Additives Value beyond chemistry

Enhanced Processing and Service Life

for Polyurethane Products
Additives for Polyurethane
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
Polymer Degradation and Stabilization . . . . . . . . . . . . . . . . . . . . . . . .4
Thermo-oxidative Degradation . . . . . . . . . . . . . . . . . . . . . . .4
Antioxidants Interrupt the Degradation Process . . . . . . . . . . .5
Photodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
Light Stabilizers Counter Photodegradation . . . . . . . . . . . . . .7
Additives for Polyurethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
Thermoplastic Polyurethane (TPU) . . . . . . . . . . . . . . . . . . . .9
Reaction Injection Molded (RIM) Polyurethane . . . . . . . . . . .12
Polyurethane Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14
Polyurethane Adhesives and Sealants . . . . . . . . . . . . . . . . .20
Polyurethane Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
Additives Data Bank . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24
Chemical Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24
Chemical Names . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27
FDA Clearance Summary . . . . . . . . . . . . . . . . . . . . . . . . . .28
Solubility Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
Table of Contents
2
3
Polyurethanes are among the most versatile polymers.
They are used in a wide variety of applications including
adhesives, sealants, coatings, fibers, reaction-injection
molded components, thermoplastic parts, elastomers and
both rigid and flexible foams.
Polyurethanes offer an impressive range of performance
characteristics and the use of appropriate stabilizers can
extend the service life of polyurethane products. Selecting
the best stabilization system depends on specific produc-
tion conditions, end-use environment and a knowledge of
the fundamental degradation mechanisms of the
polyurethane components.
Degradation of both the polyol and urethane components
will cause changes in the physical or mechanical properties
of the polyurethane. Urethanes are susceptible to degrada-
tion by free radical pathways induced by exposure to heat
or ultraviolet light. The use of primary antioxidants, such
as Irganox

, suppresses the formation of free radical

species and hydroperoxides in polyols both during storage
and conversion. UV absorbers and hindered amine
stabilizers, such as Tinuvin

and Chimassorb
TM
, protect
polyurethanes from UV light-induced oxidation.
Ciba Additives offers a variety of additives for improving
the processing and service life of polyurethane products.
For detailed information about individual products, specific
application or performance requirements, please contact
your local Ciba technical representative or regional agent.
Introduction
4
RH (Polymer)
ROO
RO + HO
Reacts with primary
antioxidants
(hindered phenols,
hindered amine
stabilizers)
R
Reacts with secondary antioxidants
(phosphites, hydroxylamines)
to yield inactive products
Reacts with
another RH
Reacts with
another RH
Oxygen
Energy,
Catalyst residues,
Light
Cycle II Cycle I
Energy,
Catalyst residues,
Light
React with primary
antioxidants
(hindered phenols,
hindered amine
stabilizers)
to yield inactive products
(ROH and H
2
O)
R
ROOH
+
Carbon centered
radicals react with
Lactone based
stabilizers
R Alkyl radicals
RO Alkoxy radicals
ROO Peroxy radicals Path of degradation
ROOH Hydroperoxide Path of stabilization
Polymer Degradation and Stabilization
Thermo-oxidative Degradation
Polyurethanes, like other organic materials,
react with molecular oxygen in a process
call autoxidation. This degradation
process results in product discoloration and
loss of physical properties.
Autoxidation may be initiated by heat, high
energy radiation (UV light), mechanical
stress, catalyst residues, or through reaction
with other impurities. Free radicals
(Figure 1) are generated which react rapidly
with oxygen to form peroxy radicals. These
peroxy radicals may further react with the
polymer chains leading to the formation of
hydroperoxides (ROOH). On exposure to
heat or light, hydroperoxides decompose to
yield more radicals that can reinitiate the
degradation process.
Figure 1. Polymer Degradation and Stabilization
Microwave Scorch Test. Sample on right
stabilized with Irganox antioxidants show
much less exotherm discoloration than
the other commercial system on the left.
See complete test procedure on page 16.
5
Antioxidants Interrupt
the Degradation Process
Antioxidants interrupt the degradation process
in different ways according to their structure.
The major classifications of antioxidants are
listed below.
Primary Antioxidants, mainly acting in Cycle I
of Figure 1 as chain-breaking antioxidants, are
sterically hindered phenols. Primary antioxidants
react rapidly with peroxy radicals (ROO) to
break the cycle. Irganox

1010, Irganox 1076,

Irganox 1098, Irganox 1135 and Irganox 245
are examples of primary antioxidants.
Secondary arylamines, another type of primary
antioxidant, are more reactive toward oxygen-
centered radicals than are hindered phenols.
Synergism between secondary arylamines
and hindered phenols leads to regeneration of
the amine from the reaction with the phenol.
Irganox 5057 is an example of a secondary
arylamine.
Secondary Antioxidants, acting in Cycle II of
Figure 1, react with hydroperoxide (ROOH) to
yield non-radical, non-reactive products and are,
therefore, frequently called hydroperoxide
decomposers. Secondary antioxidants are par-
ticularly effective in synergistic combination
with primary antioxidants. Phosphite stabilizers,
Irgafos

168 (a component of Irganox B Blends),

Irgafos 12 (a component of Irganox LC Blends)
and Irgafos 38 (a component of Irganox LM
Blends) are secondary antioxidants.
Multifunctional Antioxidants have special
molecular design and optimally combine primary
and secondary antioxidant functions in one
compound. Hindered amine stabilizers (HAS)
and dialkylhydroxylamine are prime examples of
multifunctional antioxidants. Irganox 565 is
another example of a multifunctional antioxidant.
Hindered amine stabilizers can in some cases
provide radical trapping effectiveness similar to
hindered phenols. Traditionally used as light
stabilizers, hindered amine stabilizers can also
contribute to long-term thermal stability.
Examples are Tinuvin

765, Tinuvin 123,

Tinuvin 622 and Tinuvin 770.
Dialkylhydroxylamines, a component of
FS Systems, function as radical traps as well as
hydroperoxide decomposers and reducing
agents.
Lactones, a component of our Irganox HP prod-
ucts, function as carbon-centered radical scav-
engers which inhibit autoxidation as soon as it
starts and are further capable of regenerating
phenolic antioxidants to provide new levels of
overall processing stability.
Oxygen-Centered Radical Traps
OO OOH

Ar2NH +-O-CH-CH2 A Ar2N + -O-CH-CH2
Ar2N + ArOH AAr2NH + ArO
J. Pospisil in Developments in Polymer
Stabilization, Vol. 1, Ch, 1, ed. G. Scott, Applied
Science Publ., London, 1979.
6
Photodegradation is really two distinct pro-
cesses. The first is photolysis, a complex process
occurring in several steps, which involves the
absorption of UV radiation, followed by the
formation of free radicals due to the breaking of
the absorbing species molecular bonds. The
second is autoxidation. Here, the free radicals
formed during photolysis interact with oxygen
to form peroxy radicals.
There are five separate steps during photodegra-
dation. In the following schematic, R represents
the polymer or UV absorbing component.
Step 1
RAR*
Here, the polymer absorbs UV radiation. The
energy from the absorbed UV radiation
excites the absorbing species (either polymer
molecules or impurities) and raises them to a
higher energy level (R*). These excited state
molecules are very reactive and may undergo
a wide range of processes. Two common
processes are returning to the ground state or
homolytic bond cleavage.
Step 2
R*AR
If the molecule cannot be brought to its ground
state, homolytic bond cleavage and the forma-
tion of free radicals (R) will occur.
O2 R'H
R AR* AR AROO AROOH ARO+OH
Step 1 Step 2 Step 3 Step 4 + Step 5
R'
A
Photodegradation
Step 3
O2
RAROO
In Step 3, the free radicals formed during pho-
tolysis readily react with oxygen to form peroxy
radicals. This is called autoxidation.
Step 4
R'H
ROOAROOH + R'
In Step 4, the peroxy radicals attack the poly-
mer backbone (R'H) via hydrogen abstraction,
forming hydroperoxides and more free radicals.
These free radicals (R') again readily react with
oxygen in Step 3 to form additional peroxy
radicals.
Step 5
ROOH ARO + OH
Finally in Step 5, the hydroperoxides, which are
very unstable to both UV radiation and heat,
fragment and form additional free radicals. As
the processes continue, more and more molecu-
lar bonds break, leading to a deterioration of
the desired properties.
Photolysis Autoxidation
7
Light Stabilizers Counter
Photodegradation
Polyurethanes are subject to degradation when
exposed to ultraviolet light from natural and/or
artificial sources. Degradation results in discol-
oration and/or loss of physical properties.
The main classes of light stabilizers are:
Ultraviolet Light Absorbers (UVAs)
Hindered Amine Light Stabilizers (HALS)
During Step 1
UV absorbers protect against photodegradation
by competing with the polymer for absorption
of ultraviolet light.
As shown in Figure 2, the excitation energy of
UV absorbers is rapidly and efficiently deacti-
vated by the process of tautomerization.
An ideal UVA should be very light stable, and
should have high absorption over the UV range
from 290 to 400 nanometers. Ciba Additives
pioneered the development of benzotriazole
ultraviolet light absorbers. Tinuvin P, Tinuvin 213,
Tinuvin 326, Tinuvin 327, Tinuvin 328, and
Tinuvin 571 belong to this class of UVAs.
During Step 3
Hindered amine light stabilizers (HALS) repre-
sent an alternative chemistry in light stabiliza-
tion technology. Several theories have been
advanced to explain the mechanism of stabiliza-
tion by HALS, of which the most widely held
involves efficient trapping of free radicals with
subsequent regeneration of active stabilizer
moieties, represented in Figure 3. Examples of
HALS are Tinuvin 123, Tinuvin 144, Tinuvin 622,
Tinuvin 765, Tinuvin 770, and Chimassorb 944.
R'OH + R=O
R
R'OO
N-OR
N-O N-CH
3
[O]
N
O O
R
O
R'
Figure 3. Regenerative Mechanism of HALS*
Figure 2. Schematic of Tautomerism
Molecule A absorbs UV energy, resulting in an electronic
rearrangement to form molecule B which, through the dissi-
pation of heat energy, reverts to the original form, molecule
A. This process is repeated indefinitely.
H O
N
N
+
UV
-
N
N
N
N
H O
* P.P. Klemchuk, M.E. Gande, Polymer Degradation and Stabilization,
1988, 22, 241; 1990, 27, 65
(A) (B)
8
Ciba Additives for Polyurethanes
Irganox

245
Irganox 1010
Irganox 1076
Irganox 1098
Irganox 1135
Irganox 5057
Tinuvin

P
Tinuvin 213
Tinuvin 326
Tinuvin 327
Tinuvin 328
Tinuvin 571
Tinuvin

123
Tinuvin 144
Tinuvin 622
Tinuvin 765
Tinuvin 770
0.0
0.2
0.4
0.6
0.8
1.0
270 290 310 330 350 370 390 410
Wavelength (nm)
A
Tinuvin 327
Tinuvin 328
Tinuvin 571
Tinuvin 213
60 110
Temperature (C)
160 210 260 310 360
Weight loss (%)
0
20
40
60
80
100
BHT
Irganox 1135
Irganox 5057
Irganox 1076
Irganox 245
Irganox 1010
Additives for Polyurethanes
Antioxidants
UVAs
HALS
Figure 4. UV Absorption Spectra (20 mg/l Ethyl Acetate) Figure 5. Weight Loss of Antioxidants TGA, 20C/min (air)
Uvitex

OB Optical
Brightener
9
Thermoplastic Polyurethane (TPU)
Applications
Thermoplastic polyurethanes are among the
most versatile elastomeric materials. During the
manufacture of TPUs, processing stabilizers such
as Irganox 245, Irganox 1010 or Irganox 1098
are used to protect the polymer from degrada-
tion. Due to their versatility, TPUs are used in a
wide range of applications that may require
both thermal and/or light stability.
For enhanced end-use stability, thermal stabi-
lizers including Irganox 1135, Irganox 245
or Irganox 1010 are used. Light stability can
be achieved using hindered amines alone
(Tinuvin 765 or Tinuvin 123) or in conjunction
with UV absorbers (Tinuvin 571 or Tinuvin 213).
Also available is Tinuvin B75, a liquid blend of
all three stabilizer functionalities - antioxidant
(Irganox 1135) plus hindered amine
(Tinuvin 765) plus UV absorber (Tinuvin 571).
Tinuvin B 75 provides long term stability, ease of
handling and outstanding end-use performance,
all in one liquid product.
To accommodate TPU processors, both liquid
and solid stabilizers are available.
10
Table 2. Ovenaging of Thermoplastic Polyurethane
Days to YI=20
At 120C
Unstabilized 3
0.3% Irganox 1010 6.5
0.3% Irganox 245 6.5
Sample: 2 mm injection molded dumb-bells
Test Criterion: Ovenaging time at 120C till
discoloration increases 20 Yellowness-
Index units.
Table 1 shows the impact oxidation has on
the initial color of polyurethane materials.
Oxidation is measured by the peroxide con-
centration in the polyol. The resulting color
development is measured by Yellowness
Index of the final polyurethane.
Table 1. Effect of Peroxide Concentration on
Polyurethane* Initial Color
Peroxide Conc. PUR
(ppm in the polyol) Yellowness Index
1 5
25 13
50 42
100 52
* Shoe sole formulation, non-pigmented, PUR is
polyether based.
10 0 20 30 40
E
0.5% Tinuvin 327
0.5% Tinuvin 328
0.5% Tinuvin 571
Control
Figure 6. Discoloration of TPU Plaques (1.5 mm)
Exposure: 500 Hours Light Exposure. Dry Xenon
CI 35: b.P. TC = 63C, 0.35W/m
2
Irradiance
Base Stabilization: 0.25% Irganox 1135/0.25% Tinuvin 765
20 0 40 60 80
% Retention
Control
0.5% Tinuvin 571
Elongation
Tensile Strength
100 120
0.5% Tinuvin 328
0.5% Tinuvin 327
Figure 7. Tensile Strength and Elongation Retention
of TPU Plaques (1.5 mm)
Exposure: 500 Hours Light Exposure. Dry Xenon
CI 35: b.P. TC = 63C, 0.35W/m
2
Irradiance
Base Stabilization: 0.25% Irganox 1135/0.25% Tinuvin 765
Figures 6 and 7 demonstrate the dramatic
impact of stabilizers in thermoplastic
polyurethanes. All formulations include
Irganox 1135 antioxidant and Tinuvin 765
hindered amine stabilizer. After 500 hours
Dry Xenon exposure, all three UV absorbers
(Tinuvin 571, Tinuvin 328, and Tinuvin 327)
show significant protection of color and
retention of original elongation and tensile
properties.
Antioxidants are needed to protect TPU
during processing. Both Irganox 1010 and
Irganox 245 have been used in commercial
production successfully for many years. The
stabilized TPU samples were able to sustain
two times longer ovenaging exposure than
the sample without an antioxidant (Table 2).
11
0 100 200 300 400 500
Unstabilized
0.3% Tinuvin 328
0.3% Tinuvin 213
0.4% Tinuvin 328
+ 0.4% Tinuvin 765
0.4% Tinuvin 213
+ 0.4% Tinuvin 765
Hours to delta YI of 20
37
174
132
269
443
Figure 8. Accelerated Weathering, TPU Film
Sample: TPU Film, 6 mm
Exposure: Xenotest 450
Substantial improvement in performance can be
achieved using a UVA/HALS combination vs UVA
alone, as demonstrated in Figure 8.
Table 3. Comparison of Light Stability of Aromatic
and Aliphatic Polyurethane Film
Xenon Weather-Ometer Exposure
Hours to 50% Retention
of Elongation
Aromatic Aliphatic
Control 170 3,200
0.5% Tinuvin P + 390 4,500
0.5% Irganox 1010
0.5% Chimassorb 944 900 11,500
0.5% Tinuvin 622 670 11,500
0.5% Tinuvin 765 850 13,900
Table 4. Effect of Nitrogen Oxides* on Polyester-Based
Polyurethane
Yellowness Index
After 334 Hours
Unstabilized 53
1% Tinuvin P 50
1% BHT 34
1% Tinuvin 770 15
1% Tinuvin P + Tinuvin 770 (1:1) 13
1% Tinuvin 770 + Irgafos 168 (1:1) 10
1% Tinuvin 765 9
* PUR plaques were maintained in an enclosed chamber
with nitrogen oxides present for 334 hours at 60C.
PUR is a non-pigmented shoe sole type formulation.
Table 3 compares the light stability of aromatic
vs. aliphatic based polyurethanes. Although sta-
bilizers do provide some improvement in light
stability for aromatic polyurethane, light stabiliz-
ers are particularly effective in aliphatic
polyurethane.
During storage and end use, TPUs can be
exposed to nitrogen oxides that may cause the
polymer to discolor. This discoloration can be
minimized using a hindered amine (Tinuvin 765
or Tinuvin 770) or a combination of stabilizers as
shown in Table 4.
12
0 250
Time (Hours)
500 750 1000
E
0
3
6
9
12
Control
1.5% Tinuvin B 75
1% Irganox 1010
+1% Tinuvin 770
+1% Tinuvin P
15
Figure 9. Light Stability of Black RIM Polyurethane
Plaques (2 mm)
Test Criterion: Discoloration after WOM CI 65: b.P.
TC = 63, r.H. = 60%
Reaction Injection Molded (RIM)
Polyurethane
Polyurethane parts can be made by the RIM
(reaction injection molding) process. Raw materi-
als are injected into a mold where the polymer-
ization occurs. Depending on the end use of the
product, enhanced light or long-term thermal
stability may be required. In particular, automo-
tive parts have stringent performance require-
ments for which a combination of UV absorbers
(Tinuvin 571, Tinuvin 213, Tinuvin 328), hin-
dered amine stabilizers (Tinuvin 765, Tinuvin
123, Tinuvin 770), and/or antioxidants (Irganox
1135, Irganox 1010, Irganox 245) are used.
Figure 9 shows the strong performance of UV
absorbers with hindered amine stabilizers and
antioxidants in a black PUR RIM exposed in the
Weather-Ometer.
13
50 100
Exposure Time (hours)
150 200 300 0
20
40
60
70
250
Yellowness Index
50
30
10
Unstabilized (Total conc. 0%)
Irganox 245 + Tinuvin 328 + Tinuvin 765 (1% conc. 1:2:2 ratio)
Irganox 245 + Tinuvin 571 + Tinuvin 765 (1% conc. 1:2:2 ratio)
Irganox 1135 + Tinuvin 571 + Tinuvin 765 (1% conc. 1:2:2 ratio is
Tinuvin B 75)
20 40
Exposure Time (hours)
60 80 0
20
40
60
70
Unstabilized (Total conc. 0%)
Irganox 245 + Tinuvin 328 + Tinuvin 765 (1% conc. 1:2:2 ratio)
Irganox 245 + Tinuvin 571 + Tinuvin 765 (1% conc. 1:2:2 ratio)
Irganox 1135 + Tinuvin 571 + Tinuvin 765 (1% conc. 1:2:2 ratio is
Tinuvin B 75)
Yellowness Index
50
30
10
Figure 11. PUR White Integral Foams Discoloration
Exposure: Weather-Ometer, Wet Cycle
BP = 45C; Wet Cycle 112/18
Figure 10. PUR White Integral Foams Discoloration
Exposure: Xenotest 450, Dry Cycle
BP = 45C; Relative Humidity = 65%
Figure 10 shows the reduction in yellowness
when light stabilizers are used. Tinuvin B 75, a
liquid blend of three stabilizer functionalities,
provides good control of color development in
a white integral skin polyurethane foam sample
even after hundreds of hours of dry light expo-
sure. Figure 11 is the sample exposed in a wet
cycle. Despite the more severe conditions,
Tinuvin B 75 provides excellent light stability.
14
Polyurethane Foams
Polyurethane can be foamed and shaped into
flexible, rigid and integral skin configurations.
Each of these types of applications will have
specific stabilizer requirements. When producing
flexible slabstock foams, the exotherm from the
polyol/isocyanate reaction can cause discol-
oration, called scorch, in the center of the foam.
This phenomenon is most common in flexible
slabstocks because of the size of the foam. Since
polyurethane foam is a good insulator, the
interior of the foam stays hot for many hours,
increasing the risk of scorching. Because of their
limited size, rigid and integral skin foams tend
not to be as prone to scorching as flexible slab-
stock foams.
Hindered phenolic antioxidants (Irganox 1076,
Irganox 1135) with alkylated diphenyl amines
(Irganox 5057) in the polyol provide good pro-
tection against scorch. Selection of the additive
package will be determined by a number of fac-
tors including foaming technique and end-use
characteristics. Many processors prefer Irganox
1076 and Irganox 1135 due to their lower
volatility relative to BHT.
Antioxidants are used to protect the urethane
from processing and end-use degradation and
protect polyol from oxidation during storage
and transport. Many end-use applications for
rigid and integral skin foams are subject to out-
door exposure requiring light stabilizers to pro-
vide ultraviolet protection.
15
Polyol and Flexible Polyurethane FoamStabilization
Test Methods
Polyetherpolyol Isocyanate
Analytical Determination of

Antioxidant content

Peroxide formation
(long-term storage)
Differential Scanning Colorimetry DSC

Exotherm peak of oxidation reactions

(effectiveness of antioxidants)
Foaming Formulation
Scorch Test

Microwave/Humidity exposure

Static ALU-Block Test

Dynamic ALU-Block Test

(discoloration, YI)
Differential Scanning Colorimetry (DSC)

Exotherm peak of oxidation reactions

(effectiveness of antioxidants)
Gasfading Test with NO
x

Yellowing of foam

Yellowing of textiles
a. Volatility of antioxidants
b. Reactivity with NO
x
c. Identification of reaction products
Polyurethane Flexible Foams/Textile Staining Test
Swiss Federal Laboratories for
Materials Testing and Research (EMPA)
St. Gallen, Switzerland
Sample preparation
Two foam samples of each formulation are
exposed for 3 hours to air containing 50 ppm
and 5 ppm NOx gas respectively. The samples
are then covered with two layers of cotton
textile (MOLTON), which has been previously
washed with a softener, and wrapped with
aluminium film.
Samples aging
1) The samples are put into an air-circulating
oven at 40C.
2) Another series of samples, covered with one
layer of textile, is exposed for one month in
air. These samples, under exclusion of direct
sun radiation, are not wrapped in aluminium
film and not gassed.
Measurement of the textile discoloration
1) Samples gassed with 50 ppm NOx gas.
The first textile layer is evaluated after
24 hours.
The second textile layer is evaluated after
48 hours.
2) Samples gassed with 5 ppm NOx gas.
The first textile layer is evaluated after
48 hours.
The second textile layer is evaluated after
96 hours.
3) Samples exposed in air.
The textile layer is evaluated after 1 month.
The textile discoloration is measured by
comparing the color difference between the
exposed and the unexposed textile sample.
Polyurethane Foam Test Methods
16
Microwave Scorch Test Procedure
1. A master batch is prepared containing surfactant,
water and amine catalyst.
2. An appropriate amount of the master batch is
added to 150 g polyol, along with the antioxidant
package.
3. The mixture is stirred for 10 seconds at 2600 rpm.
The tin catalyst is added and the mixture is stirred
for 18 seconds at 2600 rpm. The TDI is then
added and the mixture stirred for an additional
5 seconds at 2600 rpm.
4. The mixture is poured into an 8x8x4 cake box.
Cream times are typically 9-12 seconds, and rise
times 87-94 seconds.
5. After 2 minutes 14 seconds, a 4x4 piece of the
top skin is removed. This piece is removed with a
4x4 piece of cardboard supported by a pencil to
a 3M double-sided Scotch

Brand Tape.
6. After 5 minutes, the sample is placed inside a
microwave oven with 1 cup water in a separate
container, then microwaved at 50% power for 5
minutes 15 seconds. This microwave time is cho-
sen so that a delta E value of about 20 is obtained
for a standard formulation (e.g. 0.40% Irganox
1135 + 0.10% Irganox 5057).
17
160 170 180 190 200
Temperature (C) to reach Yellowness Index = 25
Total additive concentration = 3000 ppm
Unstabilized
BHT
Irganox 1135
BHT + Irganox 5057
(ratio 2:1)
Irganox 1135 +
Irganox 5057
(ratio 2:1)
Unstabilized = 89C
190 195 200 205 210
Temperature (C) to reach Yellowness Index = 25
Total additive concentration = 3500 ppm
Unstabilized
Irganox 1135
Irganox 1135 +
Irganox 5057
(ratio 1:1)
Figure 13. Polyether Flexible Foams Stabilization
Exposure: Dynamic Heat Test, Ovenaging for 30 Minutes
Figure 14. Polyester Flexible Foams Stabilization
Exposure: Dynamic Heat Test, Ovenaging for 30 Minutes
Processing Stabilization of
Polyurethane Foams
For polyol producers and foamers seeking lower
volatility alternatives to BHT for scorch protection,
both Irganox 1135 and Irganox 1076 are excellent
choices. Irganox 1135 in combination with
Irganox 5057 is the ideal liquid stabilizer system
for polyurethane flexible forms. Irganox 1135 has
lower volatility than BHT (see TGA data on page 8)
and the liquid nature of Irganox 1135 and Irganox
5057 provides ease of incorporation for liquid
based processing.
Figure 12 demonstrates the outstanding scorch
protection provided by a 2:1 ratio of Irganox 1135
and Irganox 5057. A 4:1 ratio of Irganox 1076 and
Irganox 5057 also provides equal performance to
the BHT system in the microwave scorch test.
In ovenaging tests carried out in an aluminum-
block oven, the foam sample stabilized with 3000
ppm of a combination of Irganox 1135 and
Irganox 5057 at 2:1 ratio showed the longest time
to reach a Yellowness Index of 25 (Figure 13).
For polyester foam samples, ovenaging tests in an
aluminum-block oven show improvement in sta-
bility, whether testing Irganox 1135 alone or in
combination with Irganox 5057 (Figure 14).
10 0 20 30 40
E
0.5% BHT/
Irganox 5057
50
4:1 Ratio
2:1 Ratio
1:1 Ratio
17
18
29
24
17
20
17
32
44
0.5% Irganox 1135/
Irganox 5057
0.5% Irganox 1076/
Irganox 5057
Figure 12. Microwave Scorch Testing of Polyether
Polyurethane Cake Box Forms
Foam Formulation: 150.00 g Polyether Polyol, 1.50 g Surfactant,
6.75 g Water, 0.375 g Amine Catalyst,
0.12 g Tin Catalyst, 92.40 g Toluene Diisocyanate
18
2 0 4 8 10
E
6
24 hours
48 hours
50 ppm NOx
0.24 % Irganox 1076
+ 0.06% Irganox 5057
0.7
1
0.24 % Irganox 1135
+ 0.06% Irganox 5057
0.8
0.7
0.24 % BHT
+ 0.06% Irganox 5057
8.8
4.4
Control
BHT-free polyether polyol
0.7
1.1
1 0 2 3 4
E
48 hours
96 hours
5 ppm NOx
0.24 % Irganox 1076
+ 0.06% Irganox 5057
1.4
1.2
0.24 % Irganox 1135
+ 0.06% Irganox 5057
0.9
0.9
0.24 % BHT
+ 0.06% Irganox 5057
2
2.6
Control
(BHT-free polyether polyol)
1.2
1.2
5 0 10 20 25
E
15
0.24 % Irganox 1076
+ 0.06% Irganox 5057
0.7
0.24 % Irganox 1135
+ 0.06% Irganox 5057
1.1
0.24 % BHT
+ 0.06% Irganox 5057
20.7
Control
(BHT-free polyether polyol) 3
Stabilization Minimizes
Textile Staining
In many applications such as automotive interiors,
furniture, mattresses, carpeting and shoulder pads
polyurethane flexible foams come in contact with tex-
tiles. Proper stabilizers are needed to prevent scorch-
ing of the foam and subsequent staining of
the textile. Figures 15, 16, and 17 show how the
proper selection of scorch inhibitors can minimize
gas fade discoloration in textiles. Irganox 1135 or
Irganox 1076 limits the discoloration associated with
NOx exposure vs. BHT. Figure 15 is an air exposed
sample. Whereas, the sample in Figure 16 was
exposed to 5 ppm NOx for 48 and 96 hours. Figure 17
shows a more severe exposure of 50 ppm NOx.
Figure 16. Gasfade Discoloration of PUR Flexible Foam
Exposure: MOLTON Textile Ovenaging at 40C
(EMPA-Test)
Figure 17. Gasfade Discoloration of PUR Flexible Foam
Exposure: MOLTON Textile Ovenaging at 40C
(EMPA-Test)
5 0 10 20 25
E
15
0.24 % Irganox 1076
+ 0.06% Irganox 5057
0.7
0.24 % Irganox 1135
+ 0.06% Irganox 5057
1.1
0.24 % BHT
+ 0.06% Irganox 5057
20.7
Control
(BHT-free polyether polyol) 3
Figure 15. Gasfade Discoloration of PUR Flexible Foam
Exposure: MOLTON Textile 1 Month Storage in Air
(EMPA-Test)
19
The micrographs in Figure 18 show that a combi-
nation of a hindered amine (Tinuvin 765) and
ultraviolet absorber (Tinuvin 328) can help protect
the cell structure of a polyether polyurethane foam
Figure 18. Surface microcrazing of Foamed Polyether Urethane
Light Stabilization
of Polyurethane Foams
during exposure to light. Note that the cell
structure of the stabilized foam looks similar to the
unexposed foam even after l50 hours of Xenon
exposure.
Exposure: 150 hours in Xenon Weather-Ometer
Magnification: 1,000X
Stabilization System: 0.5% Tinuvin 328 + 0.5% Tinuvin 765
Exposure: 150 hours in Xenon Weather-Ometer
Magnification: 1,000X
Unstabilized
Unexposed
Magnification: 1,000X
20
Polyurethane Adhesives
and Sealants
Polyurethanes are widely used for formulating
adhesives and sealants. Polyurethane adhesive
formulations include both solvent-based as well
as hot-melt. In some cases, high-performance
adhesives can replace standard mechanical
bonding methods such as nuts and bolts,
screws and welding. Appropriate stabilizers are
important in retarding degradation and main-
taining physical properties for production of
high quality adhesives. Antioxidants, such as
Irganox 1010 or Irganox 245 provide good
processing stability, and Tinuvin B 75, Tinuvin
571, Tinuvin 765 or Tinuvin 123 can provide
enhanced light stability.
Figure 19 shows that light stabilizers in combi-
nation with antioxidants (Tinuvin B 75 or a
combination of Irganox 245 and Tinuvin 571)
provide the best overall protection in this
solvent-based polyurethane adhesive.
0 1
Yellowness Index
2 3 4 5
Days
0
5
10
Unstabilized
0.75% Irganox 245 + Tinuvin 571, 1:2
0.75% Irganox 245 + Tinuvin 765, 1:2
0.75% Tinuvin B 75
0.50% Tinuvin 571
0.50% Tinuvin 765
15
20
25
Figure 19. Stabilization of Solvent-Based
Polyurethane Adhesives
Sample: 100p PUR, 30% MEK, 50p toluene, 10p hardner
Test Criterion: Yellowness Index after exposure in Xenon 150
21
0 500
Hours, Carbon Arc Weather-Ometer
1000 1500 2000
Degree of Crazing
0
1
2
3
4
5
Unstabilized
0.50% Tinuvin 765 + Irganox 245, 1:1
0.75% Tinuvin 765 + Irganox 245, 2:1
0.75% Tinuvin 765 + Tinuvin 328 + Irganox 245, 1:1:1
1.50% Tinuvin 765 + Tinuvin 328 + Irganox 245, 1:1:1
Degree of Surface Crazing:
0 = no crazing
1 = very slight crazing
2 = slight crazing
3 = moderate crazing
4 = significant crazing
5 = severe crazing
5 10 15 20
E
1.25% Irganox 245
+ Tinuvin 328
+ Tinuvin 765, 1:2:2
Unstabilized
100 hours XAW exposure
250 hours XAW exposure
1.25% Irganox 245
+ Tinuvin 213
+ Tinuvin 765, 1:2:2
15
15
11
12
9
10
Figure 20. 2-Part Polyurethane Sealant with
Amine Curative
Test Criterion: Degree of crazing after Carbon Arc
Weather-Ometer exposure
Figure 21. Light Stabilization of Polyurethane Sealant
Delta E: ASTM D1925, D65 Illuminant, 10 observer, LAV
Test Criterion: Color Development (Delta E) after Dry Xenon Arc
Weather-Ometer Exposure
In a 2-part polyurethane sealant, all stabilization
formulations show significant improvement over
the unstabilized control. After 2000 hours of
Carbon Arc exposure, the ternary blend of
Irganox 245 + Tinuvin 328 + Tinuvin 765 shows
the best performance (Figure 20).
Figure 21 shows the effects of various light stabi-
lizer/antioxidant combinations for stabilizing a
polyurethane sealant formulation. A 1:2:2 ratio of
Irganox 245:Tinuvin 213:Tinuvin765 results in the
lowest color development after Xenon exposure.
22
Polyurethane Fiber
Polyurethane fiber commonly known as
spandex is a synthetic elastomeric fiber. It is
strong with very high extensibility and recover-
ability characteristics (elasticity) making it ideal
for such textile applications as swimsuits, hosiery
and fitness garments. Production of polyure-
thane fiber typically requires antioxidants, such
as Irganox 245 or Irganox MD1024.
For enhanced performance demanded by
consumers, light stability for exterior exposure
is provided by combinations of ultraviolet light
absorbers (Tinuvin 328, Tinuvin 234 or
Tinuvin 327) with hindered amines (Tinuvin 765,
Chimassorb 944 or Tinuvin 622).
Figure 22 shows a polyurethane fiber sample in
which Tinuvin 213 and Tinuvin 234 used in
combination with Tinuvin 765 showed no signs
of failure even after 800 hours of dry Xenon
exposure. In the same test, the unstabilized
sample failed shortly after 200 hours, while the
sample with Tinuvin 328 in combination with
Tinuvin 765 failed after 496 hours. This failure is
probably because of the loss of Tinuvin 328 due
to its volatility. However, the same stabilizer
combination of Tinuvin 328 and Tinuvin 765
showed good gas fade resistance (Figure 23).
Light stability of polyurethane fibers is key for
many outdoor applications. The Xenotest data
in Figure 24 shows that a processing stabilizer
with a hindered amine light stabilizer (Tinuvin
622) does provide some protection, but with
the addition of a UV absorber (Tinuvin 234),
the time to a YI of 20 was increased by a
factor of three.
23
Figure 23. Gas Fading of Polyurethane Fiber
Exposure: NO
x
Chamber
Test Criterion: Color Development (YI) after NO
x
Exposure
Figure 22 Light Stabilization of Polyurethane Fiber
Test Criterion: Color Development (YI) after Dry Xenon Exposure
0 100 200 300
Hours
0.5% Cyanox 1790
+ 0.5% Tinuvin 622
+ 0.5% Tinuvin 234
0.5% Cyanox 1790
+ 0.5% Tinuvin 622
0.5% Cyanox* 1790
Control
100
300
80
78
* Cyanox is a registered trademark of Cytec Corporation
Figure 24. Stabilization of Polyurethane Fiber
Test Criterion: Time to reach YI = 20 after Xenotest 1200
200 400 600 800
Hours
Yellowness Index
Unstabilized
1.0% Tinuvin 328 + Tinuvin 765, 1:1
1.0% Tinuvin 213 + Tinuvin 765, 1:1
1.0% Tinuvin 234 + Tinuvin 765, 1:1
20
15
10
5
0
6.9
25
21.7*
5.4*
6
* Physical Property Failure
5 0 10 15 20
0 hours
50 hours
1.0% Tinuvin 328
+ Tinuvin 765, 1:1
0.3
6.1
Unstabilized
1.4
18.6
Yellowness Index
24
Chemical Structures of Ciba Additives for Polyurethane
Data Bank
OH
O
Irganox 245
CH
2
CH
2
CO(CH
2
CH
2
O)
3
2
Irganox 1010
OH
O
O
C
4
OH
CH
2
CH
2
COC
18
H
37
O
Irganox 1076
Irganox 5057
N
H
R R
1
R, R
1
= H, C4H9, or C8H17
and other alkyl chains.
N N O O (CH
2
)
8
C
O
C
O
H
17
C
8
O OC
8
H
17
Tinuvin 123
Tinuvin 326
N
N
N
HO
CI
CH
3
N
N
N
HO
Tinuvin 327
CI
N N O O CH
3
CH
3
(CH
2
)
8
C
O
C
O
Tinuvin 765
CH
2
H
O
N
H
H
3
C
H
3
C
CH
3
CH
3
CH
3
CH
2
CH
2
CH
2
O C
O
C
O
O
Tinuvin 622
n
N
N
N
HO
Tinuvin P
CH
3
25
N
N
N
OH
Tinuvin 213
CH
2
CH
2
CO(CH
2
CH
2
O)
N
in 13% Polyethyelene glycol
O
HN
O O C C
O O
NH
(CH
2
)
8
Tinuvin 770
N
N
N
HO
C(CH
3
)
2
CH
2
CH
3
C(CH
3
)
2
CH
2
CH
3
Tinuvin 328
N
N
N
OH
Tinuvin 571
CH
3
C
12
H
25
CH
2
HO
Irganox 1135
CH
2
O C
O
R
R = C 7-9 Branched Alkyl Esters
S
O
N
O
N
Uvitex OB
HO
Irganox 1098
CH
2
CH
2
CNH(CH
2
)
3
2
O
N H
3
C
N H
3
C
O C
O C
C
OH CH
2
C
4
H
9
O
O
Tinuvin 144
26
Chemical Names of Ciba Additives for Polyurethanes
Additive Chemical Name CAS No.
Irganox 245 Ethylene bis (oxyethylene) bis(3-tert-butyl-4-hydroxy- 36443-68-2
5(methylhydrocinnamate)
Irganox 1010 Tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy 6683-19-8
hydrocinnamate)]methane
Irganox 1076 Octadecyl 3,5-di-tert-butyl-4-hydroxyhyrocinnamate 2082-79-3
Irganox 1098 N,N-Hexamethylene-bis 23128-74-7
(3,5-di-tert-butyl-4-hydroxyhyrocinnamamide)
Irganox 1135 3,5-Di-tert-butyl-4-hydroxyhydrocinnamic acid,C7-9 125643-61-0
branched alkyl esters
Irganox 5057 N-phenylbenzen amine, reaction products with 2,4, 68411-46-1
4-trimethylpentene
Tinuvin P 2-(2-Hydroxy-5-methylphenyl)-benzotriazole 2440-22-4
Tinuvin 123 bis-(1-Octyloxy-2,2,6,6,tetramethyl-4- piperidinyl) sebacate 129757-67-1
(trivial name)
Tinuvin 144 n-Butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)bis-(1,2,2,6- 6384-3-89-0
pentamethyl-4piperridinyl)malonate
Tinuvin 213 Poly (oxy-1,2-ethanediyl), (_,(3-(3-(2H-benzotriazol-2-yl)-5- 104810-48-2
(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl)-t-hydroxy;
Poly (oxy-1,2-ethanediyl), (_-(3-(3-(2H-benzotriazol-2-yl)-5- 104810-47-1
(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropyl-t-
(3-(3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)
-4-hydroxyphenyl)-1-oxopropoxy)
Tinuvin 326 2-(5-Chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4- 3896-11-5
methylphenol
Tinuvin 327 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole 3864-99-1
Tinuvin 328 2-(2H-Benzotriazol-2-yl)-4,6-bis(1,1-dimethylpropyl)phenol 25973-55-1
Tinuvin 571 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, 125304-04-3
branched and linear
Tinuvin 622 Dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl- 65447-77-0
1-piperidineethanol
Tinuvin 765 bis(1,2,2,6,6,-Pentamethyl-4-piperidinyl) sebacate 41556-26-7
(major component)
Tinuvin 770 bis(2,2,6,6-Tetramethyl-4-piperidinyl) sebacate 52829-07-0
Uvitex OB 2,2-(2,5-thiophenediyl)bis[5-tert-butylbenzoxazole] 7128-64-5
Physical Properties of Ciba Additives for Polyurethanes
27
Additive Molecular Melting Specific TGA, in air at 20C/min. Appearance*
Weight Point (C) Gravity
at 20C Temp. at Temp at
1% Wt. Loss 10% Wt. Loss
Irganox 245 587 76-79 1.14 290 330 white powder
Irganox 1010 1178 110-125 1.15 310 355 white powder
Irganox 1076 531 50-55 1.02 230 290 white powder
Irganox 1098 640 156-161 1.04 290 330 white crystalline
powder
Irganox 1135 391 liquid 0.95-1.0 160 200 clear to slight
yellow liquid
Irganox 5057 330 0 - 5 (liquid) 0.98 130

200

pale yellow
liquid
Tinuvin P 225 128 1.38 180 205 light yellow
crystalline
powder
Tinuvin 123 737.2 liquid 0.97 160

265

pale yellow
liquid
Tinuvin 144 685 146-150 1.07 250 290 off-white
powder
Tinuvin 213 637 (comp.1) liquid 1.17 140

280

yellow to light
975 (comp. 2) amber liquid
Tinuvin 326 316 138-141 1.32 200

245

light yellow
powder
Tinuvin 327 358 154-158 1.26 180 235 pale yellow
powder
Tinuvin 328 352 79-87 1.17 190

230

off-white
powder
Tinuvin 571 394 liquid 1.0 170 245 pale yellow
liquid
Tinuvin 622 >2500 55-70 1.18 290 320 off-white
powder
Tinuvin 765 509 liquid 0.99 225

275

clear to slight
yellow liquid
Tinuvin 770 481 82-86 1.05 200

260

white powder
Uvitex OB 431 196-202 1.26 300 340 yellow powder
* Many products are available in product forms other than powders

10C/min in nitrogen

20C/min in nitrogen

10C/min in air
28
Solubilities of Ciba Additives for Polyurethanes
Additive Solubility @ 20C, Wt. %
Water n-Hexane Methanol Acetone Ethyl Acetate
Irganox 245 <0.01 <0.1 12 >50 37
Irganox 1010 <0.01 0.3 0.9 46 47
Irganox 1076 <0.01 32 0.6 19 38
Irganox 1098 <0.01 0.01 6 2 1
Irganox 1135 <0.01 >50 >50 >50 >50
Irganox 5057 <0.1 >50 20 >50 >50
Tinuvin P <0.01 1.1 0.2 2.5 3.5
Tinuvin 123 - - - - >100
Tinuvin 144 <0.01 2 1 4 29
(Benzene)
Tinuvin 213 <0.01 - - - >50
Tinuvin 326 <0.01 1 0.1 1 2
Tinuvin 327 <0.01 4 <0.1 1 5
Tinuvin 328 <0.01 16 0.4 6 16
Tinuvin 571 <0.01 >50 1 >50 >50
Tinuvin 622 <0.01 <0.01 0.05 4 3
Tinuvin 765 <0.01 >50 >50 >50 >50
Tinuvin 770 <0.01 5 38 19 24
Uvitex OB <0.01 0.2 <0.1 0.5 0.4
(Benzene)
FDA Clearance Summary
(1)
Max. Foods Temperatures
Product Existing Regulations Conc. Thickness Allowed Allowed
Irganox 245 Adhesives complying with 175.105 no restrictions no restrictions no restrictions no restrictions
Irganox 1010 All polymers used as indirect 0.5% no restrictions no restrictions no restrictions
additives in food packaging
Adhesives complying with 175.105 no restrictions no restrictions no restrictions no restrictions
Pressure sensitive adhesives 1% no restrictions no restrictions no restrictions
complying with 175.125
Irganox 1076 Adhesives complying with 175.105 no restrictions no restrictions no restrictions no restrictions
Rubber articles complying with 5% no restrictions no restrictions no restrictions
177.2600
Irganox 5057 Rubber articles complying with 5% no restrictions no restrictions no restrictions
177.2600 (total antioxidant
level)
Pressure sensitive adhesives 0.5% no restrictions no restrictions no restrictions
complying with 175.125
Tinuvin 328 Adhesives complying with 175.105 no restrictions no restrictions no restrictions no restrictions
Uvitex OB Adhesives complying with 175.105 no restrictions no restrictions no restrictions no restrictions
(1) The products listed herein have been cleared by the Food and Drug Administration for use in polymers intended for
food contact applications, in accordance with the cited regulations as printed in Title 21, U.S. Code of Federal Regulation
(21 CFR), or as amended by the Federal Register, which should be consulted before use.
Irgafos, Irganox, Tinuvin and Uvitex are registered trademarks of Ciba Specialty Chemicals. Chimassorb is a registered trademark of
Chimosa Chimica Organica S.p.A, Bologna, Italy.
SAFETY AND HANDLING
Read and understand the respective Material Safety
Data Sheet (MSDS) before handling.
Some of these products are considered to be hazardous
chemicals under the OSHA Hazard Communication
Standard (29 CFR1910.1200).
For Industrial Use Only
IMPORTANT
The following supercedes Buyers documents. SELLER
MAKES NO REPRESENTATION OR WARRANTY,
EXPRESS OR IMPLIED, INCLUDING OF MER-
CHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE. No statements herein are to be construed as
inducements to infringe any relevant patent. Under no
circumstances shall Seller be liable for incidental, conse-
quential or indirect damages for alleged negligence,
breach of warranty, strict liability, tort or contract arising
in connection with the product(s). Buyers sole remedy
and Sellers sole liability for any claims shall be Buyers
purchase price. Data and results are based on controlled
or lab work and must be confirmed by Buyer by testing
for its intended conditions of use. The product(s) has
not been tested for, and is therefore not recommended
for, uses for which prolonged contact with mucous
membranes, abraded skin, or blood is intended; or for
uses for which implantation within the human body is
intended.
Ciba Specialty Chemicals Inc.
Additives
Ciba Specialty Chemicals
Head Office
EUROPE, MIDDLE EAST, AFRICA
Ciba Specialty Chemicals Inc.
Additives
P.O. Box
CH-4002 Basel
Switzerland
NAFTA
Ciba Specialty Chemicals Corp.
Additives
540 White Plains Road
P.O. Box 2005
Tarrytown, NY 105919005
USA
SOUTH AMERICA
Ciba Especialidades Qumicas Ltda.
Av. Prof. Vincente Rao, 90
BR-04706-900 SO PAULO-SP
Brazil
ASIA PACIFIC
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(Singapore) Pte Ltd
Jurong Point Post Office
P.O. Box 264
SGP-SINGAPORE 916409
JAPAN
Ciba Specialty Chemicals
Tokyo Head Office
P.O. Box 33
Minato-ku
J-Tokyo 105
Japan
http://www.cibasc.com
Ciba Additives worldwide
Algeria, Hydra
Argentina, Buenos Aires
Australia, Thomastown/Melbourne
Austria, Vienna
Benelux Region, Groot-Bijgaarden
Brazil, So Paulo
Bulgaria, Sofia
Canada, Mississauga/Toronto
Chile, Santiago
Colombia, Santaf de Bogot
Czech Republic, Prague
Denmark, Copenhagen
Egypt, Cairo
Finland, Helsinki
France, Rueil-Malmaison
Germany, Lampertheim
Great Britain and Ireland, Macclesfield
Hungary, Budapest
India, Mumbai
Indonesia, Jakarta
Iran, Teheran
Italy, Pontecchio Marconi
Japan, Tokyo
Korean Republic, Seoul
Malaysia, Klang
Mexico, Puebla
New Zealand, Auckland
Norway, Oslo
Pakistan, Karachi
Peoples Republic of China, Shanghai
Philippines, Manila
Poland, Warsaw
Portugal, Porto
Russia, Moscow
Saudi Arabia, Al-Khobar
Singapore
Slovenia, Ljubljana
South Africa, Isando/Johannesburg
Spain, Barcelona
Sweden, Vstra Frlunda
Switzerland, Basel
Taiwan ROC, Kaohsiung
Thailand, Bangkok
Turkey, Istanbul
UAE, Abu Dhabi/Dubai
USA, Tarrytown, NY
Venezuela, Caracas
Value beyond chemistry