International Journal of Industrial Chemistry (2019) 10:49–55

https://doi.org/10.1007/s40090-019-0170-y

RESEARCH

The effect of octylated diphenylamine and Irganox 1520 antioxidants

on the stability of polybutadiene rubber
Alireza Fazlali1 · Vahab Ghaleh Khondabi1 · Mohammad Javad Sharifi2 · Mohammad Amir Nikoohemmat1

Received: 14 June 2018 / Accepted: 16 January 2019 / Published online: 13 February 2019
© The Author(s) 2019

Abstract
One of the serious problems in polybutadiene rubber (PBR) production units is the color change in products, which is due
to aging and the inability of antioxidants to protect the product, especially at high temperatures. In this study, the effects of
amine-type antioxidant [octylated diphenylamine (OD)] and non-amine-type antioxidant (Irganox 1520) on the color yel-
lowness, gel content and thermal stability of PBR, at concentrations of 500, 1000, 1500, 2500 and 4000 ppm, at temperature
of 110 °C, and different aging times (1–10 h) were investigated. The results showed that the polymer with Irganox 1520
antioxidant has a higher thermal stability, less gel formation and lower color than polymer containing OD antioxidant;
therefore, the Irganox 1520 antioxidant was more suitable.

Keywords Antioxidant · Color yellowness · Gel content · Irganox · Octylated diphenylamine · Polybutadiene rubber ·
Stability

Introduction change of nature [9, 10]. Even a simple monophosphate anti-

oxidant such as butylated hydroxytoluene (BHT) may also
Nowadays, polybutadiene products are used in the manufac- reduce the antioxidant activity and create a quinone system,
ture of various catalysts. One of the catalytic systems used is which can act as a color agent in the polymer [11–13].
cobalt acetate, which uses antioxidant for the stability of the Octylated diphenylamine (C28H43N) is a medium activ-
polymer [1]. The stabilizers of polymers should effectively ity, amine-type antioxidant for general-purpose elastomer
protect polymers from various, mostly radical-degrading, use. It is antioxidant for natural rubber (NR), styrene-buta-
processes, be compatible with the polymer, and persist in the diene rubber (SBR), nitrile-butadiene rubber (NBR) and
polymer [2–5]. Antioxidants in the polymerization reactions chloroprene rubber (CR). It has good protective character
are compounds that are used to inhibit the reaction between to heat, oxygen, flexing and crazing, and is efficient to rubber
polymers and free air oxygen. The oxidation process can be whether used together with carbon black [14]. It has obvi-
carried out at all stages of the existence of a polymer from ous thermal brittleness resistance in CR, and can increase
the moment of manufacture up to the time of consumption its protective character to ozone aging. It is also used as
and cause unwanted changes in the chemical, mechanical antioxidant and corrosion inhibitor in saline and synthetic
and electrical properties of the polymer [6–8]. If, for any lubricants, and as a general-purpose for non-blooming anti
reason, the antioxidant is not injected into the polymer, the degrading in both black and non-black stocks, and in latex
product is dark brown after a short time and its physical and applications [9].
mechanical properties are practically altered. The reason for Irganox 1520 (C25H44OS2) is a multifunctional phe-
this is the destruction of the polymer by oxidation and the nolic antioxidant for organic substrates such as elastomers,
plastics, adhesives, sealants, oils and lubricants. It effec-
* Alireza Fazlali tively protects the substrate against thermo-oxidation dur-
a‑fazlali@araku.ac.ir ing processing and long-term heat aging. It is non-stain-
ing, non-discoloring, low in volatility, and stable to light
1
Department of Chemical Engineering, Faculty and heat. Irganox 1520 is an effective stabilizer in a wide
of Engineering, Arak University, Arāk, Iran
range of solution polymerized, emulsion polymerized and
2
Department of Chemical Engineering, Faculty thermoplastic elastomers including butadiene rubber (BR),
of Engineering, Tehran University, Tehran, Iran

13
Vol.:(0123456789)
50 International Journal of Industrial Chemistry (2019) 10:49–55

styrene–butadiene rubber (SBR), nitrile–butadiene rubber Results and discussion

(NBR), isoprene rubber (IR), styrene–butadiene–styrene
(SBS) and styrene–isoprene–styrene (SIS), as well as natu- Effect of antioxidants on color yellowness
ral rubber [14, 15]. It can be used with other additives such
as secondary antioxidants, benzofuranone, light stabilizers Figure 1 shows the effect of antioxidant on the color of
and other functional stabilizers, the recommended dosage the solution of polybutadiene at different concentrations at
level of which is 0.05–0.3% [16, 17]. 110 °C. By increasing the aging time from 1 to 5 h at a spe-
In this work, considering that the technical knowledge cific concentration of both antioxidant types, the amount of
of the use of antioxidants was related to the past two dec- coloration in the polymer matrix containing Irganox 1520
ades, attempts have been made to find antioxidants more and OD increases from 6 to 11 and from 7 to 13, respec-
favorable than the antioxidants used in the technologies tively, which in fact indicates the negative effect of time
available in the polybutadiene production industry. on the antioxidant activity. However as shown in Fig. 1a–d,
increasing concentration from 500 to 2500 ppm at a given
time does not have a significant effect on the color index
and sometimes reduces it. By comparing the figures, it can
Materials and methods be said that at all times and concentrations, the color index
in Irganox 1520 was always lower than OD, which indicates
Preparation of the samples its advantage.
One of the main factors in the creation of color in the
Polybutadiene (Shazand Petrochemical Company, Iran) composition of polybutadiene is the destruction of the anti-
and toluene (99/8%, Sigma-Aldrich) as solvents, Irganox oxidant and the conversion into the quinone system due to
1520 as a phenolic antioxidant (99%, Basel, Switzerland) the presence of these products resulting from the destruction
and an octylated diphenylamine as an amine antioxidant of antioxidants, and because of the absorption of light in the
(98%, Richem, Shanghai china) were used as main materi- visible region, it creates color in the polymer matrix. Fig-
als. First, 20 g of polybutadiene was dissolved in 300 cm3 ure 2 shows the mechanism for the formation of a quinone
of toluene and the appropriate amount of antioxidant was system in the OD antioxidant [21]. As shown in Fig. 2, con-
added to it, and then in the nitrogen gas atmosphere, the jugate bonds in the OD structure formed by the resonance
sample of the toluene solvent was dried. After drying, the with the aromatic system reduce the energy level of molecu-
sample was placed in an oven at 110 °C for aging times of lar orbitals (π) and antibonding molecular orbital (π*) and
2, 4, 6, 8, and 10 h. The aging method was carried out in a transfer the maximum absorption to longer wavelengths;
manner similar to that described in ASTM D1693, ASTM eventually, they absorb into the visible region, and hence
D573 tests for plastic materials. produce color in the PBR product.
The Irganox 1520 antioxidant due to the existence of the
functional phenolic group in its chemical structure (Fig. 3)
Analytical methods [22] can acts as a first-type antioxidant, and on the other
hand, because of the functional sulfide group, it also acts
Measurement of solution color was performed with a UV as a secondary type of antioxidant. The presence of the
Spectrophotometer (DR 4000) at a wavelength of 600 nm, functional group in the ortho and para positions, relative to
based on ASTM D1209-00 [18]. For estimation of gel con- the formation of a quinone system, shows more resistance,
tent, some of the samples were made in the form of nar- which is one of the important factors of color formation.
row strings (W) and dissolved in toluene, then filtered it
through the sieve with 50-µm mesh (W 1), and weighed Effect of antioxidants on gel content
again after washing, filtering and drying (W2). Gel content
was calculated as a percentage by weight [19]: Figure 4 shows the effect of antioxidant on the gel content of
W 2 − W1 polybutadiene solution in different concentrations at 110 °C.
Gel content(%) = × 100. (1) By increasing the aging time from 2 to 10 h at a specific
W
concentration of both antioxidants, the gel content of poly-
Differential scanning calorimetry thermal analysis is mer with Irganox 1520 and OD increases from 0.5 to 2.5%
a method in which material changes at different tempera- and from 0.5 to 4%, respectively, which in fact indicates the
tures are investigated over time. Differential scanning calo- negative effect of time on the antioxidant activity. However
rimetry was performed with a DSC (METTLER-TC11) at Fig. 4a–d show that increasing concentration from 500 to
30–300 °C (10 °C/min) and atmospheric pressure [20]. 2500 ppm at a given time does not have a significant effect

13
International Journal of Industrial Chemistry (2019) 10:49–55 51

Fig. 1  Effect of IRGANOX 1520 and OD on PBR color at 110 °C and concentration of a 500 ppm, b 1000 ppm, c 1500 ppm and d 2500 ppm

on the gel content and sometimes reduces it. By comparing chains, and as the process of destruction goes up, cross-
the figures and considering that the mechanism of destruc- link increases and more energy is released into the system;
tion in polybutadiene is the type of cross-link formation, however, if the antioxidant has less enthalpy, the more
the Irganox 1520 antioxidant creates less gel in the polymer effective it will be.
system and has a better performance than OD antioxidant. Figure 7 shows the relationship between the enthalpy,
and the antioxidant type and its concentration. As shown
in this figure, with increasing concentration of each
Thermal analysis: differential scanning calorimetry antioxidant from 500 to 4000 ppm, enthalpy destruc-
tion decreases from 213.5 to 120.4 J/g and from 247.6 to
Figures 5 and 6 show DSC thermograms for both antioxi- 122 J/g for Irganox and OD, respectively, but in identical
dants at a temperature range of 30–300 °C with a tempera- concentrations, the enthalpy of the Irganox 1520 is less
ture rise rate of 10 °C/min. It is clear by refering to the than the OD, which indicates that Irganox 1520 antioxi-
therogram of DSC test, the resulting thermogram appears dant system protects the polymer against thermal degrada-
as a positive peak, that whatever the grater destruction in tion better than OD antioxidant. It can also be said that,
the polybutadiene chain, the higher number of cross-link, due to the non-amine-type antioxidant, Irganox 1520, hav-
and its exothermic enthalpy peak increases. As previously ing hydroxyl and thioether electron donors, relative to the
stated, the type of destruction mechanism in polybutadiene OD, in which nitrogen acts as an electron donor, therefore
is based on the formation of cross-link between polymeric it has a more stable radical and a better performance, and
the results show this very well.

13
52 International Journal of Industrial Chemistry (2019) 10:49–55

Fig. 2  Mechanism of OD
inhibitory effect in the polymer
system

Fig. 3  Mechanism of
IRGANOX 1520 inhibitory
effect in the polymer system

13
International Journal of Industrial Chemistry (2019) 10:49–55 53

Fig. 4  Effect of IRGANOX 1520 and OD on PBR gel content at 110 °C and concentration of a 500 ppm, b 1000 ppm, c 1500 ppm and d
2500 ppm

Conclusions of both antioxidants at a given time, the amount of color

decreases. It can be said that at different times and concen-
In this investigation, the performance of amine-type trations, the color produced by the Irganox 1520 antioxidant
(OD) and non-amine-type (Irganox 1520) antioxidants is less than OD, which indicates better performance.
in improving the stability of Polybutadiene was studied. By increasing the time at a specific concentration of
Experiments were carried out at 110 °C, atmospheric pres- both antioxidants, the gel content increases in the polymer,
sure, aging time of 1–10 h, and 500–4000 ppm of anti- while by increasing the concentration of both antioxidants
oxidant concentrations. The result of experiments dem- at a given time, the amount of gel decreases. At all times
onstrated the superiority of Irganox 1520 relative to OD and concentrations, the gel content in Irganox 1520 was
antioxidant. always lower than OD, which indicates its advantage.
By increasing the time at a specific concentration of both By increasing the concentration of both antioxi-
antioxidant types, the amount of coloration in the polymer dants, enthalpy destruction decreases, but in identical
matrix is increased, but by increasing the concentration

13
54 International Journal of Industrial Chemistry (2019) 10:49–55

Fig. 5  DSC thermogram of

PBR containing 500 ppm OD

Fig. 6  DSC thermogram of

PBR containing 4000 ppm
Irganox 1520

concentrations, the enthalpy of the Irganox 1520 is less does not significantly affect the stability of the product
than the OD, which indicates its better performance. and only increases the antioxidant use and, as a result,
According to the experiments, the Irganox 1520 con- increases the cost.
sumption range is 1500–2500 ppm. Using more amounts

13
International Journal of Industrial Chemistry (2019) 10:49–55 55

8. Mark HF (2004) Encyclopedia of polymer science and technology:

acoustic properties to cyclopentadiene and dicyclopentadiene, vol
5. Wiley, pp 163–168. https​://doi.org/10.1002/04714​40264​
9. Malik J, Krohnke C (2006) Polymer stabilization: present status
and possible future trends. C R Chim 9:1330–1337. https​://doi.
org/10.1016/j.crci.2006.02.009
10. Subudhi AW, Jacobs KA, Hagobian TA, Fattor JA, Fulco CS,
Muza SR, Rock PB, Hoffman AR, Cymerman A, Friedlander AL
(2004) Antioxidant supplementation does not attenuate oxidative
stress at high altitude. Aviat Space Environ Med 75:881–888
11. Lairez D, Adam M, Emery JR, Durand D (1992) Rheological
behavior of an epoxy/amine system near the gel point. Macromol-
ecules 25:286–289. https​://doi.org/10.1021/ma000​27a04​6
12. Moudgalya KM, Jaguste S (2001) A class of discontinuous
dynamical systems II. An industrial slurry high density polyethyl-
ene reactor. Chem Eng Sci 56:3611–3621. https:​ //doi.org/10.1016/
S0009​-2509(01)00044​-6
13. Muller R, Gerard E, Dugand P, Rempp P, Gnanou Y (1991) Rhe-
ological characterization of the gel point: a new interpretation.
Macromolecules 24:1321–1326. https​://doi.org/10.1021/ma000​
06a01​7
Fig. 7  The enthalpy of two antioxidant systems: Irganox 1520 and 14. Gruver JT, Rollmann KW (1964) Antioxidant properties of car-
OD bon black in unsaturated elastomers. Studies with cis-polybuta-
diene. J Appl Polym Sci 8:1169–1183. https​://doi.org/10.1002/
app.1964.07008​0311
Open Access This article is distributed under the terms of the Crea- 15. Fu Y, Yang C, Lvov YM, Zhang L, Wang W (2017) Antioxi-
tive Commons Attribution 4.0 International License (http://creat​iveco​ dant sustained release from carbon nanotubes for preparation of
mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu- highly aging resistant rubber. Chem Eng J 328:536–545. https​://
tion, and reproduction in any medium, provided you give appropriate doi.org/10.1016/j.cej.2017.06.142
credit to the original author(s) and the source, provide a link to the 16. Podesva J, Kovarova J (2003) Synthesis and performance of phe-
Creative Commons license, and indicate if changes were made. nolic polybutadiene-bound stabilizers. J Appl Polym Sci 87:885–
889. https​://doi.org/10.1002/app.11342​
17. Podesva J, Kovarova J, Hrdlickova M, Netopilik M (2009) Sta-
bilization of polyurethanes based on liquid OH-telechelic polyb-
References utadienes: comparison of commercial and polymer-bound antioxi-
dants. Polym Degrad Stab 94:647–650. https​://doi.org/10.1016/j.
1. Sulekha PB, Joseph R, Manjooran KB (2004) New oligomer- polym​degra​dstab​.2009.01.003
bound antioxidants in natural rubber/polybutadiene rubber and 18. ASTM D1209-05 (2011) Standard test method for color of clear
natural rubber/styrene–butadiene rubber blends. J Appl Polym liquids (platinum-cobalt scale). ASTM International, West Con-
Sci 93:437–443. https​://doi.org/10.1002/app.20427​ shohocken. http://www.astm.org. https​://doi.org/10.1520/D1209​
2. Brandt HD, Nentwig W, Rooney N, LaFlair RT, Wolf UU, Duffy -05R11​
J, Puskas JE, Kaszas G, Drewitt M, Stephan G (2011) Rubber, 5. 19. ASTM D2765-16 (2016) Standard test methods for determination
Solution rubbers. Ullmann’s encyclopedia of industrial chemistry. of gel content and swell ratio of cross linked ethylene plastics.
Wiley. https​://doi.org/10.1002/14356​007.o23_o02 ASTM International, West Conshohocken. http://www.astm.org.
3. Maiti M, Jasra R (2011) High-cis polybutadiene rubber in https​://doi.org/10.1520/D2765​-16
benign solvents and process for preparation thereof. Patent 20. ISO 11357-3 (2011) Plastics–differential scanning calorimetry
US20120296055 A1 (DSC)–part 3: determination of temperature and enthalpy of melt-
4. Singh A, Modi S, Subrahmanyam N, Munshi P, Upadhyay VK, ing and crystallization. International Organization for Standardi-
Jasra RV, Maiti M (2010) Retarding effect of aromatic solvents zation. http://www.iso.org
on cobalt(II)-based catalyst system during synthesis of high cis- 21. Cibulkova Z, Simona P, Lehocky P, Balko J (2005) Antioxidant
1,4-polybutadiene. Ind Eng Chem Res 49:9648–9654. https​://doi. activity of p-phenylenediamines studied by DSC. Polym Degrad
org/10.1021/ie101​324d Stab 87:479–486. https​://doi.org/10.1016/j.polym​degra​dstab​
5. Srivastava VK, Maiti M, Basak GC, Jasra RV (2014) Role of catal- .2004.10.004
ysis in sustainable production of synthetic elastomers. J Chem Sci 22. Meier H, Dubs P, Kunzi H, Martin R, Knobloch G, Bertterman
126:415–427. https​://doi.org/10.1007/s1203​9-014-0580-5 H, Thuet B, Borer A, Kolczak U, Rist G (1995) Some aspects
6. Das PK, DesLauriers PJ, Fahey DR, Wood FK, Cornforth of a new class of sulfur containing phenolic antioxidants. Polym
FJ (1995) Photostabilization of poly (p-phenylene sulfide). Degrad Stab 49:1–9. https:​ //doi.org/10.1016/0141-3910(95)00058​
Polym Degrad Stab 48:1–10. https​: //doi.org/10.1016/0141- -T
3910(95)00032​-H
7. Saunier J, Mazel V, Aymes-Chodur C, Yagoubi N (2012) Bloom- Publisher’s Note Springer Nature remains neutral with regard to
ing of Irganox 3­ 114® antioxidant onto a medical grade elastomer. jurisdictional claims in published maps and institutional affiliations.
Impact of the recrystallization conditions on the antioxidant poly-
morphism, on the film wettability and on the antioxidant leach-
ability. Int J Pharm 437:89–99. https​://doi.org/10.1016/j.ijpha​
rm.2012.07.060

13