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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
Photolysis Autoxidation
O2 R'H
R AR* AR• AROO• AROOH ARO•+•OH
Step 1 Step 2 Step 3 Step 4 + Step 5
A
R'•
R'H
Step 1 ROO•A ROOH + R'•
R'
UVAs Tinuvin® P
Tinuvin 213
Tinuvin 326
Tinuvin 327
Tinuvin 328
Tinuvin 571
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)
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
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)
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.
Unstabilized 37
Table 3 compares the light stability of aromatic During storage and end use, TPUs can be 11
vs. aliphatic based polyurethanes. Although sta- exposed to nitrogen oxides that may cause the
bilizers do provide some improvement in light polymer to discolor. This discoloration can be
stability for aromatic polyurethane, light stabiliz- minimized using a hindered amine (Tinuvin 765
ers are particularly effective in aliphatic or Tinuvin 770) or a combination of stabilizers as
polyurethane. 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.
12
Figure 9. Light Stability of Black RIM Polyurethane
Plaques (2 mm)
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
30
20
10
13
Yellowness Index
70
60
50
40
30
20
10
0 20 40 60 80
Exposure Time (hours)
Polyurethane Foams
Polyurethane can be foamed and shaped into Hindered phenolic antioxidants (Irganox 1076,
flexible, rigid and integral skin configurations. Irganox 1135) with alkylated diphenyl amines
Each of these types of applications will have (Irganox 5057) in the polyol provide good pro-
specific stabilizer requirements. When producing tection against scorch. Selection of the additive
flexible slabstock foams, the exotherm from the package will be determined by a number of fac-
polyol/isocyanate reaction can cause discol- tors including foaming technique and end-use
oration, called scorch, in the center of the foam. characteristics. Many processors prefer Irganox
This phenomenon is most common in flexible 1076 and Irganox 1135 due to their lower
slabstocks because of the size of the foam. Since volatility relative to BHT.
polyurethane foam is a good insulator, the
interior of the foam stays hot for many hours, Antioxidants are used to protect the urethane
increasing the risk of scorching. Because of their from processing and end-use degradation and
limited size, rigid and integral skin foams tend protect polyol from oxidation during storage
not to be as prone to scorching as flexible slab- and transport. Many end-use applications for
stock foams. 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 Polyurethane Flexible Foams/Textile Staining Test
Test Methods
Swiss Federal Laboratories for
Polyetherpolyol Isocyanate Materials Testing and Research (EMPA)
St. Gallen, Switzerland
Analytical Determination of Sample preparation
• Antioxidant content Two foam samples of each formulation are
• Peroxide formation exposed for 3 hours to air containing 50 ppm
(long-term storage) and 5 ppm NOx gas respectively. The samples
are then covered with two layers of cotton
Differential Scanning Colorimetry DSC textile (MOLTON), which has been previously
• Exotherm peak of oxidation reactions washed with a softener, and wrapped with
(effectiveness of antioxidants) aluminium film.
Samples aging
1) The samples are put into an air-circulating
oven at 40°C.
Foaming Formulation
2) Another series of samples, covered with one
Scorch Test layer of textile, is exposed for one month in
• Microwave/Humidity exposure air. These samples, under exclusion of direct
• Static ALU-Block Test sun radiation, are not wrapped in aluminium 15
film and not gassed.
• Dynamic ALU-Block Test
(discoloration, YI) Measurement of the textile discoloration
Differential Scanning Colorimetry (DSC) 1) Samples gassed with 50 ppm NOx gas.
• Exotherm peak of oxidation reactions The first textile layer is evaluated after
(effectiveness of antioxidants) 24 hours.
The second textile layer is evaluated after
Gasfading Test with NOx 48 hours.
• Yellowing of foam 2) Samples gassed with 5 ppm NOx gas.
• Yellowing of textiles The first textile layer is evaluated after
a. Volatility of antioxidants 48 hours.
b. Reactivity with NOx The second textile layer is evaluated after
c. Identification of reaction products 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.
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
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
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 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
4
1.25% Irganox 245
+ Tinuvin 328 11
+ Tinuvin 765, 1:2:2 12
3
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
O O
O
CH2— CH2—C—O—(CH2—CH2—O)3 CH2CH2 COC18H37
2 O
C
4
O O
HO CH2CH2CNH—(CH2)3 HO CH 2 CH 2 C O R
2
R = C 7-9 Branched Alkyl Esters
O OH
N 25
H3C N O C CH2 OH
N
O
C N
CH2CH2C —O—(CH2CH2O)N
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.
(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.
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.
Head Office Ciba Additives worldwide
Additives