol’s team of professionals, it has always been very important to have many
product lines facing different sectors, as it covers an extensive international market with very
specific peculiarities. Thanks to the wide range of products they have, they can therefore
offer the right solutions for every professional need.

If you are interested in any of our solutions or would like to suggest that we take care of them
exclusively for your needs, do not hesitate to contact us.

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Surfactants for HFO, the blowing agent of tomorrow in
the polyurethane industry
Concentrol, a leading company in chemical solutions, has always kept in mind that it is
necessary to leave the least possible impact on the planet. Therefore, more and more, they
take special care in the development of their new solutions and in the effect that these can
have on the environment.

As has been demonstrated throughout a life span dedicated to the industry, polyurethane has
many uses. It can both be used for the manufacture of coatings and paints, for food
preservation or for insulation and construction, among others. PU is a material that is being
used more and more due to its effectiveness, safety, lightness and great insulation qualities.
Originally, CFC gases were used for the manufacture of polyurethane foam, then HCFCs and,
years later, HFCs were used. The problem with all these fluorine-based agents is that, despite
the advances that each one of them made for the sector, they continued to be harmful to the
environment.

By constantly studying the market, Concentrol has detected the need for new silicone
surfactants necessary for the manufacture of foams from these new blowing agents – HFO
(hydrofluoroolefins), the “ecofriendly” blowing agent. For this reason, after intensive R&D
work, a new range of surfactants is currently being manufactured and marketed. These
products help producers of polyurethane systems to manufacture more environmentally
sensitive solutions.

HFO: what is it and what are its benefits?

HFO is a blowing agent that is used as a blowing agent to form polyurethane foam. It is part
of the fourth generation of refrigerants and is an element of easy conversion, safe and of low
total cost. Unlike the rest of blowing agents with these characteristics, they are not persistent,
bioaccumulative or toxic, they do not have any impact on the ozone layer and their use
implies a very small Global Warming Potential (GWP). In addition, it should be noted that the
degradation of HFO can lead to trifluoroacetic acid (TFA), which at current concentrations
does not affect marine life, humans or the environment. As explained in a Honeywell
sustainability article, “to date, the use of HFO refrigerants and blowing agents has helped
avoid the release of 170 million metric tons of CO2e into the atmosphere so far, equivalent to
emissions from more than 35 million cars, almost all licensed cars in the UK”.

All these characteristics make it the most viable alternative in terms of sustainability and
energy efficiency. Many scholars agree that HFO could be, in the not too distant future, the
substitute for HFC, which is why Concentrol will continue to bet on having suitable solutions
for its use.

The implications of silicone surfactants

One of the most important drawbacks to take into account when working with HFO has to do
with the degradations derived from its use. In the ozone layer, these blowing agents can lead
to the following two chemical reactions:

CH2= CFCF3 + OH —> CF3COF + HCHO + H₂O + O2

CH2= CFCF3 + + Cl —> CF3COF + HC(O)Cl + O2 + CO

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In the specific case of PU systems, the most common is that HFO triggers the first of these
reactions, since they carry bases (OH groups).

The first chemical reaction gives rise to reaction number three, which is the following:

CF3COF + H₂O —> CF3COOH + CO₂ + HF

The resulting reaction, formed by CF3COOH and HF, is what could lead to the degradation of
surfactants, since they can give rise to an acidic and corrosive environment with much more
aggressive conditions than those they usually have. If you want to investigate more about this
topic, you can consult the “Study on environmental and health effects of HFO refrigerants”, by
the Norwegian Environment Agency.

In the following table, you can see very visually all the HFOs that exist at this time, and those
that end up emerging after their decomposition.
Contrary to what some people think, all these degradation problems mentioned above occur
when the surfactant is formulated with HFO for several days and in closed systems, not at the
time of foaming in situ, a process that does not usually cause problems.

Besides, it is also common to carry out aging studies to see how this blowing agent behaves
over time. To analyze the aging process, several experiments are carried out that can last up
to two weeks. These tests use high temperatures (50-60 °C), which serve to simulate a longer
period of time. With these processes, it is analyzed if the surfactants support the degradation
generated by the HFO blowing agent.

Concentrol’s current solutions

Concentrol’s research team continues to focus on investigating surfactants for all types of
applications that carry HFO. Currently, in their product range they already have several
consolidated references with good results for different applications, such as:

• CONCENTROL STB PU-2248 for integral or spray PU foam.

• CONCENTROL STB PU-2272 for discontinuous insulation panels (PUR and PIR) and
appliances.
• CONCENTROL STB PU-2285 for discontinuous insulation panels (PUR and PIR) and block
foam.

The company also has others that are under development. In addition, it should be noted that
some of these references are without SVHC, that is, cyclic components.

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Concentrol works with the objective of responding to the specific needs of each client, and
therefore offers the possibility of adapting solutions based on their preferences. Contact us
and we will be happy to advise you.

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www.concentrol.com
marketing@concentrol.com
+34 972 478 091

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