STABILIZATION OF POLYMER, ITS ANALYTICS AND SOME REGULATIONS

ASPECT

BY

ONYENIKE NKECHI MARY

A SEMINAR PAPER PRESENTED TO THE

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF

SUPERVISED
BY
ENGR. M.N. CHUKWU

FEBRUARY, 2024

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 Abstract

When polymers are exposed to shear stress, heat, light, air, water, radiation, or mechanical
loading, chemical reactions may be initiated that lead to changes in molecular weight and
chemical composition. This may result in an undesired change (degradation) in appearance
(e.g., gloss, texture, color) and mechanical properties (e.g., tensile, flexural, or impact strength).
The type of degradation relates to the environment to which the plastic is exposed, for example,
UV degradation due to sunlight or thermooxidative degradation due to long-term heat aging.
Plastics can be protected by adding stabilizers. The type of stabilizer depends on the
environment against which the polymer has to be protected (e.g., processing stabilizers, UV
stabilizers, and long-term heat stabilizers). The performance of a stabilizer is determined not
only by its effectiveness in protecting the polymer against degradation, but also by its physical
properties, color, interactions with other additives, chemical resistance, toxicity, price, and other
factors.

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Introduction

Polymer stabilizers (British: polymer stabilisers) are chemical additives which may be added

to polymeric materials, such as plastics and rubbers, to inhibit or retard their degradation. [1]

Common polymer degradation processes include oxidation, UV-damage, thermal degradation,

ozonolysis, combinations thereof such as photo-oxidation, as well as reactions with catalyst

residues, dyes, or impurities. (Kröhnke, 2016) All of these degrade the polymer at a chemical

level, via chain scission, uncontrolled recombination and cross-linking, which adversely affects

many key properties such as strength, malleability, appearance and colour.

Stabilizers are used at all stages of the polymer life-cycle. They allow plastic items to be

produced faster and with fewer defects, extend their useful lifespan, and facilitate their recycling.

(Kröhnke, 2016) However they also continue to stabilise waste plastic, causing it to remain in

the environment for longer. Many different types of plastic exist and each may be vulnerable to

several types of degradation, which usually results in several different stabilisers being used in

combination. Even for objects made from the same type of plastic, different applications may

have different stabilisation requirements. Regulatory considerations, such as food contact

approval are also present. A wide range of stabilizers is therefore needed.

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Antioxidants

Antioxidants inhibit autoxidation that occurs when polymers reacts with atmospheric oxygen. [5]

Aerobic degradation occurs gradually at room temperature, but almost all polymers are at risk of

thermal-oxidation when they are processed at high temperatures. The molding or casting of

plastics (e.g. injection molding) require them to be above their melting point or glass transition

temperature (~200-300 °C). Under these conditions reactions with oxygen occur much more

rapidly. Once initiated, autoxidation can be autocatalytic. (Pospı́šil, 2017). As such, even though

efforts are usually made to reduce oxygen levels, total exclusion is often not achievable and even

exceedingly low concentrations of oxygen can be sufficient to initiate degradation. Sensitivity to

oxidation varies significantly depending on the polymer in question; without stabilizers

polypropylene and unsaturated polymers such as rubber will slowly degrade at room temperature

where as polystyrene can be stable even at high temperatures. (Gryn'ova, et al., 2011)

Antioxidants are of great importance during the process stage, with long-term stability at ambient

temperature increasingly being supplied by hindered amine light stabilizers (HALs).

Antioxidants are often referred to as being primary or secondary depending on their mechanism

of action.

Primary antioxidants (radical scavengers)

Primary antioxidants (also known as chain-breaking antioxidants) act as radical scavengers and

remove peroxy radicals (ROO•), as well as to a lesser extent alkoxy radicals (RO•), hydroxyl

radicals (HO•) and alkyl radicals (R•). Oxidation begins with the formation of alkyl radicals,

which are formed when the high temperatures and high shear stress experienced during

processing snaps the polymer chains in a homolytic manner. These alkyl radicals react very

rapidly with molecular oxygen (rate constants ≈ 107–109 mol–1 s–1) to give peroxy radicals,

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(Gijsman, 2018) which in turn abstract hydrogen from a fresh section of polymer in a chain

propagation step to give new alkyl radicals. The overall process is exceedingly complex and will

vary between polymers[11] but the first few steps are shown below in general:

R-R → 2 R•

R• + O2 → ROO•

ROO• + RH → ROOH + R•

Due to its rapid reaction with oxygen the scavenging of the initial alkyl radical (R•) is difficult

and can only be achieved using specialised antioxidants (Osawa, 2018). the majority of primary

antioxidants react instead with the longer lasting peroxy radicals (ROO•). Hydrogen abstraction

is usually the rate determining step in the polymer degradation and the peroxy radicals can be

scavenged by hydrogen donation from an alternative source, namely the primary antioxidant.

This converts them into an organic hydroperoxide (ROOH). The most important commercial

stabilizers for this are hindered phenols such as BHT or analogues thereof and secondary

aromatic amines such as alkylated-diphenylamine. Amines are typically more effective, but

cause pronounced discoloration, which is often undesirable (i.e., in food packaging, clothing).

The overall reaction with phenols is shown below:

ROO• + ArOH → ROOH + ArO•

ArO• → nonradical products

The end products of these reactions are typically quinone methides, which may also impart

unwanted colour.[13] Modern phenolic antioxidants have complex molecular structures, often

including a propionate-group at the para position of the phenol (i.e. they are ortho-alkylated

analogues of phloretic acid).[14] The quinone methides of these can rearrange once to give a

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hydroxycinnamate, regenerating the phenolic antioxidant group and allowing further radicals to

be scavenged.[15][16] Ultimately however, primary antioxidants are sacrificial and once they are

fully consumed the polymer will begin to degrade.

Secondary antioxidants (hydroperoxides scavengers)

Secondary antioxidants act to remove organic hydroperoxides (ROOH) formed by the action of

primary antioxidants. Hydroperoxides are less reactive than radical species but can initiate fresh

radical reactions:[6]

ROOH + RH → RO• + R• + H2O

As they are less chemically active they require a more reactive antioxidant. The most commonly

employed class are phosphite esters, often of hindered phenols e.g. Tris(2,4-di-tert-

butylphenyl)phosphite.[17] These will convert polymer hydroperoxides to alcohols, becoming

oxidized to organophosphates in the process: (Pelzl, et al., 2018).

ROOH + P(OR')3 → OP(OR')3 + ROH

Transesterification can then take place, in which the hydroxylated polymer is exchanged for a

phenol:[20]

ROH + OP(OR')3 → R'OH + OP(OR')2OR

This exchange further stabilizes the polymer by releasing a primary antioxidant, because of this

phosphites are sometimes considered multi-functional antioxidants as they can combine both

types of activity. Organosulfur compounds are also efficient hydroperoxide decomposers, with

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thioethers being particularly effective against long-term thermal aging, they are ultimately

oxidise up to sulfoxides and sulfones.[21]

Antiozonant

Antiozonants prevent or slow down the degradation of material caused by ozone. This is

naturally present in the air at very low concentrations but is exceedingly reactive, particularly

towards unsaturated polymers such as rubber, where it causes ozone cracking. The mechanism of

ozonolysis is different from other forms of oxidation and hence requires its own class of

antioxidant stabilizers. These are primarily based on p-phenylenediamine and work by reacting

with ozone faster than it can react with vulnerable functional groups in the polymer (typically

alkene groups). They achieve this by having a low ionization energy which allows them to react

with ozone via electron transfer, this converts them into radical cations that are stabilized by

aromaticity. Such species remain reactive and will react further, giving products such as 1,4-

benzoquinone, phenylenediamine-dimers and aminoxyl radicals (Chwetlick, et al., 2016). Some

of these products can then be scavenged by antioxidants.

Light stabilizers

Light stabilizer are used to inhibit polymer photo-oxidation, which is the combined result of the

action of light and oxygen. Like autoxidation this is a free radical process, hence the antioxidants

described above are effective inhibiting agents, however additional classes of additives are also

beneficial, such as UV absorbers, quenchers of excited states and HALS (Singh, & Sharma,

2018).

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UV absorbers

UV susceptibility varies significantly between different polymers. Certain polycarbonates,

polyesters and polyurethanes are highly susceptible, degrading via a Photo-Fries rearrangement.

UV stabilisers absorb and dissipate the energy from UV rays as heat, typically by reversible

intramolecular proton transfer. This reduces the absorption of UV rays by the polymer matrix

and hence reduces the rate of weathering. Phenolic benzotriazoles (e.g. UV-360, UV-328) and

hydroxyphenyl-triazines (e.g. Bemotrizinol) are used to stabilise polycarbonates and acrylics,

(Zweifel, et al., 2019) oxanilides are used for polyamides and polyurethanes, while

benzophenones are used for PVC.

Strongly light-absorbing PPS is difficult to stabilize. Even antioxidants fail in this electron-rich

polymer. The acids or bases in the PPS matrix can disrupt the performance of the conventional

UV absorbers such as HPBT. PTHPBT, which is a modification of HPBT are shown to be

effective, even in these conditions.

Importance of Polymer Stabilizer

Polymer stabilizers play a crucial role in enhancing the performance and durability of polymers

by protecting them from degradation caused by various environmental factors such as heat, light,

oxygen, and mechanical stress.

1. Preventing Degradation: Polymers are susceptible to degradation over time when

exposed to environmental factors. Stabilizers act as protective agents, inhibiting or

slowing down degradation reactions such as oxidation, hydrolysis, and thermal

decomposition.

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 2. Extending Service Life: By safeguarding polymers against degradation, stabilizers help

extend their service life. This is particularly important in applications where polymers are

exposed to harsh conditions or prolonged use, such as outdoor construction materials,

automotive components, and packaging.

3. Maintaining Properties: Degradation can lead to undesirable changes in the physical

and mechanical properties of polymers, including discoloration, embrittlement, and loss

of strength. Stabilizers help maintain these properties, ensuring that the polymer retains

its performance characteristics over time.

4. Enhancing Processability: Some stabilizers also improve the processability of polymers

during manufacturing processes such as extrusion, molding, and recycling. They can act

as processing aids, reducing melt viscosity, improving flow properties, and enhancing the

overall efficiency of production processes.

Analytics and Some Regulation of Stabilization of Polymer

Spectroscopic Techniques:

o FTIR (Fourier Transform Infrared Spectroscopy): Used to analyze chemical

bonds and functional groups in polymers, aiding in identifying degradation

products and assessing stabilization efficiency.

o UV-Vis Spectroscopy: Useful for monitoring changes in polymer color, which

can indicate degradation.

o NMR (Nuclear Magnetic Resonance): Provides detailed structural information

about polymers and degradation products.

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Thermal Analysis:

o DSC (Differential Scanning Calorimetry): Measures changes in heat flow

associated with phase transitions and chemical reactions, allowing assessment of

thermal stability and degradation kinetics.

o TGA (Thermogravimetric Analysis): Measures weight changes as a function of

temperature, providing information on thermal stability and decomposition

temperatures.

Chromatographic Techniques:

o GC-MS (Gas Chromatography-Mass Spectrometry): Separates and identifies

volatile degradation products, aiding in understanding degradation mechanisms.

o HPLC (High-Performance Liquid Chromatography): Useful for separating

and quantifying degradation products, additives, and stabilizers.

Regulations

Different regions have specific regulations governing the use of polymers in various

applications, including packaging, medical devices, automotive parts, etc. These regulations

often address aspects such as safety, environmental impact, and performance requirements. For

example:

 Food Packaging Regulations: Ensuring that polymers used in food packaging meet

safety standards to prevent migration of harmful substances into food.

 Medical Device Regulations: Ensuring biocompatibility and stability of polymers used

in medical devices.

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  Environmental Regulations: Addressing the recyclability and biodegradability of

polymers to minimize environmental impact.

 Product Performance Standards: Establishing minimum performance requirements for

polymers used in specific applications, such as automotive components or construction

materials.

Compliance with these regulations often requires thorough testing and documentation of

polymer properties, including stability, mechanical properties, and chemical composition.

Manufacturers must ensure their products meet relevant regulatory requirements to ensure safety

and compliance with the law.

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Conclusions

Stabilization of polymers is an important problem and there are lots of investigations, having

both practical and/or theoretical (fundamental) contribution. Modern trends for solving the

problem are related to the synthesis of functional (polymerizable) stabilizers, providing

resistance to wet treatment, solvents and migration stabilization, by their incorporation in the

polymer chain.An important new trend is the synthesis of com- pounds that are a combination in-

one molecule of two different by their mechanism of action stabilizers, with a polymerizable

group. The investigations connected to the synthesis of the structures, where a chromophore, a

stabilizer and a polymerizable group are combined in one molecule, presenting the possibility

for “one-step” coloration and stabilization of polymers are of special interest. All these trends

have very important ecological contribution, presenting a possibility to obtain the polymers with

ecologically more compatible behavior

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 References

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antioxidant activity of phosphite esters". Polymer Degradation and Stability. 15 (2):
97–108.

Gijsman, P, (2018). "Polymer Stabilization". Handbook of Environmental Degradation of

Gryn'ova, Ganna; Hodgson, Jennifer L.; Coote, Michelle L. (2011). "Revising the mechanism of
polymer autooxidation". Org. Biomol. Chem. 9 (2): 480–490

Kröhnke, C. (2016). "Polymer Stabilization". Reference Module in Materials Science and

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Degradation and Stability. 20 (3–4): 203–23

Pelzl, Bernhard; Wolf, Rainer; Kaul, Bansi Lal (2018). "Plastics, Additives". Ullmann's
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Pospı́šil, J.; Habicher, W.-D.; Pilař, J.; Nešpůrek, S.; Kuthan, J.; Piringer, G.-O.; Zweifel, H.
(2017). "Discoloration of polymers by phenolic antioxidants". Polymer Degradation
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Singh, Baljit; Sharma, Nisha (2018). "Mechanistic implications of plastic degradation". Polymer
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