Introduction Of Polymer Science

Experiment No :- 3

AIM:-
To carry out the polymerization process of Polyethylene Terephathalate(PET) using ethylene
glycol and terephathalic acid.
APPARATUS:
• Beaker
• Glass rod
• Themometer
• Stirrer
• Heater
• Pipette
• Safety Equipment
CHEMICALS:-
Terephthalic Acid (TPA)
Ethylene Glycol (EG)
CHEMICAL REACTION:-
The synthesis of polyethylene terephthalate (PET) generally involves two main chemical
reactions: esterification (or transesterification) and polycondensation. Here’s a breakdown of
these reactions:
1. Esterification Reaction
In the first step, terephthalic acid (TPA) reacts with ethylene glycol (EG) to form bis(2-
hydroxyethyl) terephthalate (BHET) and water. The reaction can be represented as:
Terephthalic Acid+Ethylene Glycol→BHET+Water
C6H4(COOH)2 + HO-CH2-CH2-OH→ C6H4(COOCH2-CH2OH)2 + H2O

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COOH

O
OH
OH O
+
O
HO HO
O

COOH

Ethylene Glycol Terephthalic BHET(Bi 2-Hydroxi Ethyl

Acid Terephalate)

2. Polycondensation Reaction
In the second step, BHET undergoes polycondensation to form PET. This reaction involves the
elimination of water as the polymer chains grow. The reaction can be represented as:
nC6H4(COOCH2-CH2OH) → (C10H8O4)n + nH2O

CH2CH2
O
O COO
CO
OH
O
O
HO
O

n + 2H2O

BHET PET

Overall Reaction
The overall process can be summarized as:
nC6H4(COOH)2 + nHO-CH2-CH2-OH → (C10H8O4)n + nH2O

Summary
• Esterification: TPA + EG → BHET + H₂O
• Polycondensation: BHET → PET + H₂O
These reactions typically require heat and sometimes a catalyst to proceed efficiently, resulting
in the formation of the polymer PET.
Key Points

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• Reactants: Terephthalic acid and ethylene glycol.

• Products: Polyethylene terephthalate (PET) and water.
• Conditions: The reactions typically require heat for efficiency.
This sequence of reactions leads to the formation of PET, a widely used polymer in textiles and
packaging.
THEORY:-
The synthesis of polyethylene terephthalate (PET) is based on the principles of polymer
chemistry, particularly the mechanisms of esterification and polycondensation. Here’s a
theoretical overview:
1. Polymer Chemistry Basics
• Polymers are large molecules composed of repeating structural units (monomers)
connected by covalent bonds.
• Condensation Polymerization is a type of polymerization where monomers join
together with the elimination of a small molecule, often water.
2. Monomers
The two primary monomers in PET synthesis are:
• Terephthalic Acid (TPA): An aromatic dicarboxylic acid with the formula
C6H4(COOH)2. Its structure contributes to the thermal and chemical stability of PET.
• Ethylene Glycol (EG): A simple diol with the formula HO-CH2-CH2-OH. It provides
flexibility to the polymer chain.
3. Reaction Mechanisms
a. Esterification
• The reaction between TPA and EG forms bis(2-hydroxyethyl) terephthalate (BHET)
through esterification.
• This process involves the formation of ester bonds (−COO−-COO-−COO−) and
releases water as a by-product.
b. Polycondensation
• In the second step, BHET undergoes polycondensation, where multiple BHET
molecules react to form long chains of PET.
• This reaction continues until a high molecular weight polymer is achieved, again with
the release of water.
4. Thermodynamics and Kinetics

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• Equilibrium: The esterification reaction can reach an equilibrium, so removing water

or using excess reactants can drive the reaction towards the product formation.
• Temperature: Higher temperatures favor the reaction rate and polymerization but can
also lead to side reactions if not controlled.
Summary
The synthesis of PET through condensation polymerization illustrates fundamental concepts in
polymer chemistry, such as the role of monomers, reaction mechanisms, thermodynamics, and
the importance of catalysts. Understanding these principles helps in manipulating the synthesis
process to achieve desired polymer properties.
PROCEDURE:-
Step 1: Esterification
1. Preparation:
o In a round-bottom flask, combine stoichiometric amounts of terephthalic acid
(TPA) and ethylene glycol (EG). The typical molar ratio is 1:2 (TPA).
2. Mixing:
o Stir the mixture using a magnetic stirrer to ensure thorough mixing of the
reactants.
3. Heating:
o Gradually heat the flask to around 180-200 °C.
o Use a condenser to prevent the loss of volatile components (like water) during
the reaction.
4. Water Removal:
o As the reaction proceeds, water will be formed and should be continuously
removed (using a distillation setup or a condenser).
5. Completion:
o Continue heating until the reaction is complete (indicated by the cessation of
water formation). This may take several hours.
Step 2: Polycondensation
1. Transition to Polycondensation:
o After the esterification is complete, further increase the temperature to about
250-270 °C under reduced pressure (if using a vacuum pump).
2. Polymer Formation:

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o Maintain these conditions to allow the formation of high molecular weight PET.
Continue to remove water by applying vacuum or maintaining an inert
atmosphere.
3. Cooling:
o Once the desired molecular weight is reached, remove the heat and allow the
reaction mixture to cool gradually.
Step 3: Isolation and Purification
1. Precipitation:
o The solid PET can be precipitated by adding the reaction mixture to a large
volume of distilled water or another non-solvent. This helps to remove
unreacted monomers.
2. Filtration:
o Filter the precipitated PET using vacuum filtration to collect the polymer.
3. Washing:
o Wash the collected polymer with distilled water to remove any residual
impurities.
4. Drying:
o Dry the purified PET under vacuum or in an oven at a low temperature (around
60-80 °C) to remove any remaining moisture.
Step 4: Characterization
1. Characterization:
o Analyze the synthesized PET using techniques such as:
▪ Nuclear Magnetic Resonance (NMR) Spectroscopy for structural
confirmation.
▪ Gel Permeation Chromatography (GPC) to determine molecular
weight.
▪ Differential Scanning Calorimetry (DSC) to assess thermal properties
OBSERVATION:-
During the synthesis of polyethylene terephthalate (PET), several observations can be made at
various stages of the process. Here’s a breakdown of what to look for:
1. Esterification Stage

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• Appearance of the Mixture: Initially, the mixture of terephthalic acid and ethylene
glycol will be a solid and a liquid, respectively. As they begin to mix, the solution will
become more homogeneous.
• Heating Changes: As the temperature increases, you may notice:
o The solid terephthalic acid dissolving into the liquid ethylene glycol.
o Bubbles forming in the mixture as water is produced, which may escape as
vapor.
• Odor: There may be a faint odor from the reactants and by-products, which should be
monitored in a fume hood.
2. Water Removal
• Condensation: Water vapor can be seen condensing in the condenser. The rate of water
removal may indicate the progress of the reaction.
• Volume Change: The volume of the liquid mixture may decrease as water is
continuously removed.
3. Polycondensation Stage
• Color Change: As polycondensation progresses, the mixture may darken slightly,
indicating the formation of the polymer.
• Viscosity Increase: The mixture will become more viscous over time as the molecular
weight of the polymer increases.
• Formation of Solid PET: Eventually, solid polymer may start to precipitate or form at
the bottom of the flask, indicating successful polymerization.
CALCULATION:-
To perform calculations related to the synthesis of polyethylene terephthalate (PET), typically
need to consider the stoichiometry of the reaction, calculate yields, and determine molecular
weights. Here’s a step-by-step guide to some common calculations:
Assume that all calculations are based on 25% material take by weight……so we calculate first
for 1 Mol and after we directly convert into it in 25%.
1. Stoichiometry
Balanced Reaction:
n C6H4(COOH)2 + n HO-CH2-CH2-OH → (C10H8O4)n + n H2On
Example Calculation: Determining Required Moles
Assuming you want to synthesize PET using 1 mole of terephthalic acid (TPA):

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• Required Ethylene Glycol (EG):

o Since the stoichiometric ratio is 1:2 (TPA), you will need 2 moles of EG.
2. Molecular Weights
Calculate the molecular weights of the reactants and products:
• Terephthalic Acid (TPA): C6H4(COOH)2
o C: 12.01 g/mol×8=96.08 g/mol
o H: 1.008 g/mol×6=6.048 g/mol
o O: 16.00 g/mol×4=64.00 g/mol
o Total: 96.08+6.048+64.00=166.13 g/mol
o So we take 41.5 gm for 0.25%
• Ethylene Glycol (EG): HO-CH2-CH2-OH
o C: 12.01 g/mol×2=24.02 g/mol
o H: 1.008 g/mol×6=6.048 g/mol
o O: 16.00 g/mol×2=32.00 g/mol
o Total: 24.02+6.048+32.00=62.07 g/mol
o So we take 31 gm for 0.25% on the basis of 1:2 ratio
• Bis(2-hydroxyethyl) Terephthalate (BHET):
o Formula: C10H10O4
o C: 12.01 g/mol×10=120.1 g/mol
o H: 1.008 g/mol×10=10.08 g/mol
o O: 16.00 g/mol×4=64.00 g/mol
o Total: 120.1+10.08+64.00=194.18 g/mol
3. Yield Calculation

If you start with 1 mole of TPA (166.13 g), and it completely reacts:
• Moles of EG needed: 2 moles×62.07 g/mol=124.14 g/mol
Total mass of reactants for 25% material:
• TPA: 41.5 g
• EG: 31 g
• Total: 41.5+31 =72.5 g

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If the theoretical yield of PET is calculated based on the moles of BHET produced
(assuming complete conversion):
• Moles of PET produced = 1 mole of TPA (based on stoichiometry).
• Molecular weight of PET: C10H8O4=192 g/mol
• So we can get PET out of 48 gm.(25% of total yield%)
Theoretical yield:
Yield=1 mol×192 g/mol=192 g But for us 48 gm.
4. Percent Yield Calculation
The actual yield obtained from the reaction is, say, 39.89 g:
Percent Yield = (Actual Yield/Theoretical Yield)×100=(39.89 g/48 g)×100 = 83.10%

Summary of Calculations
• Calculate the required moles based on stoichiometry.
• Determine molecular weights of reactants and products.
• Calculate theoretical yield based on the amount of starting materials.
• Calculate percent yield based on actual yield obtained.
These calculations are essential for understanding the efficiency and effectiveness of the PET
synthesis process.
RESULT:-
PET synthesis typically results in the formation of a high-molecular weight thermoplastic
polymer.PET is synthesized through a polymerization reaction.
Structure:- PET is a long chain polymer with repeating units of (-C6H4COOCH2CH2O-) in its
backbone.
Properties:- The resulting PET has good strength,clarity,and flexibility, and can be processed
into fibers,films, or bottles.
By-products:- depending on the synthesis route, the by-products could be water,methanol,and
ethylene glycol,all of which can be recycled back into the process.
The overall result is a durable, transparent, and recyclable plastic that has a wide range of
industrial applications.
PROPERTY:-
1.Mechanical properties:-
• High strength and rigidity

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• Impact resistance
• Wear resistance
• Flexibility
2.Thermal properties:-
• Melting Temperature(250-260 C)
• Glass transition Temperature(67-81 C)
• Crystallinity
3.Chemical properties:-
• Chemical resistance
• Hydrolysis
4.Optical properties:-
• Transparency
• Gloss and clarity

APPLICATIONS OF PET:-
Polyethylene terephthalate (PET) is a versatile plastic widely used in various applications due
to its excellent properties. Here are some key applications:
1. Beverage Bottles: PET is commonly used for manufacturing soft drink and water
bottles because it is lightweight, strong, and resistant to impact.
2. Food Packaging: PET is used for food containers, trays, and flexible packaging due to
its barrier properties, which help preserve food freshness and quality.
3. Textiles: PET fibers are used in clothing, upholstery, and carpets. It is often blended
with other fibers to enhance durability and resilience.
4. Automotive Parts: PET is used in automotive applications, including interior
components and external parts, due to its strength and chemical resistance.
5. Electronics: PET is used as an insulating material in electronics and electrical
components, as well as in screens and other display technologies.
6. 3D Printing: PETG, a glycol-modified version of PET, is popular in 3D printing due
to its ease of use and strength.

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7. Medical Devices: PET is used in various medical applications, including containers for
pharmaceuticals and medical packaging, because it is biocompatible and can be
sterilized.
8. Construction: PET is used in construction materials, such as insulation and roofing
membranes, due to its durability and resistance to moisture.
These diverse applications highlight PET's importance in everyday products and various
industries, contributing to its status as one of the most widely used plastics globally.
SAFETY AND HAZARDS:-
Polyethylene terephthalate (PET) is generally considered safe for use in various applications,
particularly in food and beverage packaging. However, there are some safety and hazard
considerations to be aware of:
Safety
1. Food Contact: PET is approved for food and beverage contact by regulatory agencies
like the FDA, meaning it does not leach harmful substances when used properly.
2. Recyclability: PET is recyclable and is commonly accepted in recycling programs,
which helps reduce environmental impact.
3. Low Toxicity: PET has low toxicity levels, making it safe for use in consumer products.
Hazards
1. Heat Sensitivity: PET can deform at high temperatures (above 70°C or 158°F), which
can be a concern if used in applications that involve heat.
2. Chemical Resistance: While PET is resistant to many chemicals, it can be degraded
by certain solvents and strong acids.
3. Microplastics: When PET products are improperly disposed of or break down in the
environment, they can contribute to microplastic pollution, which poses risks to
ecosystems and human health.
4. Recycling Contamination: PET can be contaminated with other materials during
recycling, potentially leading to unsafe products if not properly processed.
5. Environmental Impact: The production and incineration of PET can generate
greenhouse gases and other pollutants, contributing to environmental concerns.
Summary

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Overall, while PET is considered safe for most uses, awareness of its limitations and potential
environmental impacts is important. Proper handling, recycling, and disposal can help mitigate
these concerns.

References:-

1. https://doi.org/10.52305/EXUA6721
2. Polyethylene terephthalate - Wikipedia
3. https://doi.org/10.1016/B978-0-12-824489-0.00006-4
4. https://doi.org/10.1016/j.polymertesting.2020.106707

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