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Antioxidant Trends that Enhance Durable Plastic Products

SpecialChem - Jan 25, 2010

Don Rosato

Types of Antioxidants
Primary Antioxidants
Secondary Antioxidants
Multifunctional and Other Antioxidant Advances
Antioxidant Suppliers/Plastics Antioxidant Market Report

Overview

Antioxidant Use in Plastics

More recent advances in high-performance antioxidants address increasingly stringent requirements including more
severe processing/use conditions and/or environmental concerns, while still focusing on the main objective of maintaining
plastic properties. Though required in only low concentrations, without antioxidant use, many plastic products would
have a short life, and many plastics could not even be manufactured without the protective attributes of antioxidants. On
a global basis, antioxidants valued at US$ 2.2 billion were used in plastics in 2008. This use is projected to grow to US$
2.87 by 2015 for an average annual growth rate (AAGR) of 4.5%.

Antioxidant Demand by Region

(Source: Acmite Market Intelligence)

Antioxidant Selection

Intrinsic sensitivity to oxidation varies greatly from one thermoplastic to another. While
polystyrene and polymethyl methacrylate are quite stable, even at processing temperatures,
polypropylene (PP) exhibits oxidative sensitivity at room temperature. Furthermore highly
unsaturated polymers such as copolymers derived from butadiene or isoprene are particularly
sensitive to oxidation. At the same time, antioxidants differ widely from each other in terms of
reactivity/effectiveness and are selected based on the antioxidant needs of specific plastics in a
given application.

However, other factors are equally important in selecting the most suitable antioxidant. These
include antioxidant volatility, compatibility with the matrix polymer (impacting migration/blooming
behavior) color stability, physical format (e.g. liquid, powder), transformation products Polymer Antioxidants
(taste/odor considerations), food contact application regulations, and performance versus cost (Source: Songwon

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considerations. Synergistic or additive combinations of two or more antioxidants are increasingly

International Americas)
used particularly in high-performance applications where a single antioxidant can only rarely
provide complete polymer stability. However care must be taken when combining mixtures of
antioxidants and other stabilizers as antagonistic effects can also result such as that which may be encountered in
combining hindered amines with thiosynergists.

Types of Antioxidants

The Autoxidation Cycle

Once oxidation starts, as it invariably will, it sets off a chain reaction which accelerates degradation unless
antioxidants/stabilizers are used to interrupt the oxidation cycle. Polymer oxidation sometimes termed 'autoxidation'
proceeds starting from generation of a free radical. These react rapidly with oxygen to form peroxy radicals which in
turn further react with the polymer chains to form hydroperoxides (ROOH). Cleavage of these hydroperoxides, for
example on exposure to heat, produces additional free radicals that reinitiate the process to continuously fuel the
degradation cycle. The key to effective protection against oxidation is the use of different types of
antioxidants/stabilizers that can intercept radicals and degradation products at different stages of the chain reaction in
order to bring the degradation cycle to a halt.

The Autoxidation Cycle

(Source: Ciba)

Antioxidants are used to provide polymer protection both against oxidation during melt processing and through the
product's life cycle as a 'long term thermal stabilizer.' Such long term thermal stabilizers differ from melt processing
stabilizers in that they must function at temperatures considerably below the polymer melting point.

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Effective Temperatures for Stabilizers

(Source: Ciba)

Primary Antioxidants

'Primary antioxidants,' sometimes referred to as free radical scavenging antioxidants, retard oxidation through chain
terminating reactions. They are predominantly hindered phenols, and, in certain applications (elastomers, polyol)
secondary aromatic amines. These antioxidants with reactive OH or NH groups are hydrogen donors that provide
antioxidant protection by transferring protons to the oxygen based free radical species to transform them into
hydroperoxides. Without their use, the oxygen-based radicals would attack the polymer, resulting in further degradation.
Phenolic stabilizers are offered in a wide range of molecular weights, product forms, and functionalities. Some of the
most frequently used stabilizers in this family are sterically hindered phenols which are effective during both melt
processing and long term thermal aging. Secondary aromatic amines are also excellent hydrogen donors, often more
active than hindered phenols however they tend to be more discoloring particularly on exposure to light or combustion
gases.

Hindered phenols are active over a broad temperature range from ambient up to approximately 300°C. As a result they
can be used to provide antioxidant protection during polymer melt processing (high temperatures for short duration),
while also conferring long-term thermal stability (moderate temperatures over extended periods), as well as aging
resistance over the lifetime of the plastic material. These antioxidants have proved to be of great importance in making
polypropylene a significant commercial success in such higher heat applications as automotive components. Hindered
phenolics are also widely used to protect engineering plastics that have high processing temperatures.

Secondary Antioxidants

'Secondary antioxidants' are typically used in combination with primary antioxidants to realize synergistic stabilization
effects. Hydroperoxides, the by-products formed by the reaction of hydrogen donors of primary antioxidants with
oxygen-based radicals are inherently unstable and can also decay into free radicals. Secondary antioxidants, commonly
referred to as hydroperoxide decomposers, are needed to transform these materials into thermally stable non-radical
products. These antioxidants, typically organophosphorous compounds (phosphites/phosphonites), and thiosynergists,
prevent the split of hydroperoxides into extremely reactive alkoxy and hydroxy radicals.

Phosphites/phosphonites are extremely effective at elevated temperatures (150-300°C), and serve as processing
stabilizers during compounding, and melt processing (e.g. molding, extrusion). Some organophosphorous compounds
are sensitive to water and can hydrolyze to form acidic species so hydrolysis resistant compounds are primarily used.
Esters of 3,3-thiodipropionic acid are the most frequently used antioxidants of the sulfur-derived hydroperoxide
decomposers. The most common of these are based on lauric or stearic acid. As thiosynergists are only effective below
150°C they can only provide long-term thermal and aging stability.

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Multifunctional and Other Antioxidant Advances

Irgatec NC 66 is proprietary antioxidant system developed by Ciba to address the unique stabilizing requirements of
nanoclay-based nanocomposites. The material is specifically developed to enhance the heat stability of nanoclay
composites while processing, to permit faster, hotter processing conditions. The additive package also reduces odor
upon processing, retards yellowing during aging, and improves long-term heat and light stability. This patented blend of
phenolic and other antioxidant functionalities, plus calcium organic salts, and metal oxides works on the different
elements of a nanocomposite that are known to increase risk of degradation, including the nanoclay, compatibilizer, and
impact modifier.

Multifunctional antioxidants are a relatively recent advance that beneficially combines both primary and secondary
antioxidant functions in one compound. Combining multiple stabilizing functions in one molecule eliminates the
requirement for co-stabilizers to be used (e.g. phosphites, thioesters) greatly simplifying antioxidant storage, handling,
and formulation. Irganox 1520 and Irganox 1726 from Ciba are two principal antioxidant products in this new class of
stabilizers.

Multifunctional Antioxidant
(Source: Ciba)

Chemtura is showcasing plastic additives that offer a greener profile such as its Weston NPF 705, a nonyl phenol free
phosphate stabilizer. Weston NPF 705 is a drop-in, liquid replacement for TNPP (tris [nonylphenyl] phosphate), an
industry-standard secondary antioxidant which is used in linear-low density polyethylene (LLDPE), high-density
polyethylene (HDPE), polyvinyl chloride (PVC), and styrene-butadiene rubber (SBR).

Antioxidant Suppliers/Plastics Antioxidant Market Report

Company Tradename Website

Chemtura Corporation Anox, Lowinox, Weston www.chemtura.com
Ciba (BASF) Irganox, Irgatec www.ciba.com
Songwon Int'l Americas Songnox www.songwonind.com
Acmite Market Intelligence World Plastics Additives Market www.acmite.com

Table 1: Antioxidant Suppliers/Market Reports

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