PETROLEUM-BASED AND

BIO-BASED POLYMERS
Group 1 Members:
Didik Nur Sahid 1806148403
M. Azhar Abdullah 1806199442
Nicholas William 1806227585
Shafira Hakim Y. 1806182372
Sisfa Shabela 1706021202

Thursday, 18 March 2021

 PROBLEM STATEMENT

“ Petroleum-based and bio-based polymers

along with their production methods in
facing environmental issue regarding
biodegradibility by polymer classification

”
 OUTLINE: SUBTOPICS
● Polymer Overview
● PLA (Classification, Application, Characteristics)
● PLA Synthesis
● Cycle of PLA
● PET Characteristics, Classification, Application, and Synthesis
● Number Average Molecular Weight and Weight Average Molecular
Weight
● Condensed step growth Polymerization
● Kinetics of polymerization
 Table of Contents

01 INTRODUCTION

02 PROBLEMS &
SOLUTIONS

03 CONCLUSION
 1
INTRODUCTION
 Polymer Overview
1. Polymer: Substance composed of molecules which have long
sequences of one or more species of atoms or groups of atoms linked
to each other by primary, usually covalent, bonds.
2. Polymers are widely used in our daily life because it can be very
resistant to chemicals, seemingly limitless characteristics and colors,
and can be used to make items that have no alternatives from other
materials.
3. Generally, polymers are either petroleum or bio-based.

Polymer forms Polymer Classification

 Polymer Overview
Polymer in daily life
Polymers can also be synthesized by several
methods:
1. Radical polymerization
2. By underlying polymerization mechanism: Step-
growth and chain
3. Linear step polymerization: Polycondensation
and polyaddition
4. Cationic and Anionic polymerization
5. Catalytic polymerization
 Polymer Overview
Initiators
•Cationic polymerization - strong acids and Lewis
acids (to covert the alkene into a cation)
•Anionic polymerization - strong bases, alkali
metals, and organolithium compounds (to convert
the alkene monomer to an anion)

Radical polymerization

Catalytic polymerization
 Polymer Overview
• Polymerizations in which the polymer chains grow step-wise by
reactions that can occur between any two molecular species are
known as step-growth polymerizations.
• Polymerizations in which a polymer chain grows only by reaction of
monomer with a reactive end-group on the growing chain are known
as chain-growth polymerizations, and usually require an initial reaction
between the monomer and an initiator to start the growth of the
chain.

Step and chain polymerization

 PLA (Poly Lactic Acid)
PLA (Poly Lactic Acid) adalah polymer yang terbuat dari lactic acid sebagai monomernya dimana polimer
ini termasuk biodegradable polymer.

PLA digolongkan sebagai Biodegradable polimer karena kemampuannya terdegredasi sempurna secara
biologis
 PLA (Poly Lactic Acid)
PLA (Poly Lactic Acid) adalah polymer yang terbuat dari lactic acid sebagai monomernya dimana polimer
ini termasuk biodegradable polymer.

PLA digolongkan sebagai Biodegradable polimer karena kemampuannya terdegredasi sempurna secara
biologis
Peta konsep Biodegradable polymer
 Lactic Acid

Asam laktat adalah cairan pekat tak berwarna, tak berbau, larut di dalam air

Asam laktat dapat dihasilkan melalui proses fermentasi atau secara sintesis kimiawi. Reaksi dasar proses
kimiawi adalah mengubah laktonitril (asetaldehid sianohidrin) menjadi asam laktat.
 Pembuatan PLA
Direct Condensation Polimerization

Kondensasi Dehidrasi Azeotropik

Polimerisasi Pembukaan cincin

 Aplikasi PLA
Kemasan Benang jahit Pembungkus
medis Medis kapsul

Bahan dasar
Botol dan cangkir
Compact disc

Kaos, tas
Synthesis PLA
❑ Lactic acid (IUPAC: 2
hydroxypropanoic ❑ Asam laktat dapat dihasilkan melalui proses
acid) fermentasi atau secara sintesis kimiawi.
❑ Fermentasi (murah, menghasilkan asam
laktat dengan kemurnian tinggi)
 Direct Condensation Polymerization

❑ Low Molecular Wight

❑ Coupling/esterification-
promoting agents
❑ Terdapat Chain extending
agents yang tidak bereaksi
❑ Terdapat agen isocyanate
yang bersifat toxic.
❑ Berbahaya bagi lingkungan,
tidak food-grade
 Azeotropic Dehydration Condensation

• Pelarut Difenil Eter, Xilena,

Kloroform (memudahkan
pemisahan air dari
produk)
• Katalis logam timah
• High molecular weight
• Low Purity
 Ring Opening Polymerization
❑ Polycondensation,
Depolymerization, and ring
opening polymerization
❑ Use Catalyst (Timah Tetrafenil,
Timah (II) Klorida, Tin (II) 2-
ethylhexaoate, FDA (Food and
Drug Administration)
❑ High molecular weight
(Strength, Tensile strength,
Compressive strength,
Elongation, Toughness )
❑ Food-grade
❑ High Purity
 PET Properties and Characteristics
Properties Information
Technical Name Polyethylene terephthalate (PET or
PETE)
Chemical Formula C12H14O4
Density 1.41 g/cm3
Melting Point 265 οC
Boiling Point > 350 οC (decomposes)
Molecular Weight (of repeating 192 g/mol
unit)
Weight Average MW 30,000-80,000 g/mol
Figure 1. Semi-Crystalline
Polyethylene Terephthalate
Solubility in Water Practically insoluble
Color and Formulation The semicrystalline material might
appear transparent or white Some of the most significant properties of PET are:
1. Chemical Resistance → do not react with water
2. Strength to Weight Ratio → lightweight
3. Shatterproof → not easily break
4. Transmissivity → transparent
5. Availibility → wide availibility
 PET Classification
Modified Co-Polymer
Example:
Modified PET in Film Application

Homopolymer
Product
Example:
Textile Application; Polyester Fabric
 PET Application
01 02 03
PET are widely used PET is successfully
for mineral water and being used in many
carbonated soft PET has wide applications in
drinks applications in the electrical
textile industry industry
 Carother's Theory
• Number average degree of polymerization with respect to monomer units

• No: number of molecules initially present

• N: number of molecules remaining after time ‘t’
• Extent of reaction p
 Carother's Theory
• Number average molar mass Mn is defined as:

• Mo: mean molar mass of a monomer unit

 Kinetics of
Polymerization
• General form rate of reaction: • For equimolar [A]=[B]=c

• With catalyst: • Integrated with c=c0 at t = 0

 Kinetics of
Polymerization
• If there is no additional catalyst • For equimolar [A]=[B]=c
--> reaction is self-catalyzed
A is assumed as the catalyst

• Integrated with c=c0 at t = 0

• In terms of extent of reaction p

 2
PROBLEM AND
SOLUTION
 Problem and Solution: Assignment 1
Your group has been assigned to write an article titled “ Polymers in our daily
life” for student bulletin in campus. The article should give the readers broad
information on polymer. The group has to design and decide what information
will be written in this article. There are minimum of 10 issues that you have to
explain in the draft of article.

Issues:
1. Overview 7. Polymer base (petroleum and bio)
2. Important words 8. Synthesis mechanism
3. Definition of polymers 9. Polymers in Daily Life
4. Polymer Structure 10. Manufacture process for polymers
5. Polymer Classification 11. Availability in future prospect
6. Polymer characteristics
 Problem and Solution: Assignment 2

1. What charactiristics owned by polylactic acid (PLA) to make it has broad applications?

1. Biodegradable
2. Biocompatible
3. Recyclable dengan hidrolisis laktat
4. Pembuatannya tanpa pelarut yg bersifat racun
5. Dapat terbakar sempurna menjadi co2 dan air
 Problem and Solution: Assignment 2
2. How do you explain the cycles of PLA above?
3. What method of synthesis of PLA that you will
choose to obtain PLA for food packaging? Explain the
reasons.
❑ We choose ring opening polymerization, because it produces high
purity, High molecular weight (Strength, Tensile strength,
Compressive strength, Elongation, Toughness ) and food grade.
Besides that, ring opening polymerization use Tin (II) 2-
ethylhexanoate catalyst which has received permission from the
FDA (Food and Drug Administration)
 Problem and Solution: Assignment 2
4. What factors should be considered if you will use PLA to replace petroleum-based polymers
for packaging material.?

Bio
degradable

Terbakar Bio
Sempurna Compactible

Tidak
recyclable
beracun
 Pertimbangan lain

Ketahanan
Harga Kekuatan
Panas
 Problem and Solution: Assignment 3

3.1 How is polyester PET synthesized? If the reaction involved in the process is step-
growth polymerization with condensation reaction, show the reaction that involve
two type of monomers to form PET.

Monomers:

→ PET is synthesized by the condensation step-growth polymerization that consists

of two monomers which are ethylene glycol and terephthalic acid
 3.2 How do you explain the condensation
step-growth polymerization in general?

By definition:

● Condensed polymerization – repeat units having less atoms than in the

monomers they originate from
● Step-growth polymerization – grows step-wise by reactions between pairs
of mutually reactive functional groups provided by the monomer(s).
 Linear Step Polymerization
● Reaction between pairs of mutually reactive functional groups from initial
monomers

● Main factor --> number of functional groups, like formation of ester linkages
from carboxylic acid + hydroxyl

● Monofunctional i.e. acetic acid + ethyl alcohol

incapable of further reaction --> not polymer

● Difunctional i.e. terephthalic acid + ethylene glycol

 Polycondensation

● General formation of polyester

● Polyesters may also be prepared from single monomers which contain

both types of functional group, e.g. w-hydroxy carboxylic acids
 Problem and Solution: Assignment 3

3.3 How do you describe number-average molecular weight and weight-average

molecular weight? What the difference between each other?

Number-Average Molecular Weight: Weight-Average Molecular Weight:

∞
𝑇𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 = ෍ 𝑀𝑖 𝑁𝑖
𝑖=1 σ∞
𝑖=1 𝑁𝑖 (𝑀𝑖 )
2
𝑀𝑊 =
∞ σ∞𝑖=1 𝑁𝑖 𝑀𝑖
𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 = ෍ 𝑁𝑖
𝑖=1

σ∞
𝑖=1 𝑀𝑖 𝑁𝑖
𝑀𝑛 =
σ∞𝑖=1 𝑁𝑖
 Number-Average Molecular Weight and
Weight-Average Molecular Weight
Example:
Consider a polymer sample comprising of 5 moles of polymer molecules
having molecular weight of 40.000 g/mol and 15 moles of polymer molecules
having molecular weight of 30.000 g/mol.
Number-Average Molecular Weight:
𝑇𝑜𝑡𝑎𝑙 𝑊𝑒𝑖𝑔ℎ𝑡 = 5 𝑚𝑜𝑙 × 40 𝑔/𝑚𝑜𝑙 + 15 𝑚𝑜𝑙 × 30 𝑔/𝑚𝑜𝑙 = 650000 𝑔
σ∞
𝑖=1 𝑀𝑖 𝑁𝑖
𝑀𝑛 = 𝑇𝑜𝑡𝑎𝑙 𝑁𝑢𝑚𝑏𝑒𝑟 = 5 𝑚𝑜𝑙 + 15 𝑚𝑜𝑙 = 20 𝑚𝑜𝑙
σ∞𝑖=1 𝑁𝑖
650000 𝑔
𝑀𝑛 = = 325000 𝑔/𝑚𝑜𝑙
20 𝑚𝑜𝑙
Weight-Average Molecular Weight:

σ∞
𝑖=1 𝑁𝑖 (𝑀𝑖 )
2 (5 𝑚𝑜𝑙 40000 𝑔/𝑚𝑜𝑙 2 ) + 15 30000 𝑔/𝑚𝑜𝑙 2 )
𝑀𝑊 = 𝑀𝑊 =
σ∞ 5 𝑚𝑜𝑙(40000 𝑔/𝑚𝑜𝑙) + 15(30000 𝑔/𝑚𝑜𝑙)
𝑖=1 𝑁𝑖 𝑀𝑖
𝑀𝑊 = 330769 𝑔/𝑚𝑜𝑙
 Number-Average Molecular Weight and
Weight-Average Molecular Weight
Example:

Number-Average Molecular Weight:

Weight-Average Molecular Weight:

 Number-Average Molecular Weight and
Weight-Average Molecular Weight
Example:

Weight-Average Molecular Weight:

 Problem and Solution: Assignment 3
3.4 In a polymer plant, mixture of polymers with specific molecular weight will have certain physical
properties as well. In the plant, the polymers available are those with molecular weights of 10,000
and 200,000. How do you mix them so the polymer obtained has number -average molecular
weight 50,000? Will you use different ways to obtain the weight-average molecular weight?

Number-Average Molecular Weight: 50000𝑛1 + 50000𝑛2 = 10000𝑛1 + 200000𝑛2

σ∞
𝑖=1 𝑀𝑖 𝑁𝑖
40000𝑛1 = 150000𝑛2
𝑀𝑛 =
σ∞𝑖=1 𝑁𝑖
15 7.5
𝑛1 = 𝑛 = 𝑛
4 2 2 2
𝑛1 𝑀1 + 𝑛2 𝑀2 𝑛1 = 7.5; 𝑛2 = 2
𝑀𝑁 =
𝑛1 + 𝑛2 Prove:
7.5 𝑚𝑜𝑙 (10000 𝑔/𝑚𝑜𝑙) + 2 (200000 𝑔/𝑚𝑜𝑙)
𝑛1 (10000) + 𝑛2 (200000) 50000𝑔/𝑚𝑜𝑙 =
50000 = 7.5 + 2
𝑛1 + 𝑛2
75000𝑔/𝑚𝑜𝑙 2 + 400000𝑔/𝑚𝑜𝑙 2
50000 𝑔/𝑚𝑜𝑙 =
9.5 𝑚𝑜𝑙
50000𝑔/𝑚𝑜𝑙 = 50000𝑔/𝑚𝑜𝑙
 Problem and Solution: Assignment 3
3.4 (Con’t) In a polymer plant, mixture of polymers with specific molecular weight will have certain
physical properties as well. In the plant, the polymers available are those with molecular weights of
10,000 and 200,000. How do you mix them so the polymer obtained has number -average molecular
weight 50,000? Will you use different ways to obtain the weight-average molecular weight?

Weight-Average Molecular Weight:

σ∞
𝑖=1 𝑁𝑖 (𝑀𝑖 )
2
(7.5 𝑚𝑜𝑙 10000 𝑔/𝑚𝑜𝑙 2 ) + 2 200000 𝑔/𝑚𝑜𝑙 2 )
𝑀𝑊 = 𝑀𝑊 =
σ∞𝑖=1 𝑁𝑖 𝑀𝑖 7.5 𝑚𝑜𝑙(10000 𝑔/𝑚𝑜𝑙) + 2(200000 𝑔/𝑚𝑜𝑙)

𝑛1 𝑀1 2 + 𝑛2 𝑀2 2 𝑀𝑊 = 170000 𝑔/𝑚𝑜𝑙
𝑀𝑊 =
𝑛1 𝑀1 + 𝑛2 𝑀2
3.5
● PET Synthesis
● ethylene glycol + dimethylterephthalate 2 moles each.
● t = 75 seconds Reactants left: 0.0002 moles.

a) Equation of reaction?
b) Degree of reaction (p), average degree of polymerization (Xn), and
average number molecular weight of PET (Mn)
c) rate constant of polymerization (k), if assuming that polymerization
reaction is stoichiometric and no catalyst used.
ethylene glycol + dimethylterephthalate

Dimers can react with other molecules to form trimer or tetramer

Degree of reaction (p), average degree of polymerization
(Xn), and average number molecular weight of PET (Mn)
● N0: Molecules (of repeat unit) initially present = 2 moles
● N: Remaining molecules (of repeat unit) = 0.0002 moles
● Degree of reaction (p) = 0.9999

● average degree of polymerization (Xn) = 10,000

● average number molecular weight of PET (Mn) (Mo C10H8O4 = 192)

192*10,000 = 1.92*10^6
C). rate constant of polymerization (k), if assuming that
polymerization reaction is stoichiometric and no catalyst used.

● When, equimolar, assuming the reaction is catalyzed by A:

● The differential equation of concentration over time becomes

● When integrated becomes:

p = 0.9999 c0 = 2 mol/L t = 75s k'' = 1.67*10^5

 3
CONCLUSION
 CONCLUSION
Based on the solution of the problem it is concluded that:
1. Polymers are long chain molecules with properties dominated by their
chain behaviour and the nature of their chemical make-up or
constitution.
2. Biodegradable and recycling puts PLA in first place. While PET is non-
biodegradable, but it is totally recyclable.
3. An understanding of the molecular construction of polymers provides an
insight into how improved materials can be developed.
 REFERENCES
● Fred W. Billmeyer, Jr., Textbook of polymer science, 3rd ed.,
Wiley‐Interscience, New York, 1984, 578 pp.
● Young, Robert J ; Lovell, Peter A. / Introduction to Polymers : Third Edition. 3
ed. Boca Raton, FL, USA : CRC Press, 2011. 668 p.
● Classification of Polymers. https://eng.libretexts.org/
● Molecular Weight of Polymers. https://chem.libretexts.org/
● Molecular Weight Problem Example. http://people.virginia.edu/
Thank You
Do you have any questions?

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