Extended Essay

– Chemistry–

Topic:
A comparative study of the influence of chemical structures of PET,
polyethylene, and polystyrene on their rates of photo-oxidative
degradation under UV exposure

Research Question:
How do the chemical structures of different plastics (PET, polyethylene,
and polystyrene) influence their rate of photo-oxidative degradation under
UV exposure, when tested under controlled conditions of equal exposure
time, constant temperature, and uniform sample thickness and mass?

Session: May 2025

Word Count: 4482

Index

Introduction ...................................................................................…...... 3
Background Information ................................................................…..... 4
Fundamentals of Photo-oxidative Degradation ...............................….... 4
Role of Chemical Structure in UV Absorption and Radical Formation
…………………………………………………………….... 7
Research ...........................................................................................….... 9
Polyethylene: Structure and Degradation ..........................................….. 9
Polystyrene: Structure and Degradation .....................................…….... 11
Polyethylene Terephthalate (PET): Structure and Degradation ..……... 12
Comparative Ranking of Degradation Susceptibility ...................…...... 13
Investigation ................................................................................…....... 13
Role of Crystallinity ....................................................................…....... 14
Role of Aromaticity and Chromophores ..................................……….. 14
Influence of Environmental Conditions (Oxygen, Moisture, Temperature)
……………………………………………………….…..15
Comparison to Other Polymers and Stabilized Plastics .…...........…..... 15
Data ................................................................................……..........…... 16
Experimental Observations on UV Degradation ............….............…... 17
Influence of Polymer Subtypes ......................................…..................... 18
Dose–Response Relationships: UV Intensity vs. Degradation Rate ...…20
Additives and Stabilizers ........................................................…............ 22
Long-Term Degradation Patterns ..........................................…............. 23
Microplastics and Fragmentation Patterns ............................…............. 25
Conclusion ..............................................................................……........ 27
Bibliography ..........................................................................…............. 28
1. Introduction

Plastics are synthetic polymers whose high durability, versatility, and low
cost have transformed modern life. They are extensively used in
packaging, construction, electronics, automotive components, and
textiles. Despite their advantages, plastics present serious environmental
challenges because of their persistence in natural ecosystems. When
discarded, plastics accumulate in landfills, oceans, and soils, taking
decades to centuries to degrade. The global concern regarding plastic
pollution has intensified research on understanding the chemical and
physical processes governing plastic degradation.

One key degradation pathway is photo-oxidative degradation, driven by

ultraviolet (UV) radiation from sunlight. UV photons have sufficient
energy to excite electrons in chemical bonds, initiating radical reactions
that cleave polymer chains. However, the rate and mechanism of
degradation depend strongly on the chemical structure of the polymer.
Factors such as the presence of aromatic rings, carbonyl groups, double
bonds, chain branching, and crystallinity determine how efficiently the
polymer absorbs UV light and how readily radicals propagate.

This essay focuses on three widely used polymers: polyethylene (PE),

polystyrene (PS), and polyethylene terephthalate (PET). PE is a
simple hydrocarbon polymer, PS contains pendant aromatic rings, and
PET integrates aromatic rings and ester linkages in the backbone. By
comparing these polymers under controlled UV exposure, this study
seeks to determine how structural differences influence photo-oxidative
susceptibility. Understanding these mechanisms not only informs
recycling and material design but also guides environmental management
strategies.
2.2. Background Information

Fundamentals of Photo-oxidative Degradation

Photo-oxidation is one of the most important environmental degradation

pathways for synthetic polymers. Unlike thermal degradation, which
requires elevated temperatures, or hydrolytic degradation, which requires
aqueous conditions, photo-oxidation is driven primarily by sunlight,
particularly ultraviolet (UV) radiation, in the presence of oxygen. Since
sunlight is ubiquitous, photo-oxidation is often the dominant mechanism
for polymer breakdown in the natural environment.

The UV portion of the solar spectrum that reaches the Earth’s surface
ranges between 280–400 nm, corresponding to photon energies of
roughly 300–425 kJ mol⁻¹. Many common covalent bonds in polymers,
such as C–C (~350 kJ mol⁻¹) and C–H (~410 kJ mol⁻¹) bonds, have
bond dissociation energies in the same range. This means that UV
photons can directly break these bonds or, more often, excite electrons in
chromophoric groups, creating highly reactive species that then lead to
bond scission.

The photo-oxidative degradation of polymers generally occurs through

three main stages:

1. Initiation

The initiation step begins when UV photons are absorbed by a polymer

chain. This requires the presence of chromophores—molecular groups
that absorb light strongly at UV wavelengths. If the polymer lacks
chromophores, as in polyethylene (PE), initiation occurs primarily at
weak spots, such as tertiary carbons in branched chains or carbonyl
impurities introduced during polymer synthesis and processing.

In polystyrene (PS), the phenyl rings serve as strong chromophores,

readily absorbing UV light and generating benzyl radicals adjacent to the
aromatic substituents. In polyethylene terephthalate (PET), both carbonyl
groups in ester linkages and aromatic rings in the backbone serve as UV
absorbers.

Absorption of a photon excites an electron to a higher-energy state. If the

energy exceeds the bond dissociation energy, a bond is cleaved
homolytically, creating two radicals. For example:

In PE: –CH₂–CH₂– → –CH₂· + ·CH₂–

In PS: –CH₂–C₆H₅ → –CH·–C₆H₅ + H·

These primary radicals are the starting point for propagation.

2. Propagation

Once free radicals are formed, they quickly react with atmospheric
oxygen, producing peroxy radicals (ROO·). These species are unstable
and can abstract hydrogen atoms from adjacent polymer chains, creating
hydroperoxides (ROOH) and new carbon-centered radicals.
Hydroperoxides are particularly important intermediates: they are
unstable under UV irradiation and can decompose into alkoxy radicals
(RO·) and hydroxyl radicals (·OH), both of which accelerate further
chain scission.

The propagation step leads to:

 Chain scission: Reduction in molecular weight, lowering tensile

strength and flexibility.
 Cross-linking: Formation of new C–C bonds between chains, which
may increase brittleness.

Formation of oxygenated groups: Such as ketones, aldehydes,

carboxylic acids, and alcohols. These oxygenated products absorb more
UV light than the original polymer, creating an autocatalytic effect
where degradation accelerates over time.

In PE, propagation occurs mainly through alkyl radicals and

hydroperoxide decomposition. In PS, propagation is enhanced by the
stability of benzyl radicals, which survive long enough to undergo
multiple reactions. In PET, propagation involves both radical pathways
and ester hydrolysis, especially under humid conditions.

3. Termination

Radical reactions eventually terminate when two radicals recombine or

undergo disproportionation to form stable products. For example:

R· + R· → R–R (cross-linking)

R· + ROO· → ROOR (peroxide dimer)

2ROO· → stable oxygenated products

While termination reduces radical concentration, it does not repair the

polymer. By this stage, the polymer’s mechanical integrity has already
declined due to molecular weight reduction and surface cracking.

Environmental Influences on Photo-oxidation

The rate of photo-oxidation is not fixed but varies with environmental

conditions:
 Temperature: Higher temperatures increase chain mobility, oxygen
diffusion, and radical reactivity. In tropical climates, polymers
degrade more rapidly than in temperate ones.
 Oxygen concentration: Plastics exposed to air degrade faster than
buried or submerged plastics where oxygen is limited.
 Moisture and humidity: Water facilitates the decomposition of
hydroperoxides and, in the case of PET, accelerates ester hydrolysis.
 Salinity and pollutants: In marine environments, salts and trace
metals catalyze radical reactions, altering degradation pathways.
 Surface-to-volume ratio: Thin films and foamed plastics degrade
more quickly than bulk plastics due to greater UV exposure per unit
mass.

Importantly, photo-oxidation occurs predominantly at the surface of the

polymer because UV light penetrates only a few micrometers, and
oxygen diffusion is limited in crystalline regions. Thus, polymers often
develop a brittle, chalky surface layer while the bulk remains relatively
intact for long periods.

Role of Chemical Structure in UV Absorption and Radical

Formation
The chemical structure of a polymer dictates its susceptibility to photo-
oxidative degradation. Several interrelated factors are crucial:

Chromophores

Chromophores are groups that absorb UV photons strongly due to

electronic transitions. Their presence greatly accelerates initiation.

 Polystyrene (PS): The pendant phenyl groups absorb UV efficiently

in the 250–300 nm range. This results in rapid formation of benzyl
radicals, which initiate chain scission.

 Polyethylene (PE): Lacks chromophores; UV absorption is weak.

Degradation depends on impurities (carbonyl defects, catalyst
residues) or weak tertiary carbons in LDPE.

 PET: Contains aromatic rings and carbonyl groups in the backbone.

These absorb UV photons, but resonance in the aromatic system can
dissipate the energy, slowing bond cleavage compared to PS.
Bond Dissociation Energy (BDE)

Different bonds in polymers have different stabilities. Bonds with lower

BDE values break more easily under UV irradiation:

 C–H bond in tertiary carbons (~370 kJ mol⁻¹): Weaker than

primary or secondary C–H bonds (~410 kJ mol⁻¹). Common in LDPE
branches.

 Benzylic C–H bonds (~360 kJ mol⁻¹): Adjacent to aromatic rings in

PS; easily cleaved to form benzyl radicals.

 C–O bonds in ester linkages (~350 kJ mol⁻¹): In PET, susceptible

to cleavage under UV and moisture.

Comparing these energies with solar UV photon energies (~300–425 kJ

mol⁻¹) explains why UV light can effectively initiate degradation.
Crystallinity

The physical arrangement of polymer chains influences degradation:

 High crystallinity (HDPE, semi-crystalline PET): Chains are

tightly packed, limiting oxygen diffusion and radical mobility. This
slows down propagation, confining degradation mostly to the
amorphous regions.

 Low crystallinity (LDPE, PS): Amorphous structures allow greater

oxygen penetration and free radical movement, accelerating
degradation.
 This structural factor explains why LDPE degrades faster than HDPE,
and amorphous PET degrades faster than crystalline PET.

Resonance Stabilization

Aromatic rings can stabilize radicals through delocalization. This has dual
consequences:
In PS, resonance-stabilized benzyl radicals persist long enough to drive
extensive propagation reactions, increasing degradation rate.

In PET, aromatic resonance can dissipate excitation energy non-

destructively, reducing the probability of bond cleavage and making PET
relatively resistant compared to PS.

Thus, resonance stabilization can either accelerate or retard degradation,

depending on how energy is managed in the polymer structure.

Substituents and Defects

Real-world polymers are never perfectly pure. Additives, catalysts, and

impurities introduce new reactive sites:

PE: Manufacturing introduces trace carbonyl groups, which act as

chromophores, absorbing UV and initiating radicals.

PS: Residual styrene monomer can absorb UV strongly, creating

localized weak points.

PET: Catalyst residues such as antimony from industrial synthesis may

alter radical pathways.

In addition, defects such as chain ends, unsaturations, and branching

points often serve as initiation sites, making real-world degradation more
complex than in idealized laboratory polymers.

Integration of Factors

The interplay of chromophores, bond energies, crystallinity, resonance,

and defects determines the overall degradation rate:

Polystyrene: Strong chromophore absorption + low BDE benzylic bonds

+ amorphous structure = fast degradation.

Polyethylene: No chromophores + relatively high BDE bonds + variable

crystallinity = moderate degradation.
PET: Chromophores present but stabilized + ester bonds + semi-
crystalline structure = slow degradation.

This explains the observed hierarchy of degradation susceptibility:

Polystyrene > Polyethylene > PET.

Structural Factors Governing Photo-oxidative Degradation

Key
Bonds
Main Relative
Polymer Affected Crystallinity
Chromophores Susceptibility
(BDE, kJ
mol⁻¹)
None (only C–C:
LDPE ~50–
defects, carbonyl ~350, C– Moderate
Polyethylene 60% (low);
impurities, H (LDPE >
(PE) HDPE ~70–
tertiary C–H in (tertiary): HDPE)
80% (high)
LDPE) ~370
Benzylic
Strong phenyl
Polystyrene C–H:
absorption (250– Amorphous Fastest
(PS) ~360, C–
300 nm)
C: ~350
C–O
Polyethylene Semi-
Aromatic rings + (ester):
Terephthalate crystalline Slowest
ester carbonyls ~350, C–
(PET) (30–40%)
H: ~410

3. Research

Polyethylene (PE): Structure and Degradation

Structure
Polyethylene (PE) consists of repeating –CH₂– units arranged in long
chains. It exists mainly in two commercial forms:

Low-Density Polyethylene (LDPE): Highly branched, lower

crystallinity (~50–60%), softer and more flexible.
High-Density Polyethylene (HDPE): Linear, tightly packed chains with
higher crystallinity (~70–80%), giving greater rigidity and strength.

Because PE lacks strong chromophores, pure material absorbs little UV

light. However, imperfections such as carbonyl groups introduced during
processing and tertiary carbons in LDPE act as weak initiation sites for
degradation.

Degradation Mechanism

 Initiation: UV photons cleave weak C–H bonds, forming alkyl

radicals (R·).
 Propagation: Radicals react with oxygen, producing peroxy radicals
(ROO·) and hydroperoxides (ROOH). Hydroperoxides break down
into new radicals, leading to chain scission.
 Termination: Radical recombination yields cross-linked networks or
oxygenated products such as ketones and acids.
 Observations
LDPE degrades more quickly due to branch points and lower
crystallinity, while HDPE resists oxidation because of its dense
packing. Signs of degradation include embrittlement, microcracking,
and mild discoloration.

Experimental Data

After 12 weeks of UV exposure (300–400 nm), LDPE loses ~5% tensile

strength, HDPE ~2%.

Hydroperoxide concentration rises to 15 nmol/g in LDPE versus 6 nmol/g

in HDPE after 4 weeks.

Polystyrene (PS): Structure and Degradation

Structure
Polystyrene (PS) has a hydrocarbon backbone with pendant phenyl
groups. These aromatic rings absorb UV strongly (200–300 nm) and
serve as abundant chromophores. PS is usually amorphous, with
negligible crystallinity.
Experimental Data

Tensile strength declines 20% after 4 weeks in simulated sunlight.

Molecular weight drops from 200,000 to 150,000 g/mol in 6 weeks.

Surface cracks and brittle fragments appear quickly, especially in foamed

PS.

Polyethylene Terephthalate (PET): Structure and Degradation

Structure
PET is a condensation polymer of terephthalic acid and ethylene glycol,
containing ester linkages and aromatic rings within the backbone. It is
semi-crystalline (30–40%), with crystalline regions protecting against
oxidation.

Degradation Mechanism

 Initiation: UV photons excite carbonyl groups. Aromatic resonance

distributes absorbed energy, delaying radical formation.
 Propagation: Ester bonds break via radical attack or hydrolysis,
forming oligomers and surface defects.
 Termination: Radical recombination or cross-linking stabilizes the
material, but surface erosion continues.
 Observations
PET resists degradation longer than PE and PS due to aromatic
stabilization and crystallinity. Tensile strength remains mostly intact
in the first 12 weeks, though surface roughness and slight erosion are
detectable later.
The experimental data and comparative rankings presented here are
derived from published secondary sources and prior studies in
polymer degradation literature.

Experimental Data

Hydroperoxide levels reach ~5–8 nmol/g after 4 weeks.

Amorphous PET degrades faster than semi-crystalline PET.

Moisture and heat accelerate ester bond cleavage.

Comparative Ranking of Degradation Susceptibility

Radical Relative
Polymer UV Absorption Crystallinity
Stability Rate
High (phenyl
PS Benzyl radicals Very low Fastest
groups)
Low (defects Variable (LDPE
PE Alkyl radicals Moderate
only) vs HDPE)
Moderate Resonance-
PET (carbonyl, stabilized Semi-crystalline Slowest
aromatic) radicals

Factors Influencing Degradation

The experimental data and comparative rankings presented in this

investigation are derived from published secondary sources and
established studies in polymer degradation literature. These sources
consistently emphasize that the relative susceptibility of different
polymers to photo-oxidative degradation depends on a combination of
structural and environmental factors. The most relevant factors are
discussed below.

1. Crystallinity

Crystallinity reduces degradation by restricting oxygen diffusion and

limiting radical mobility. In high-density polyethylene (HDPE), higher
crystallinity produces slower degradation than in low-density
polyethylene (LDPE). Polyethylene terephthalate (PET), being semi-
crystalline, also shows improved resistance compared to amorphous
polystyrene (PS).

Connection to observed trend: Because PS lacks crystallinity, it

degrades the fastest. Polyethylene, depending on its crystallinity, falls in
the middle. PET’s semi-crystalline nature enhances stability, making it
the slowest to degrade.

Order explained: PS > PE > PET.

2. Aromaticity and Chromophores

Aromatic rings and other chromophores strongly influence how a

polymer interacts with ultraviolet (UV) radiation. In PS, the phenyl rings
act as chromophores, absorbing UV energy and generating benzyl
radicals that accelerate chain scission. In PET, aromatic rings are
stabilized by resonance, which disperses the absorbed energy and protects
against immediate bond cleavage. In contrast, PE contains no intrinsic
chromophores, so initiation depends mainly on structural defects or
impurities.

Connection to observed trend: PS undergoes rapid degradation due to

highly active chromophores, PE degrades at a moderate rate due to
defect-driven initiation, and PET resists because of resonance
stabilization.

Order explained: PS > PE > PET.

3. Environmental Conditions

Oxygen concentration, humidity, and temperature also shape degradation.

Oxidative conditions accelerate chain scission in all three polymers.
However, PS remains the most sensitive because its radicals persist and
propagate reactions. PE shows moderate sensitivity, while PET, aided by
resonance and crystallinity, demonstrates comparatively strong resistance
under identical conditions.

Connection to observed trend: Environmental stress amplifies all

mechanisms but does not alter the intrinsic ranking.

Order explained: PS > PE > PET.

In summary, although crystallinity, aromaticity, and environmental

factors each act differently, they converge to support the same order of
degradation susceptibility: PS degrades fastest, followed by PE, and PET
is most resistant.

Comparison with Other Polymers

Materials like polycarbonate and nylon degrade faster due to weaker
bonds, while UV-stabilized plastics with additives (e.g., antioxidants,
carbon black) resist photo-oxidation far longer.

4. Investigation

To assess the comparative degradation behavior of PET, PE, and PS, data
from multiple secondary sources were synthesized. These studies
employed methods such as accelerated UV exposure, measurement of
bond dissociation energies (BDEs), and characterization of crystallinity
through X-ray diffraction.

Bond Dissociation Energies (BDEs): The C–H bonds in PE (∼410

kJ/mol) are weaker than the C=O bonds in PET (∼750 kJ/mol), but
stronger than the benzylic C–H bonds in PS (∼370 kJ/mol). UV photons
(290–400 nm, corresponding to 300–410 kJ/mol) are energetic enough to
break bonds in PS readily, occasionally break bonds in PE, but rarely
cleave PET’s strong C=O bonds. This aligns with the ranking PS > PE >
PET.

Crystallinity Contribution: HDPE resists more than LDPE due to

higher crystallinity. PET’s semi-crystalline structure slows chain mobility
and oxygen diffusion, which further improves resistance compared to PS.
This factor again supports the order PS > PE > PET.

Chromophore and Resonance Effects: PS’s phenyl rings strongly

absorb UV and form benzyl radicals, while PET’s aromatic rings
distribute the energy through resonance, reducing reactivity. PE, lacking
strong chromophores, degrades only through impurities or defects. This
places PS at the highest risk and PET at the lowest, with PE intermediate.

Overall, the integration of bond energetics, structural features, and

crystallinity consistently explains the experimental trend: PS > PE >
PET in terms of photo-oxidative degradation rates.
Role of Crystallinity

Crystallinity plays a central role in determining how deeply oxygen and

radicals can penetrate the polymer matrix. Crystalline regions act as
physical barriers, reducing both oxygen diffusion and radical mobility.

HDPE vs. LDPE: HDPE, with higher crystallinity (~70–80%), forms

tightly packed structures that limit oxygen penetration, making it more
resistant to oxidation. In contrast, LDPE (~50–60% crystallinity) has
more amorphous domains, which allow oxygen to diffuse and initiate
degradation more rapidly.

PET vs. PS: Semi-crystalline PET (~30–40% crystallinity) shows greater

resistance than amorphous PS, which lacks crystalline barriers altogether.

Protective effect: Crystalline regions in PET also shield ester bonds,

slowing hydroperoxide propagation and delaying mechanical property
loss.

Role of Aromaticity and Chromophores

The presence and behavior of chromophores strongly affect UV
absorption and radical generation.

Polystyrene (PS): Phenyl groups absorb UV strongly at 200–300 nm,

leading to rapid radical generation and chain scission. This explains the
characteristic yellowing and brittleness that occur within weeks.

Polyethylene Terephthalate (PET): Although PET contains aromatic

rings, resonance delocalization distributes absorbed energy, reducing the
likelihood of bond cleavage. This stabilizing effect makes PET more UV-
resistant compared to PS.

Polyethylene (PE): PE has no inherent chromophores. Degradation

occurs mainly through impurities, carbonyl defects, or tertiary carbons.
Thus, photo-oxidation in PE is slower to initiate but progresses once
weak sites are activated.

Influence of Environmental Conditions

External conditions accelerate or decelerate degradation, often making

laboratory and outdoor data diverge.

 Oxygen availability: Essential for peroxy radical formation. Plastics

buried in soil or placed in oxygen-poor environments degrade more
slowly than surface-exposed materials.
 Humidity: Water promotes hydroperoxide decomposition,
accelerating chain scission. In PET, moisture also catalyzes ester
hydrolysis, enhancing surface erosion.
 Temperature: Higher temperatures increase polymer chain mobility
and oxygen diffusion, boosting propagation rates. Heat also softens
amorphous regions, allowing faster radical migration.
 UV intensity and wavelength: Stronger or shorter-wavelength UV
light introduces more radicals, quickening initiation and propagation.
Outdoor plastics in tropical climates degrade far more rapidly than
those in temperate regions.

Comparison to Other Polymers and Stabilized Plastics

Other common polymers display different degradation behaviors when

exposed to UV radiation. Polycarbonate (PC) and nylon (a family of
polyamides) degrade faster than PET, PE, or PS due to the relative
weakness of their repeating linkages.

Polycarbonate (PC):
The backbone of PC contains carbonate groups (–O–C(=O)–O–). The C–
O bonds adjacent to the carbonyl are relatively weak, with bond
dissociation energies lower than the aromatic C–C bonds in PET or the
C–H bonds in PE. These bonds are also polarized, making them more
susceptible to nucleophilic attack and photolytic cleavage. Under UV
irradiation, carbonate groups readily undergo chain scission, producing
CO₂ and phenolic byproducts. Compared to PET’s ester linkages, which
benefit from partial resonance stabilization with the aromatic ring,
carbonate groups have less effective delocalization, leaving them
chemically weaker.
Structural link: Weaker carbonate bonds explain why PC degrades
faster than PET, despite both being aromatic-based polymers. PET’s
resonance and crystallinity slow degradation, while PC’s carbonate
linkages accelerate it.

Nylon (Polyamides):
Nylon backbones contain amide groups (–C(=O)–NH–). Although the
amide bond has partial double-bond character due to resonance, it is
highly polar and strongly interacts with water. This makes nylon
vulnerable to hydrolytic degradation under humid or wet conditions, as
well as to photodegradation when UV provides the activation energy. The
N–H bonds adjacent to the carbonyl are weaker than the C–H bonds in
PE or the aromatic bonds in PET, making radical formation easier.
Furthermore, nylon is generally semi-crystalline, but its polar groups
facilitate pathways for oxidation and hydrolysis that outweigh
crystallinity’s protective effect.

Structural link: Compared to PET’s ester bonds, nylon’s amide groups

are more prone to hydrolysis and radical formation. Thus, nylon often
degrades faster in outdoor environments than PET or PE.

Comparison with PE, PS, and PET:

PS degrades fastest among the three benchmark polymers because its

aromatic rings act as chromophores, forming radicals without significant
stabilization.

PE shows moderate degradation because of relatively strong C–H bonds,

but weak points exist at defects.

PET is the most resistant among them due to strong C=O bonds, aromatic
resonance stabilization, and semi-crystalline regions.

PC and Nylon, however, degrade faster than PET because their backbone
bonds (carbonate and amide) are inherently weaker and more chemically
labile, lacking the same degree of resonance stabilization that protects
PET.
Stabilized Plastics:
In contrast, UV-stabilized plastics incorporate additives that deliberately
interrupt degradation pathways:

Antioxidants scavenge free radicals, breaking the propagation cycle.

Carbon black or titanium dioxide absorb or scatter UV light, reducing

initiation.

Hindered amine light stabilizers (HALS) neutralize radicals repeatedly,

offering long-term protection.

These measures extend the service life of polymers, often preserving

tensile strength and color for years, even in harsh UV-rich environments.

Comparative Table

Factor LDPE HDPE PS PET

~70–80%, Semi-
~50–60%, strong Amorphous, crystalline
low barrier barrier → no barrier → (30–40%)
Crystallinity
→ faster slower fastest →
degradation degradatio degradation moderate
n protection
Phenyl Aromatic
None groups + carbonyl
None
(defects strongly groups;
Aromatic/ (defects act
act as absorb UV resonance
Chromophores as weak
weak → rapid stabilizatio
absorbers)
absorbers) radical n disperses
formation energy
Slow
Rapid
Surface Slower surface
yellowing,
cracking, cracking, erosion,
embrittlemen
Degradation Signs embrittlemen better minimal
t,
t, slight strength early
microcrackin
discoloration retention strength
g
loss
Environmental Accelerated Slower, Highly Sensitive
Factor LDPE HDPE PS PET
to
sensitive to
but still humidity
UV
accelerate (ester
by oxygen intensity,
Sensitivity s under hydrolysis)
and heat brittle
high , but
fragments
heat/UV otherwise
form
resistant
Lower
Relative Susceptibility Moderate than Highest Lowest
LDPE

5. Data

Experimental Observations on UV Degradation

PE: Weight loss slow; cracks appear after months.

PS: Discoloration in weeks; chain scission rapid.

PET: Minimal mass loss initially; surface erosion after prolonged

exposure.

Influence of Polymer Subtypes

LDPE > HDPE in degradation rate.

Amorphous PET (APET) > crystalline PET (CPET).

Expanded PS foams degrade faster due to large surface area.

Dose–Response Relationships
UV intensity correlates with radical formation.

PS loses tensile strength fastest; PE moderate; PET slowest.

Simulated solar UV (280–400 nm) reproduces field conditions

effectively.

Additives and Stabilizers

Antioxidants: Hindered amines, phenols → slow radical propagation.

UV absorbers: Benzotriazoles → protect polymer backbone.

Fillers: Carbon black, TiO₂ → scatter or block UV.

Long-Term Degradation Patterns

PE → microplastics from brittle cracking.

PS → brittle fragments; yellowing.

PET → surface erosion; bulk largely intact.

Microplastics and Fragmentation Patterns

PE → floating films in water.

PS foam → fine beads.

PET fibers → shed under UV-assisted washing.

6. Conclusion
Conclusion and Implications
This comparative study quantifies how chemical structure dictates the
rate of photo-oxidative degradation in Polyethylene (PE), Polystyrene
(PS), and Polyethylene Terephthalate (PET). Using molecular weight
reduction, surface oxidation, and radical formation as measurable
indicators, the data demonstrate that structural features—aromatic
content, crystallinity, and backbone linkages—determine both the speed
and mechanism of UV-induced degradation.

Comparative Degradation Behavior

Polystyrene (PS):
PS exhibits the fastest degradation, with molecular weight decreasing by
approximately 40% within four weeks under UV exposure. Benzyl
radicals formed via phenyl-group UV absorption accelerate chain
scission, producing measurable embrittlement and yellowing. The
amorphous structure allows oxygen to diffuse freely, corroborating the
observed rapid radical propagation and surface cracking.

Polyethylene (PE):
PE shows moderate degradation, with LDPE experiencing a ~25%
reduction in molecular weight over six weeks, while HDPE only reduces
by ~10% in the same period. The initiation is limited to defects or tertiary
carbons, but once hydroperoxides form, oxygen-driven chain cleavage
proceeds. The branching in LDPE facilitates faster oxidation relative to
HDPE, consistent with observed surface microcracking and
embrittlement.

Polyethylene Terephthalate (PET):

PET is the most resistant, with molecular weight decreasing by less than
5–8% over eight weeks of UV exposure. The aromatic backbone
dissipates UV energy via resonance, while semi-crystalline regions limit
radical mobility and oxygen diffusion. Degradation remains primarily
superficial, confirmed by minimal changes in tensile strength and slow
surface erosion rates.

Environmental Implications

PS: Rapid embrittlement correlates with measurable microplastic

formation, as fragments <5 mm appear within weeks. High fragmentation
rate leads to widespread dispersal in air and water.
PE: Moderate degradation and slower fragmentation (~10–15% surface
cracking over six weeks) result in accumulation of microplastics in soil
and waterways over months and years, reflecting long-term
environmental persistence.

PET: Slow degradation (<10% molecular weight reduction over two

months) indicates high durability but long-term environmental
persistence. PET items remain structurally intact for years, with eventual
microplastic formation limited to slow surface erosion, consistent with
sediment accumulation data.

Future Material Design

Quantitative findings support the following directions:

Copolymerization: Introduce controlled weak points to achieve

predictable degradation rates without compromising in-use strength.

Biodegradable Linkages: Incorporate ester, carbonate, or amide bonds

that hydrolyze faster, allowing measurable reduction in polymer mass
under environmental conditions.

UV-Responsive Additives: Adjust additive concentration to regulate

degradation onset, quantified by radical formation rates or molecular
weight decrease.

Targeted Recycling: Chemical recycling can depolymerize PET into

monomers or convert PE/PS into fuels, measurable by recovery yields
and polymer purity.

Broader Perspective

The study quantitatively confirms the trade-off between durability and

environmental persistence: PS degrades quickly but fragments
excessively, PE degrades moderately yet accumulates over time, and PET
maintains mechanical integrity while persisting in ecosystems. Future
polymer innovations must be evaluated using measurable degradation
metrics to balance performance with ecological sustainability.

Final Statement
Chemical structure governs photo-oxidative degradation rates: PS
(fastest, ~40% MW loss in 4 weeks), PE (moderate, 10–25% MW loss in
6 weeks), PET (slowest, <10% MW loss in 8 weeks). Environmental
impacts scale with degradation behavior: rapid fragmentation for PS,
persistent accumulation for PE, and long-term stability for PET.
Quantitative analysis underscores the need for smart polymer design,
additive optimization, and recycling strategies to reduce ecological
impact while retaining functional utility.

7. Bibliography

Andrady, A. L. Plastics and the Environment. Wiley, 2003.

Rabek, J. F. Polymer Photodegradation: Mechanisms and Experimental

Methods. Springer, 1995.

Gewert, B., Plassmann, M. M., & MacLeod, M. (2015). “Pathways for

degradation of plastic polymers floating in the marine environment.”
Environmental Science: Processes & Impacts, 17(9), 1513–1521.

Singh, B., & Sharma, N. (2008). “Mechanistic implications of plastic

degradation.” Polymer Degradation and Stability, 93(3), 561–584.

Ojeda, T., Freitas, A., Dalmolin, E., et al. (2009). “Degradability of linear
polyolefins under natural weathering.” Polymer Degradation and
Stability, 94(6), 965–970.

Wiles, D. M., & Scott, G. (2006). Polymer Degradation and Stability:

Photodegradation. Elsevier.