POLYMER DEGRADATION AND STABILIZATION

BY

IFIJEN CLARE EKIOMON

ENG/2162290243

A SEMINAR PAPER PRESENTED TO THE

DEPARTMENT POLYMER TECHNOLOGY,
SCHOOL OF ENGINEERING TECHNOLOGY, AUCHI POLYTECHNIC AUCHI

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF

HIGHER NATIONAL DIPLOMA (HND) IN DEPARTMENT POLYMER
TECHNOLOGY.

SUPERVISED
BY
ENGR. DR. M.D AYO

FEBRUARY, 2024

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 OUTLINE

Introduction
Polymer Degradation:

Photo Degradation

Thermal Degradation

Chemical degradation

Biological degradation

Polymer Stabilizers

Antioxidants

Conclusion

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Introduction

Polymer degradation is a change in the properties—tensile strength, color, shape, etc. of a

polymer or polymer-based product under the influence of one or more environmental factors

such as heat, light or chemicals such as acids, alkalis, and some salts. Degradation is often due to

a change in the chemical and physical structure of the polymer chain, which in turn leads to a

decrease in the molecular weight of the polymer. These changes are usually undesirable, such as

cracking and chemical disintegration of products or, more rarely, desirable, as in biodegradation,

or deliberately lowering the molecular weight of a polymer for recycling. Such changes occur

primarily because of the effect of these factors on the chemical composition of the polymer. The

changes in properties are often termed ―aging (Jellinek, 2018).

Polymer degradation includes all changes in both the chemical structure and physical properties

of polymers or polymer-based products that lead to the loss of properties such as tensile strength,

color, shape, etc., under the influence of processing conditions, or one or more environmental

factors. In a finished product, such a change is to be prevented or delayed. The degradation of

polymers to form smaller molecules may proceed by random scission or specific scission.

Degradation can be useful for recycling/reusing polymer waste to prevent or reduce

environmental pollution. The degradation of high density Polyethelne occurs by random scission

– a random breakage of the bonds within the polymer. Degradation can also be induced

deliberately to assist in structure determination. As the recognition of polymer degradation

improves, conservation guidelines are beginning to emerge (Ballauff, 2014).

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Fig.1.1 : Schematic presentation of polymer degradation

Polymer Degradation:

Definition: Process which deteriorates polymer properties or their outward appearance.

Polymer degradation is a change in the properties—tensile strength, color, shape, etc.—of a

polymer or polymer-based product under the influence of one or more environmental factors

such as heat, light or chemicals such as acids, alkalis and some salts. These changes are usually

undesirable, such as cracking and chemical disintegration of products or, more rarely, desirable,

as in biodegradation, or deliberately lowering the molecular weight of a polymer for recycling.

The changes in properties are often termed "aging". (Ballauff, 2014).

Polymeric molecules are very large (on the molecular scale), and their unique and useful

properties are mainly a result of their size. Any loss in chain length lowers tensile strength and is

a primary cause of premature cracking.

1. Photo Degradation

Many natural and synthetic polymers are attacked by ultraviolet radiation, and

products using these materials may crack or disintegrateto give lower molecular weight

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molecules if they are not UV-stable. The problem is known as UV degradation, and is a

common problem in products exposed to sunlight. Continuous exposure is a more serious

problem than intermittent exposure, since attack is dependent on the extent and degree of

exposure (Dan, & Guillet, 2013).

Many pigments and dyes can also be affected, and the problem known as photo

tendering can affect textiles such as curtains or drapes

Common synthetic polymers that can be attacked include polypropylene and

LDPE, where tertiary carbon bonds in their chain structures are the centers of attack.

Ultraviolet rays interact with these bonds to form free radicals, which then react further

with oxygen in the atmosphere, producing carbonyl groups in the main chain. The

exposed surfaces of products may then discolor and crack, and in extreme cases,

complete product disintegration can occur (Montroll, 2020)

In fibre products like rope used in outdoor applications, product life will be low

because the outer fibres will be attacked first, and will easily be damaged by abrasion for

example. Dis coloration of the rope may also occur, thus giving an early warning of the

problem.

Polymers which possess UV-absorbing groups such as aromatic rings may also be

sensitive to UV degradation. Aramid fibers like Kevlar, for example, are highly UV-

sensitive and must be protected from the deleterious effects of sunlight (Netopilik, et al.,

2020).

---CH2-CH2-CH2-CH2 –CO-CH2-CH2-CH2-CH2-CH2-CH2-CH2 -----

UV rays

---CH2-CH2-CH2-CH2 –CO-CH3+CH2=CH2-CH2-CH2-CH2 -CH2 -----

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2. Thermal Degradation

Thermal degradation of polymers is molecular deterioration as a result of

overheating. At high temperatures the components of the long chain backbone of the

polymer can begin to be broken (chain scission) and react with one another to change the

properties of the polymer. The chemical reactions involved in thermal degradation lead to

physical and optical property changes relative to the initially specified properties.

Thermal degradation generally involves changes to the molecular weight (and molecular

weight distribution) of the polymer and typical property changes include reduced

ductility and embrittlement, chalking, color changes, cracking, general reduction in most

other desirable physical properties. (Ballauff, 2014).Thermal breakdown products may

include a complex mixture of compounds, including but not limited to carbon monoxide,

ammonia, aliphatic amines, ketones, nitriles, and hydrogen cyanide, which may be

flammable, toxic and/or irritating. The specific materials generated will vary depending

on the additives and colorants used specific temperature, time of exposure and other

immediate environmental factors.

For example the PVC eliminates HCl, under 100–120 °C.

CH2(Cl)CHCH2CH(Cl)→CH=CH-CH=CH+2HCl

3. Chemical degradation

a) Solvolysis

Step-growth polymers like polyesters, polyamides and polycarbonates can be degraded by

solvolysis and mainly hydrolysis to give lower molecular weight molecules. The hydrolysis

takes place in the presence of water containing an acid or a base as catalyst (Román- et al.,

2020).

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b) Ozonolysis

Cracks can be formed in many different elastomers by ozone attack. Tiny traces of the gas in

the air will attack double bonds in rubber chains, with Natural rubber, polybutadiene,

Styrene-butadiene rubber and NBR being most sensitive to degradation. The problem of

ozone cracking can be prevented by adding anti-ozonants to the rubber before vulcanization.

c) Oxidation

The polymers are susceptible to attack by atmospheric oxygen, especially at elevated

temperatures encountered during processing to shape. Many process methods such as

extrusion and injection moulding involve pumping molten polymer into tools, and the high

temperatures needed for melting may result in oxidation unless precautions are taken. For

example, a forearm crutch suddenly snapped and the user was severely injured in the

resulting fall. The crutch had fractured across a polypropylene insert within the aluminium

tube of the device, and infra-red spectroscopy of the material showed that it had oxidised,

possible as a result of poor moulding. (Norrish, 2017) Oxidation is usually relatively easy to

detect owing to the strong absorption by the carbonyl group in the spectrum of polyolefins.

Polypropylene has a relatively simple spectrum with few peaks at the carbonyl position (like

polyethylene). Oxidation tends to start at tertiary carbon atoms because the free radicals

formed here are more stable and longer lasting, making them more susceptible to attack by

oxygen. The carbonyl group can be further oxidised to break the chain, this weakens the

material by lowering its molecular weight, and cracks start to grow in the regions affected

d) Chlorine-induced cracking

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Another highly reactive gas is chlorine, which will attack susceptible polymers such

as acetal resin and polybutylene pipework. There have been many examples of such pipes

and acetal fittings failing in properties in the US as a result of chlorine-induced cracking. In

essence, the gas attacks sensitive parts of the chain molecules (especially secondary, tertiary,

or allylic carbon atoms), oxidizing the chains and ultimately causing chain cleavage. The

root cause is traces of chlorine in the water supply, added for its anti-bacterial action, attack

occurring even at parts per million traces of the dissolved gas. The chlorine attacks weak

parts of a product, and in the case of an acetal resin junction in a water supply system, it is

the thread roots that were attacked first, causing a brittle crack to grow. Discoloration on the

fracture surface was caused by deposition of carbonates from the hard water supply, so the

joint had been in a critical state for many months. The problems in the US also occurred

to polybutylene pipework, and led to the material being removed from that market, although

it is still used elsewhere in the world (Webb, et al., 2013).

e) Galvanic action

Polymer degradation by galvanic action was first described in the technical literature in

1990. This was the discovery that "plastics can corrode", i.e. polymer degradation may

occur through galvanic action similar to that of metals under certain conditions and has been

referred to as the "Faudree Effect". In the aerospace field, this finding has largely

contributed to aircraft safety, mainly those aircraft that use CFRP and has resulted in a wide

body of follow-up research and patents. Normally, when two dissimilar metals such as

copper (Cu) and iron (Fe) are put into contact and then immersed in salt water, the iron will

undergo corrosion, or rust. This is called a galvanic circuit where the copper is the noble

metal and the iron is the active metal, i.e., the copper is the positive (+) electrode and the

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iron is the negative (-) electrode. A battery is formed. It follows that plastics are made

stronger by impregnating them with thin carbon fibers only a few micrometers in diameter

known as carbon fiber reinforced polymers (CFRP). This is to produce materials that are

high strength and resistant to high temperatures. The carbon fibers act as a noble metal

similar to gold (Au) or platinum (Pt). When put into contact with a more active metal, for

example with aluminum (Al) in salt water the aluminum corrodes. However, in early 1990,

it was reported that imide-linked resins in CFRP composites degrade when bare composite

is coupled with an active metal in salt water environments. This is because corrosion not

only occurs at the aluminum anode, but also at the carbon fiber cathode in the form of a very

strong base with a pH of about 13. This strong base reacts with the polymer chain structure

degrading the polymer. Polymers affected include bismaleimides (BMI), condensation

polyimides, triazines, and blends thereof. Degradation occurs in the form of dissolved resin

and loose fibers. The hydroxyl ions generated at the graphite cathode attack the O-C-N bond

in the polyimide structure. Standard corrosion protection procedures were found to prevent

polymer degradation under most conditions (Vohlídal, et al., 2013).

Biological degradation

Biodegradable polymers are a specific type of polymer that breaks down after its

intended purpose to result in natural byproducts such as gases (CO2, N2), water, biomass,

and inorganic salts. Biodegradable plastics can be biologically degraded by microorganisms

to give lower molecular weight molecules. To degrade properly biodegradable polymers need

to be treated like compost and not just left in a landfill site where degradation is very difficult

due to the lack of oxygen and moisture. These polymers are found both naturally and

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 synthetically made, and largely consist of ester, amide, and ether functional groups. Their

properties and breakdown mechanism are determined by their exact structure. These

polymers are often synthesized by condensation reactions, ring opening polymerization, and

metal catalysts. There are vast examples and applications of biodegradable polymers

(Middleton, 2020).

The great benefit of a biodegradable drug delivery system is the ability of the drug

carrier to target the release of its payload to a specific site in the body and then degrade into

nontoxic materials that are then eliminated from the body via natural metabolic pathways

Polymer Stabilizers

Stabilizers for polymers are used directly or by combinations to prevent the various

effects such as oxidation, chain scission and uncontrolled recombination’s and cross-linking

reactions that are caused by photo-oxidation of polymers. Polymers are considered to get

weathered due to the direct or indirect impact of heat and ultraviolet light. The effectiveness of

the stabilizers against weathering depends on solubility, ability to stabilize in different polymer

matrix, the distribution in matrix, evaporation loss during processing and use (Gijsman, 2018).

Antioxidants

Polymers will change over time when exposed to radiation, excessive heat and/or corrosive

enviroments. These changes are the result of oxidative degradation caused by free radicals which

form through hydrogen abstration or homolytic scission of carbon-carbon bonds when polymers

are exposed to heat, oxygen, ozone, or light. These changes can have a dramatic effect on the

service life and properties of the polymer.

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To prevent or slow down degradation, antioxidants and UV stabilizers are often added. The two

main classes of antioxidants are free-radical scavengers and peroxide scavengers. The free-

radical scavengers are sometimes called primary antioxidants or radical chain terminators

whereas peroxide scavengers are often called secondary antioxidants or hydroperoxide

decomposers (chwetlick, 2016).

Primary Antioxidants ( free –radical scavengers)

As the name suggests, free-radical scavengers react with chain-propagating radicals such as

peroxy, alkoxy, and hydroxy radicals in a chain terminating reaction. To be more specific, these

antioxidants donate hydrogen to the alkoxy and hydroxy radicals which converts them into inert

alcohols and water respectively.

Typical commercial primary antioxidants are hindered phenols and secondary aromatic amines.

These compounds come in a wide range of molecular weights, structures, and functionalities

The most widely used primary antioxidants are sterically hindered phenols. They are very

effective radical scanvengers during both processing and long-term thermal aging, and are

generally non-discoloring. The mechanism of scavenging oxy radicals is shown below :

Fig.2.2 : The mechanism of scavenging oxy radicals.

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The most effective primary antioxidants are secondary aromatic amines. However, they cause

noticeable discoloation and can only be used if discolation is not a problem, like carbon filled

rubber products. They also function as antiozonants and metal ion deactivators.

Secondary antioxidants (peroxide scavengers)

As the name suggests, peroxide scavengers (secondary antioxidants) decompose hydroperoxides

(ROOH) into nonreactive products before they decompose into alkoxy and hydroxy radicals.

They are often used in combination with free radical scavengers (primary antioxidants) to

achieve a synergistic inhibition effect. The most common secondary antioxidants are trivalent

phosphorus compounds (phosphites). They reduce hydroperoxides to the corresponding alcohols

and are themselves transformed into phospates.

The general mechanism of peroxide decomposition.

Another class of secondary antioxidants are thioethers or organic sulfides. They decompose two

molecules of hydroperoxide into the corresponding alcohols and are transformed to sulfoxides

and sulfones:

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Organic sulfides are very effective hydrogen peroxide decomposers during long-term thermal

aging and are often used in combination with other antioxidants that provide good protection

during processing, like hindered phenols.

In order to choose the most effective stabilizer package, it is important to know what temperature

range the polymer will be exposed to. A good stabilizer package should protect the plastic during

both processing, where high temperatures are encountered to melt and form the resin, and during

lifetime when exposed to its upper service temperature decomposers (chwetlick, 2016) .

Conclusion

In conclusion from the foregoing, It is important that understanding about the mechanism that

lead to polymer degradation can go a long way in helping the researchers and the technologists to

induce the different types of degradation in the plastic. These degradations can further be

enhanced by the addition of the additives in the plastic and by understanding the various factors

responsible for these degradations. It is also concluded from this discussion that plastic

degradation could be enhanced by its modification with natural polymers and this acquaintance

can further be exploited for environmental waste management.

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