UNIT 1

(Advanced Materials for Smart Devices)

Sustainable polymers ( PLA, PGA, PHBV)

Sustainable polymers are materials designed to minimize environmental impact throughout their
lifecycle, from production to disposal. These polymers are materials derived from renewable,
recycled and waste carbon resources and their combinations, which at the end of life can be
recycled, biodegraded or composted.

Types of Sustainable Polymers:

1. Biodegradable Polymers:Polymers like Polylactic acid (PLA), polyhydroxyalkanoates

(PHA).
2. Bio-based Polymers: Bio-polyethylene (bio-PE), bio-polyethylene terephthalate (bio-
PET).
3. Recycled Polymers: Recycled high-density polyethylene (HDPE).

Synthesis and Application of Polylactic Acid (PLA)

PLA is a biodegradable and bio-based polymer primarily derived from renewable resources like
corn starch, sugarcane, and other plant materials. It is widely used as an environmentally friendly
alternative to petroleum-based plastics, particularly in packaging, 3D printing, and medical
applications.

Synthesis of PLA

The synthesis of PLA generally occurs in two main steps: the production of lactic acid (or
lactide) and its polymerization into PLA.

The synthesis of Polylactic Acid (PLA) involves the polymerization of lactic acid or its dimer,
lactide, through different processes. The most common method is the ring-opening
polymerization (ROP) of lactide. Here’s a breakdown of the chemical reactions involved in the
synthesis of PLA.

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1. Fermentation: Production of Lactic Acid

The first step in the PLA synthesis process is the production of lactic acid. This is typically done
through the microbial fermentation of carbohydrates (like glucose from corn starch) using
bacteria such as Lactobacillus. The fermentation reaction is:

C6H12O6 2 CH3CH(OH)COOH
(Glucose) (lactic acid)

2. Formation of Lactide (Cyclic Dimer of Lactic Acid)

The lactic acid monomer undergoes a condensation reaction to remove water and form a dimer
called lactide. The reaction typically occurs under heat:

2 CH3CH(OH)COOH dehydration (CH3CHCOO)2 +H2O2

(lactide)

In this step, lactic acid molecules are heated to drive off water and convert the monomer into
lactide, a cyclic dimer that is easier to polymerize.

There are three possible forms of lactide:

 L-lactide (two L-lactic acid units)

 D-lactide (two D-lactic acid units)
 meso-lactide (one L- and one D-lactic acid unit)

3. Ring-Opening Polymerization (ROP)

The polymerization of PLA from lactide occurs via ring-opening polymerization, which is the
most common industrial method. This reaction uses a catalyst, such as tin(II) octoate and an
initiator like an alcohol, to open the lactide ring and form long PLA chains. The general reaction
is:

Catalyst
n (CH3CHCOO)2 [−CH(CH3)COO−]
n (polylactic acid)

Here, the cyclic lactide molecule opens up and links with others to form a long polymer chain
(PLA). This reaction can be controlled to produce either low molecular weight or high
molecular weight PLA, depending on the conditions and catalysts used.

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4. Direct Polycondensation (Alternative Method)

In an alternative process, direct polycondensation of lactic acid is used, though this method is
less common for industrial PLA due to lower molecular weight products. This process involves
the dehydration of lactic acid monomers:

dehydration
n CH3CH(OH)COOH [−CH(CH3)COO−]n + n H2O
(lactic acid) (PLA)

In this case, lactic acid molecules join to form PLA, with water being a byproduct of the
reaction. However, this method can result in incomplete polymerization and lower-quality PLA,
requiring further processing.

Properties of PLA

1. Biodegradability:
o PLA is fully biodegradable under industrial composting conditions (high
temperature and humidity), breaking down into water, carbon dioxide, and
biomass.
o In home compost or natural environments, PLA may take longer to degrade
compared to commercial settings.
2. Renewability:
o PLA is derived from renewable plant resources, making it a more sustainable
alternative to conventional plastics derived from petroleum.
3. Mechanical Properties:
o Tensile strength: PLA has a relatively high tensile strength and stiffness, making
it suitable for packaging, fibers, and 3D printing.
o Brittleness: While PLA has good strength, it can be brittle and prone to cracking
under stress. To improve flexibility, additives or copolymers like
polycaprolactone (PCL) are sometimes mixed with PLA.
4. Thermal Properties:
o Glass transition temperature (Tg): Around 55–60°C, meaning PLA starts to
soften at this temperature, limiting its use in high-temperature applications.
o Melting point: Around 150–180°C, allowing it to be processed in various
applications like injection molding and 3D printing.
5. Transparency:

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 o PLA can be produced as a clear, glass-like material, making it suitable for use in
transparent packaging and films.

6. Barrier Properties:
o PLA has decent oxygen barrier properties, which is useful in food packaging,
although it is not as good as petroleum-based plastics like PET.
7. Biocompatibility:
o PLA is non-toxic and biocompatible, making it ideal for medical applications
such as sutures, drug delivery systems, and biodegradable implants.

Applications of PLA

 Packaging: PLA is commonly used in food containers, bottles, and packaging films.
 3D Printing: PLA is one of the most popular filaments for 3D printing due to its ease of
use and low toxicity.
 Medical Devices: PLA is used in biodegradable sutures, stents, and scaffolds for tissue
engineering.
 Textiles: PLA can be used to make fibers for clothing and biodegradable bags.

Synthesis and Application of Polyglycolic Acid (PGA)

Polyglycolic acid (PGA) is a biodegradable polymer that is part of the polyesters family. It is
synthesized from glycolic acid and has significant applications in medical and environmental
fields.

Synthesis:

Polyglycolic acid is a versatile biodegradable polymer synthesized primarily through the

polymerization of glycolic acid. Its unique properties and applications in the medical and
environmental sectors make it a key material in the pursuit of sustainable solutions. As research
continues, its uses are likely to expand, further enhancing its role in biocompatible and eco-
friendly technologies.

The polymerization of polyglycolic acid (PGA) typically involves the ring-opening

polymerization (ROP) of glycolic acid, particularly in its cyclic dimer form. Here’s a detailed
overview of the polymerization reaction:

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Properties:

 Biodegradability: PGA degrades in the body through hydrolysis, making it suitable for
medical applications.
 Mechanical Properties: High tensile strength and modulus, suitable for sutures and
implants.
 Thermal Properties: Melting temperature around 225°C, making it stable for various
applications.

Applications:

1. Medical Applications:
o Sutures: PGA is widely used in absorbable sutures due to its biocompatibility and
biodegradability.
o Drug Delivery Systems: PGA can be formulated into microspheres for controlled
drug release.
o Tissue Engineering: Used as scaffolding materials for cell growth and tissue
regeneration.
2. Environmental Applications:
o Biodegradable Packaging: PGA can be used in packaging materials that
decompose naturally, reducing plastic waste.
o Agricultural Films: Used for mulch films that can biodegrade, minimizing
environmental impact.
3. Biomedical Devices:
o Implants: Used in various biodegradable implants for tissue repair and
regeneration.
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 o Wound Dressings: PGA can be incorporated into dressings that promote healing
while degrading over time.

Synthesis and Application of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

(PHBV)
PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)) is a biopolymer belonging to the
family of polyhydroxyalkanoates (PHAs). It's synthesized by various microorganisms,
particularly bacteria, through the fermentation of carbon sources. It is a thermoplastic
linear aliphatic polyester.

Synthesis of PHBV

It is obtained by the copolymerization of 3-hydroxybutanoic acid and 3-

hydroxypentanoic acid.

Properties of PHBV

1. Biodegradability: PHBV is biodegradable, breaking down into harmless byproducts

through microbial action, which makes it an environmentally friendly alternative to
conventional plastics.
2. Mechanical Properties:
o It exhibits good tensile strength and elasticity, although these properties can vary
based on the ratio of 3-hydroxybutyrate (3HB) to 3-hydroxyvalerate (3HV) in the
copolymer.
o PHBV can have a glass transition temperature (Tg) around 5°C and a melting
temperature (Tm) around 170°C.
3. Thermal Properties: PHBV shows thermal stability, which is advantageous for
processing. However, it can be more sensitive to heat compared to conventional plastics.
4. Barrier Properties: It has good gas barrier properties, making it suitable for packaging
applications.

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Applications of PHBV

1. Packaging: Due to its biodegradability and good mechanical properties, PHBV is used in
biodegradable packaging materials, such as films, containers, and bags.
2. Medical Applications:
o Sutures and Scaffolds: PHBV is biocompatible, making it suitable for use in
medical sutures and tissue engineering scaffolds.
o Drug Delivery Systems: Its ability to degrade in the body allows for controlled
drug release applications.
3. Agriculture: PHBV can be used to create biodegradable mulch films, which help reduce
plastic waste in farming.
4. 3D Printing: Its thermoplastic nature makes it suitable for 3D printing applications,
allowing for the creation of biodegradable products and components.
5. Textiles: PHBV fibers can be used in the textile industry for creating eco-friendly fabrics.

Leaching of Micro-plastics

Leaching of microplastics refers to the process by which chemicals contained within

microplastics are released into the environment, particularly water bodies, as the plastics break
down or degrade. Microplastics are tiny plastic particles less than 5 mm in size, and they can
originate from a variety of sources, such as larger plastic debris breaking down, synthetic fibers
from clothing, or microbeads in personal care products.

When microplastics enter ecosystems, especially water, they can leach harmful chemicals. This
happens in two primary ways:

1. Additives in plastics: Many plastics contain chemical additives like plasticizers (e.g.,
phthalates), stabilizers, and flame retardants. These chemicals can leach out of the plastic
particles over time and potentially contaminate soil and water, posing risks to wildlife
and humans.
2. Adsorption of pollutants: Microplastics can also absorb and carry external pollutants
(such as heavy metals or persistent organic pollutants like PCBs) from the surrounding
environment. Once ingested by marine organisms or other animals, these toxic substances
can enter food chains.

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Leaching of microplastics is a growing environmental concern, as it can affect water quality,
ecosystems, and human health, particularly through bioaccumulation in food webs.

reventing the leaching of microplastics requires efforts to reduce both the production of
microplastics and their release into the environment. Here are some strategies to minimize
leaching:

1. Reduce Plastic Use

 Minimize single-use plastics: Avoid products with excessive plastic packaging and
choose alternatives like reusable bags, glass, or metal containers.
 Choose natural fibers: Opt for clothing made from natural materials like cotton, wool,
or hemp, as synthetic fibers (like polyester) shed microplastics during washing.

2. Proper Waste Management

 Recycling: Ensure plastic waste is properly sorted and recycled to prevent it from
entering ecosystems where it can break down into microplastics.
 Improved waste disposal: Encourage proper disposal of plastics and promote systems
that prevent littering or leakage of plastic into the environment.

3. Use of Advanced Filtration Systems

 Washing machine filters: Install filters in washing machines to capture microfibers from
synthetic clothes during washing, preventing them from entering water systems.
 Water treatment upgrades: Municipal wastewater treatment plants can be upgraded to
better capture microplastics before they are discharged into rivers and oceans.

4. Designing Eco-friendly Products

 Biodegradable plastics: Promote the development of biodegradable plastics that break

down into non-toxic components.
 Safer plastic additives: Manufacturers can design plastics with fewer harmful additives,
reducing the risk of leaching toxic chemicals.

5. Legislation and Policy

 Banning microbeads: Support or implement bans on microbeads (tiny plastic particles)

in personal care products, which directly contribute to microplastic pollution.
 Plastic regulations: Advocate for regulations that restrict the production and use of
certain harmful plastic additives that can leach into the environment.
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6. Public Awareness

 Education and outreach: Increase public awareness about the dangers of microplastic
pollution and how everyday actions contribute to it. This can help drive behavior change
and support for policy measures.

By taking these steps, society can reduce the release of microplastics and prevent the harmful
chemicals in plastics from leaching into ecosystems.

Microplastic pollution in the environment is a major concern for governments and companies
worldwide attempting to understand and reduce the damage they cause. As well as the direct
damage these plastic pellets can also act as chemical reservoirs that leach chemical contaminants
into the environment and further damage ecosystems. The Column spoke to Manuel Miró from
the University of the Balearic Islands, Spain, about his research into the pollution caused by
chemical leaching from microplastics.

Factors that affect leaching

The leaching of chemicals from microplastics is affected by a variety of factors, including:

Sunlight: Sunlight can cause photochemical degradation, which can lead to the release of
chemicals.
Water flow: Microplastics in flowing water may release plasticisers at a faster rate.
pH levels: Acidic and basic pH levels are more aggressive to plastic materials than neutral pH
levels.
Plasticizer content: The concentration of plasticizers in microplastics can affect the rate of
leaching
Effects on organisms
When aquatic organisms consume microplastics, they can be harmed by the physical ingestion
of the microplastics, as well as by the toxic chemicals that leach out during digestion.
Effects on the environment
Microplastics can contribute to a buildup of plasticisers in the environment. They can also
release dissolved organic carbon (DOC), which can stimulate the growth of marine microbial
communities.
Microplastic sources
Microplastics can come from a variety of sources, including washing machines and synthetic
clothing.