Additives for Polyurethane

Enhanced Processing and Service Life

for Polyurethane Products

Additives Value beyond chemistry

Table of Contents

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 1
FDA Clearance Summary . . . . . . . . . . . . . . . . . . . . . . . . . .28
Solubility Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .28
2
Introduction

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 3
stabilizers, such as Tinuvin® and ChimassorbTM, 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.
 Polymer Degradation and Stabilization

Figure 1. Polymer Degradation and Stabilization

Thermo-oxidative Degradation
R• Alkyl radicals
Polyurethanes, like other organic materials, RO• Alkoxy radicals
react with molecular oxygen in a process ROO• Peroxy radicals Path of degradation
ROOH Hydroperoxide Path of stabilization
call “autoxidation.” This degradation
process results in product discoloration and
loss of physical properties.
RH (Polymer) Energy,
Autoxidation may be initiated by heat, high Catalyst residues,
Light Carbon centered
energy radiation (UV light), mechanical radicals react with
stress, catalyst residues, or through reaction Reacts with R• Lactone based
another RH stabilizers
with other impurities. Free radicals React with primary
antioxidants
(Figure 1) are generated which react rapidly (hindered phenols,
Oxygen
hindered amine
with oxygen to form peroxy radicals. These
peroxy radicals may further react with the
stabilizers)
to yield inactive products
Cycle II Cycle I
(ROH and H2O)
polymer chains leading to the formation of RO• + HO•
ROO•
hydroperoxides (ROOH). On exposure to
Energy,
heat or light, hydroperoxides decompose to Catalyst residues, Reacts with
yield more radicals that can reinitiate the Light another RH
Reacts with primary
degradation process. antioxidants
(hindered phenols,
R•
+ hindered amine
4 ROOH stabilizers)
Reacts with secondary antioxidants
(phosphites, hydroxylamines)
to yield inactive products

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.
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.
Oxygen-Centered Radical Traps
OO• OOH
´ ´
Ar2NH + -O-CH-CH2 A Ar2N• + -O-CH-CH2
Ar2N• + Ar’OH A Ar2NH + Ar’O•
J. Pospisil in “Developments in Polymer
Stabilization,” Vol. 1, Ch, 1, ed. G. Scott, Applied
Science Publ., London, 1979.
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 5
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.
 Photodegradation

Photolysis Autoxidation

O2 R'H
R AR* AR• AROO• AROOH ARO•+•OH
Step 1 Step 2 Step 3 Step 4 + Step 5
A

R'•

Photodegradation is really two distinct pro- Step 3

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
6 formed during photolysis interact with oxygen
to form peroxy radicals.
O2
R•A ROO•
In Step 3, the free radicals formed during pho-
tolysis readily react with oxygen to form peroxy
radicals. This is called autoxidation.

There are five separate steps during photodegra-

dation. In the following schematic, R represents Step 4
the polymer or UV absorbing component.

R'H
Step 1 ROO•A ROOH + R'•

In Step 4, the peroxy radicals attack the poly-

RA R* mer backbone (R'H) via hydrogen abstraction,
forming hydroperoxides and more free radicals.
Here, the polymer absorbs UV radiation. The
These free radicals (R'•) again readily react with
energy from the absorbed UV radiation
oxygen in Step 3 to form additional peroxy
“excites” the absorbing species (either polymer
radicals.
molecules or impurities) and raises them to a
higher energy level (R*). These excited state
molecules are very reactive and may undergo Step 5
a wide range of processes. Two common
processes are returning to the ground state or
homolytic bond cleavage. ROOH A RO• + •OH

Finally in Step 5, the hydroperoxides, which are

Step 2
R*A R•
If the molecule cannot be brought to its ground
state, homolytic bond cleavage and the forma-
tion of free radicals (R•) will occur.
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.
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 Figure 2. Schematic of Tautomerism

UV absorbers protect against photodegradation

(A) (B)
by competing with the polymer for absorption
of ultraviolet light. H O + H O
N N
UV
As shown in Figure 2, the excitation energy of N N
UV absorbers is rapidly and efficiently deacti- N
-∆
N
7
vated by the process of tautomerization.
Molecule A absorbs UV energy, resulting in an electronic
An ideal UVA should be very light stable, and rearrangement to form molecule B which, through the dissi-
should have high absorption over the UV range pation of heat energy, reverts to the original form, molecule
from 290 to 400 nanometers. Ciba Additives A. This process is repeated indefinitely.
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 Figure 3. Regenerative Mechanism of HALS*

Hindered amine light stabilizers (HALS) repre- R•

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
[O]
involves efficient trapping of free radicals with N-CH3 N-O • N-OR
subsequent regeneration of active stabilizer
moieties, represented in Figure 3. Examples of R'OO•
HALS are Tinuvin 123, Tinuvin 144, Tinuvin 622,
Tinuvin 765, Tinuvin 770, and Chimassorb 944. R'OH + R=O
N
O O
O R

R'

* P.P. Klemchuk, M.E. Gande, Polymer Degradation and Stabilization,

1988, 22, 241; 1990, 27, 65
 Additives for Polyurethanes

Ciba Additives for Polyurethanes

Antioxidants Irganox® 245

Irganox 1010
Irganox 1076
Irganox 1098
Irganox 1135
Irganox 5057

UVAs Tinuvin® P
Tinuvin 213
Tinuvin 326
Tinuvin 327
Tinuvin 328
Tinuvin 571

HALS Tinuvin® 123

Tinuvin 144
Tinuvin 622
8 Tinuvin 765
Tinuvin 770

Optical Uvitex® OB
Brightener

Figure 4. UV Absorption Spectra (20 mg/l Ethyl Acetate) Figure 5. Weight Loss of Antioxidants TGA, 20°C/min (air)

A Weight loss (%)

1.0 100

0.8 80

60
0.6

40
0.4
20
0.2
0
60 110 160 210 260 310 360
0.0 Temperature (°C)
270 290 310 330 350 370 390 410
Wavelength (nm) BHT
Irganox 1135
Tinuvin 327 Irganox 5057
Tinuvin 328 Irganox 1076
Tinuvin 571 Irganox 245
Tinuvin 213 Irganox 1010
Applications

Thermoplastic Polyurethane (TPU)

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). 9
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.
 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
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.
Figure 6. Discoloration of TPU Plaques (1.5 mm)

Exposure: 500 Hours Light Exposure. Dry Xenon

1 5 CI 35: b.P. T°C = 63°C, 0.35W/m2 Irradiance
Base Stabilization: 0.25% Irganox 1135/0.25% Tinuvin 765
25 13
50 42 Control

100 52
0.5% Tinuvin 571
* Shoe sole formulation, non-pigmented, PUR is
polyether based.
0.5% Tinuvin 328
10
0.5% Tinuvin 327
Antioxidants are needed to protect TPU
during processing. Both Irganox 1010 and
0 10 20 30 40
Irganox 245 have been used in commercial ∆E
production successfully for many years. The
stabilized TPU samples were able to sustain
two times longer ovenaging exposure than Figure 7. Tensile Strength and Elongation Retention
the sample without an antioxidant (Table 2). of TPU Plaques (1.5 mm)

Exposure: 500 Hours Light Exposure. Dry Xenon

Table 2. Ovenaging of Thermoplastic Polyurethane CI 35: b.P. T°C = 63°C, 0.35W/m2 Irradiance
Base Stabilization: 0.25% Irganox 1135/0.25% Tinuvin 765
Sample: 2 mm injection molded dumb-bells
Test Criterion: Ovenaging time at 120°C till
discoloration increases 20 Yellowness-
Index units. Tensile Strength

Days to YI=20
At 120°C
Elongation
Unstabilized 3
0.3% Irganox 1010 6.5
0.3% Irganox 245 6.5
0 20 40 60 80 100 120
% Retention

Control
0.5% Tinuvin 571
0.5% Tinuvin 328
0.5% Tinuvin 327
Substantial improvement in performance can be
achieved using a UVA/HALS combination vs UVA
alone, as demonstrated in Figure 8.

Figure 8. Accelerated Weathering, TPU Film

Sample: TPU Film, 6 mm

Exposure: Xenotest 450

Unstabilized 37

0.3% Tinuvin 328 174

0.3% Tinuvin 213 132

0.4% Tinuvin 328 269

+ 0.4% Tinuvin 765

0.4% Tinuvin 213 443

+ 0.4% Tinuvin 765

0 100 200 300 400 500

Hours to delta YI of 20

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 11
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.

Table 3. Comparison of Light Stability of Aromatic Table 4. Effect of Nitrogen Oxides* on Polyester-Based
and Aliphatic Polyurethane Film Polyurethane
Xenon Weather-Ometer Exposure
Yellowness Index
Hours to 50% Retention After 334 Hours
of Elongation

Unstabilized 53
Aromatic Aliphatic
1% Tinuvin P 50
Control 170 3,200 1% BHT 34
0.5% Tinuvin P + 390 4,500 1% Tinuvin 770 15
0.5% Irganox 1010
1% Tinuvin P + Tinuvin 770 (1:1) 13
0.5% Chimassorb 944 900 11,500
1% Tinuvin 770 + Irgafos 168 (1:1) 10
0.5% Tinuvin 622 670 11,500 1% Tinuvin 765 9
0.5% Tinuvin 765 850 13,900
* PUR plaques were maintained in an enclosed chamber
with nitrogen oxides present for 334 hours at 60°C.
PUR is a non-pigmented shoe sole type formulation.
 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.

12
Figure 9. Light Stability of Black RIM Polyurethane
Plaques (2 mm)

Test Criterion: Discoloration after WOM CI 65: b.P.

T°C = 63°, r.H. = 60%
∆E
15

12

0
0 250 500 750 1000
Time (Hours)

Control
1.5% Tinuvin B 75
1% Irganox 1010
+1% Tinuvin 770
+1% Tinuvin P
Figure 10 shows the reduction in yellowness Figure 10. PUR White Integral Foams Discoloration
when light stabilizers are used. Tinuvin B 75, a
liquid blend of three stabilizer functionalities, Exposure: Xenotest 450, Dry Cycle
BP = 45°C; Relative Humidity = 65%
provides good control of color development in
a white integral skin polyurethane foam sample Yellowness Index
even after hundreds of hours of dry light expo- 70

sure. Figure 11 is the sample exposed in a wet 60

cycle. Despite the more severe conditions,
50
Tinuvin B 75 provides excellent light stability.
40

30

20

10

0 50 100 150 200 250 300

Exposure Time (hours)

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)

13

Figure 11. PUR White Integral Foams Discoloration

Exposure: Weather-Ometer, Wet Cycle

BP = 45°C; Wet Cycle 112/18

Yellowness Index
70

60

50

40

30

20

10

0 20 40 60 80
Exposure Time (hours)

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)
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.
Polyurethane Foam Test Methods
Polyol and Flexible Polyurethane Foam Stabilization
Test Methods
Polyetherpolyol
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 NOx
• Yellowing of foam
• Yellowing of textiles
a. Volatility of antioxidants
b. Reactivity with NOx
c. Identification of reaction products
Polyurethane Flexible Foams/Textile Staining Test
Swiss Federal Laboratories for
Isocyanate 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 40°C.
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 15
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.
 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 8”x8”x4” cake box.

Cream times are typically 9-12 seconds, and rise
times 87-94 seconds.

5. After 2 minutes 14 seconds, a 4”x4” piece of the

top skin is removed. This piece is removed with a
4”x4” piece of cardboard supported by a pencil to
16 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).
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

Figure 13. Polyether Flexible Foams Stabilization
protection provided by a 2:1 ratio of Irganox 1135
and Irganox 5057. A 4:1 ratio of Irganox 1076 and Exposure: Dynamic Heat Test, Ovenaging for 30 Minutes
Irganox 5057 also provides equal performance to
the BHT system in the microwave scorch test. Unstabilized Unstabilized = 89°C

In ovenaging tests carried out in an aluminum- BHT

block oven, the foam sample stabilized with 3000 17
ppm of a combination of Irganox 1135 and Irganox 1135

Irganox 5057 at 2:1 ratio showed the longest time

BHT + Irganox 5057
to reach a Yellowness Index of 25 (Figure 13). (ratio 2:1)

For polyester foam samples, ovenaging tests in an Irganox 1135 +

Irganox 5057
aluminum-block oven show improvement in sta- (ratio 2:1)

bility, whether testing Irganox 1135 alone or in 160 170 180 190 200

combination with Irganox 5057 (Figure 14). Temperature (°C) to reach Yellowness Index = 25
Total additive concentration = 3000 ppm

Figure 12. Microwave Scorch Testing of Polyether

Polyurethane Cake Box Forms Figure 14. Polyester Flexible Foams Stabilization

Foam Formulation: 150.00 g Polyether Polyol, 1.50 g Surfactant, Exposure: Dynamic Heat Test, Ovenaging for 30 Minutes
6.75 g Water, 0.375 g Amine Catalyst,
0.12 g Tin Catalyst, 92.40 g Toluene Diisocyanate

17 Unstabilized
0.5% BHT/ 18
Irganox 5057
29

24 Irganox 1135
0.5% Irganox 1135/ 17
Irganox 5057
20
Irganox 1135 +
17 Irganox 5057
0.5% Irganox 1076/ (ratio 1:1)
Irganox 5057 32
44

0 10 20 30 40 50 190 195 200 205 210

∆E Temperature (°C) to reach Yellowness Index = 25

4:1 Ratio Total additive concentration = 3500 ppm

2:1 Ratio
1:1 Ratio
 Stabilization Minimizes Figure 15. Gasfade Discoloration of PUR Flexible Foam
Control
Textile Staining (BHT-free polyether polyol)
Exposure:
3
MOLTON Textile 1 Month Storage in Air
(EMPA-Test)
In many applications — such as automotive interiors, 0.24 % BHT
20.7
+ 0.06% Irganox 5057
furniture, mattresses, carpeting and shoulder pads — Control
(BHT-free polyether polyol) 3
polyurethane flexible foams come in contact with tex- 0.24 % Irganox 1135 1.1
+ 0.06% Irganox 5057
tiles. Proper stabilizers are needed to prevent scorch-
0.24 % BHT
ing of the foam and subsequent staining of +0.24 % Irganox
0.06% Irganox1076
5057 0.7
20.7
+ 0.06% Irganox 5057
the textile. Figures 15, 16, and 17 show how the
0.24 % Irganox 1135
proper selection of scorch inhibitors can minimize + 0.06% Irganox 5057 0
1.1
5 10 15 20 25
gas fade discoloration in textiles. Irganox 1135 or ∆E
Irganox 1076 limits the discoloration associated with 0.24 % Irganox 1076
0.7
+ 0.06% Irganox 5057
NOx exposure vs. BHT. Figure 15 is an air exposed
sample. Whereas, the sample in Figure 16 was 0 5 10 15 20 25
exposed to 5 ppm NOx for 48 and 96 hours. Figure 17 ∆E

shows a more severe exposure of 50 ppm NOx.

18 Figure 16. Gasfade Discoloration of PUR Flexible Foam Figure 17. Gasfade Discoloration of PUR Flexible Foam

Exposure: MOLTON Textile Ovenaging at 40°C Exposure: MOLTON Textile Ovenaging at 40°C
(EMPA-Test) (EMPA-Test)

Control 0.7
Control 1.2 BHT-free polyether polyol
(BHT-free polyether polyol) 1.1
1.2

0.24 % BHT 8.8

0.24 % BHT 2
+ 0.06% Irganox 5057 4.4
+ 0.06% Irganox 5057 2.6

0.24 % Irganox 1135 0.8

0.24 % Irganox 1135 0.9
+ 0.06% Irganox 5057 0.7
+ 0.06% Irganox 5057 0.9

0.24 % Irganox 1076 0.7

0.24 % Irganox 1076 1.4 + 0.06% Irganox 5057 1
+ 0.06% Irganox 5057 1.2

0 2 4 6 8 10
0 1 2 3 4
∆E
∆E
50 ppm NOx
5 ppm NOx 24 hours
48 hours 48 hours
96 hours
Light Stabilization
of Polyurethane Foams
The micrographs in Figure 18 show that a combi- during exposure to light. Note that the cell
nation of a hindered amine (Tinuvin 765) and structure of the stabilized foam looks similar to the
ultraviolet absorber (Tinuvin 328) can help protect unexposed foam even after l50 hours of Xenon
the cell structure of a polyether polyurethane foam exposure.
Figure 18. Surface microcrazing of Foamed Polyether Urethane

Unexposed
Magnification: 1,000X

19

Exposure: 150 hours in Xenon Weather-Ometer

Magnification: 1,000X
Unstabilized

Exposure: 150 hours in Xenon Weather-Ometer

Magnification: 1,000X
Stabilization System: 0.5% Tinuvin 328 + 0.5% Tinuvin 765
 Polyurethane Adhesives Figure 19. Stabilization of Solvent-Based
Polyurethane Adhesives
and Sealants
Sample: 100p PUR, 30% MEK, 50p toluene, 10p hardner
Polyurethanes are widely used for formulating Test Criterion: Yellowness Index after exposure in Xenon 150
adhesives and sealants. Polyurethane adhesive Yellowness Index
formulations include both solvent-based as well 25
as hot-melt. In some cases, high-performance
adhesives can replace standard mechanical 20

bonding methods such as nuts and bolts,

15
screws and welding. Appropriate stabilizers are
important in retarding degradation and main- 10
taining physical properties for production of
high quality adhesives. Antioxidants, such as 5
Irganox 1010 or Irganox 245 provide good
processing stability, and Tinuvin B 75, Tinuvin 0
0 1 2 3 4 5
571, Tinuvin 765 or Tinuvin 123 can provide Days
enhanced light stability. Unstabilized
0.75% Irganox 245 + Tinuvin 571, 1:2
Figure 19 shows that light stabilizers in combi- 0.75% Irganox 245 + Tinuvin 765, 1:2
0.75% Tinuvin B 75
nation with antioxidants (Tinuvin B 75 or a 0.50% Tinuvin 571
combination of Irganox 245 and Tinuvin 571) 0.50% Tinuvin 765
20 provide the best overall protection in this
solvent-based polyurethane adhesive.
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.

Figure 21. Light Stabilization of Polyurethane Sealant

Figure 20. 2-Part Polyurethane Sealant with
Amine Curative Delta E: ASTM D1925, D65 Illuminant, 10° observer, LAV
Test Criterion: Color Development (Delta E) after Dry Xenon Arc
Weather-Ometer Exposure
Test Criterion: Degree of crazing after Carbon Arc
Weather-Ometer exposure

Degree of Crazing Unstabilized 15

5 15

4
1.25% Irganox 245
+ Tinuvin 328 11
+ Tinuvin 765, 1:2:2 12
3

2 1.25% Irganox 245 9

+ Tinuvin 213
+ Tinuvin 765, 1:2:2 10
1
21
0 5 10 15 20
0 500 1000 1500 2000
∆E
Hours, Carbon Arc Weather-Ometer

Unstabilized 100 hours XAW exposure

0.50% Tinuvin 765 + Irganox 245, 1:1 250 hours XAW exposure
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 3 = moderate crazing
1 = very slight crazing 4 = significant crazing
2 = slight crazing 5 = severe crazing
 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
22 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.
Figure 22 Light Stabilization of Polyurethane Fiber

Test Criterion: Color Development (YI) after Dry Xenon Exposure

Yellowness Index
25

21.7*

20

15

10

6 6.9
5.4*
5

0
200 400 600 800
Hours

Unstabilized 23
1.0% Tinuvin 328 + Tinuvin 765, 1:1
1.0% Tinuvin 213 + Tinuvin 765, 1:1
1.0% Tinuvin 234 + Tinuvin 765, 1:1
* Physical Property Failure

Figure 23. Gas Fading of Polyurethane Fiber Figure 24. Stabilization of Polyurethane Fiber

Exposure: NOx Chamber Test Criterion: Time to reach YI = 20 after Xenotest 1200
Test Criterion: Color Development (YI) after NOx Exposure

Unstabilized 1.4 Control 80

18.6

0.5% Cyanox* 1790 78

0.3
1.0% Tinuvin 328
+ Tinuvin 765, 1:1 6.1 0.5% Cyanox 1790 100
+ 0.5% Tinuvin 622
0 5 10 15 20
0.5% Cyanox 1790
Yellowness Index 300
+ 0.5% Tinuvin 622
+ 0.5% Tinuvin 234

0 hours 0 100 200 300

50 hours Hours

* Cyanox is a registered trademark of Cytec Corporation

 Data Bank
Chemical Structures of Ciba Additives for Polyurethane

Irganox 245 Irganox 1010 Irganox 1076

OH OH
OH

O O
O
CH2— CH2—C—O—(CH2—CH2—O)3 CH2CH2 COC18H37
2 O
C
4

Irganox 5057 Tinuvin 123

R R1
24 O O
N H17C8O OC (CH2)8 CO N OC8H17
N
H
R, R1 = H, C4H9, or C8H17
and other alkyl chains.

Tinuvin P Tinuvin 326 Tinuvin 327

HO HO HO
N N N
N N N
N N N
CH3 CI CI
CH3

Tinuvin 622 Tinuvin 765

H3C O O
CH3
O O CH3 N O C (CH2)8 C O N CH3
H O
N CH2 CH2 O C CH2 CH2 C O CH3
H
CH3
H3C
n
Irganox 1098 Irganox 1135

O O
HO CH2CH2CNH—(CH2)3 HO CH 2 CH 2 C O R

2
R = C 7-9 Branched Alkyl Esters

Tinuvin 144 Tinuvin 213

O OH
N 25
H3C N O C CH2 OH
N
O
C N
CH2CH2C —O—(CH2CH2O)N

H3C N O C C4H9 in 13% Polyethyelene glycol

O

Tinuvin 328 Tinuvin 571

HO C(CH3)2CH2CH3 OH C12H25
N N
N N
N N
C(CH3)2CH2CH3 CH3

Tinuvin 770 Uvitex OB

O O N N
HN NH
O C (CH2)8 C O
O S O
 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
26 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
Additive Molecular Melting Specific TGA, in air at 20°C/min. Appearance*
Weight Point (°C) Gravity
at 20°C 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 27
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

† 10°C/min in nitrogen
†† 20°C/min in nitrogen
††† 10°C/min in air
 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
28 (21 CFR), or as amended by the Federal Register, which should be consulted before use.

Solubilities of Ciba Additives for Polyurethanes

Additive Solubility @ 20°C, 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)

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 Buyer’s 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). Buyer’s sole remedy
and Seller’s sole liability for any claims shall be Buyer’s
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.
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