Title of PBL:

Petroleum-Based and
Bio-Based Polymers
Group 3
Andiko Belia Ian Ajrin Rohman
Fathiyah Aulia Darmawan Muhammad Tesar Pamungkas
Farhan Nabil Prasetya presented on March 18th, 2021
 2

Problem Statement

Identification, application, and reaction kinetics of polymer:

petroleum-based polymer & bio-based polymer

Objectives

● To understand polymer by identifying its characteristics, types,

applications, history, and future.
● To understand polylactic acid life cycle and characteristics as
packaging material.
● To understand type of polymerization and kinetics involved in
its reaction.
 3

OUTLINE : SUBTOPICS
Title Slide 1
Problem Statement 2
Outline 3
Assignment 1. Polymers in Our Daily Life 4-7
Assignment 2. Polylactic Acid: Cycle and Characteristics 8 - 15
Assignment 3. Step-Growth Polymerization (Polyethylene Terephthalate) 16 - 24
Conclusion 25
References 26
 4
Assignment 1. Article

http://bit.ly/Group3PolymerArticle
 Article Summary 5

History of Polymer Societal Applications

PART
I Agriculture
• 1820 - 1932 Packaging
• Concept shift Materials
1st age from colloid to
Corrosion
polymer
Control
• 1933 – 1960s
PART • Utilization of
Medical
Application
II 2nd age polymer in daily
life due to world
war II
• 1960s – now

3rd age • SUP utilization Polymers are basic to present day life. The
PART shift to
advanced-MUP
most essential is reasonable polymers raised

III the way of life and made material wealth all

the more promptly accessible.
 Article Summary 6

General Classification Fabrication Method

PART
I
Casting. The polymer is Molding. Heat and
solidified in a mold by pressure are used to
chemical or physical change the shape of
procedures. the polymer.

thermoplastic thermoset
PART Polymer
II Fabrication
Technology

Extrusion. A screw (or E lectrospinning.

more) is used to Polymers as a
PART process the polymer
with heat and pressure.
suspension in a
suitable solvent.
III bio-based petroleum-
based
 Article Summary 7

Future Perspective Polymers Shift to Bio-Based and

PART Bio-Degradable Polymers
I
Cumulative Plastic Production
• No commercial
(1950 - 2015)
biodegradable
Properties &
polymers currently
Cost. used solely: cost & 12%
mechanical. 10%

PART 60% 18%

II
• A tightly contr- incinerated recycled discarded reused
olled disposal
Degradation

6R
infrastructure is
reducemfnfjakredesignkkfjas
PART required.
kljfloveremovefkamfmakgye
III oakkreuserjdusmjekrecycleck
movement dsokadsrecovermfgdrgdrgrlf
 8

Assignment 2

Society started to concern more about

sustainability.

Polylactic Acid (PLA) is currently the mostly used

bio-based and bio-degradable plastic allover
the world since it is claimed as a polymer that
has the best mechanical properties out of all
other bio-based types.

Let’s see what makes PLA popular among other

bio-based plastic starting from the next slide.
 What characteristics owned by polylactic acid (PLA) to 9

make it has broad applications?

Mechanical Properties
Note! PLA has the poor
→ Describe the behavior of the material under the toughness limited.
effect of different loading modes (tensile, impact,
shear, pressure)
Problem in application requiring
PLA plastic deformation at higher

>
Young’s Modulus Polypropylene (PP) level of stress.
Tensile Strength Polystyrene (PS)
Flexura Strength Polyethylene (PE)
Motivated research for
toughening PL A over the last
Polypropylene (PP) five years.

<
Elongation at a Polyethylene (PE)
break Polyethylene
Impact Strength terephtalate (PET) Oyama [31] reported the use of poly(ethylene-glycidy
Polyamide (PA) methacrylate) (EGMA) as a toughening agent for PLA.
 Characteristics Owned by PLA 10

Thermal Properties Barrier Properties

PLA is semi-crystalline or amorphous How can the material prevent the diffusion of
environmental substance (i.e. Gasses such as oxygen
that can cause food oxidation).

The permeability
• Glass transition
coefficients of
temp. (Tg) → CO2, O2, N2, and
aprx. 55oC H2O(g) for PLA :
• Melting temp.
• lower than PS
(Tm) → approx. • higher than that
180oC
of PET

The Tg increased rapidly with increasing

molecular weight, then it reached a constant the crystallinity of PLA → strongly affected the barrier properties
value. • the decrease in crystallinity → negative aspect in terms of
the mechanical and barrier properties
 Characteristics Owned by PLA 11

Biodegradable Properties NOTE!

The biodegradability rate of PLA polymers

The action of microorganisms on the material
and its conversion into carbon dioxide or
methane and water.
in soil under real conditions was lower than the
rate of waste accumulation.
Increase biodegradablity → adding by mixing
it with natural materials (stratch/glucose)

PLA sample surface had many corrosive

holes af ter four months degradation,
showing that the PLA was degraded.

Molecular weight values below 5 kDa could be

obtained af ter 57 days of the degradation,
which was in consistent to the calculation.
 How do you explain the cycles of PLA above? 12

2. Biomass extracted into stratch

3. Fermentation of lactic acid
4. Plolymerization to make PLA granule
5. Manufacturing process
6. Decomposition by microorganism
7. Plant does photosythesis using
decomposition of PLA
1. Plant storages photosynthesis product in
the form of biomass

Factors affecting fermentation

- Temperature
- Oxygen Level
- Substrate
- Water
 What method of synthesis of PLA that you will choose
to obtain PLA for food packaging? Explain the reasons.
PLA Synthesis Methods
1. Polikondensasi langsung (direct
condensation-polymerization)
• Low weighted PLA (very brittle)
• Need to add coupling agent
• Very long time to remove water
(hard)
2. Kondensasi dehidrasi azeotropik
(Azeotropic dehydration
condensation)
• MW up to 15.400
• Use azeotrop solution → easy to
separate product with solvent on
athpospheric pressure
• Higher MW = higher boiling point
13
3. Polimerisasi pembukaan Choosen!
cincin (ring opening Considerration!
polymerization, ROP) • Mechanical disturbance
• Thermal disturbance
• MW = 2.104—6,8.105
• Process : Deformation → Gap
• condensation→ → Environtmental Contamination
depolymerization (forming Solved by high MW.
lactide)→ ring opening
Considerration!
• Easy to manipulate the • Gasses diffusion
process to upgrade the
Andvance optimizaition by mixing
quality due to cyclic phase with another polymers to increase
• Easy to control process time the quality
(by picking solvent and
catalyst)
*ROP is a chain-growth polymerisation where one end of the polymer chain
carries a reactive centre for the addition of cyclic monomers.
 What Factor Should be considered if you will use PLA to 14

replace petroleum-based polymers for packaging

material ?

Beneficial
Degradable : Slowly degrade over a period of months to
two years
Environmental : Compared to the manufacture of the same
bottle consumes 36% less energy and
produces 44% less carbon dioxide
Properties : - Excellent transparency
- 20 times better oxygen barrier properties
than polystyrene
- Better mechanical performance than
polystyrene
- Relatively good water resistance
- Good chemical resistance to fats and oils
- Better ultraviolet light barrier than LDPE
 What Factor Should be considered if you will use PLA to 15

replace petroleum-based polymers for packaging

material ?

Consideration
• High cost. Low availability, limited molecular weight.
• The production of PLA granules is less favorable compared to
PET granules (on equal mass bases).
• The mechanical and barrier properties do not match fossil-
based
It can have excessive brittleness and unsatisfactory barrier to
oxygen and to water compared to benchmark another polymer
such as PET.
 16

Assignment 3

However, PLA is not the mostly used type of plastic

allover the world. The most popular plastic is
Polyethylene Terephthalate (PET), a clear, strong,
and lightweight plastic suitable for food and
beverages packaging.

We are going to learn how PET is made starting

from its process and reaction mechanism starting
from the next slide.
How is polyester PET synthesized? If the reaction involved in the process is 17

step-growth polymerization with condensation reaction, show the reaction

that involve two type of monomer to form PET.

Esterification
240-260°C

Transesterification
210 °C
Manganese acetate
as catalyst 280 °C
Low Pressure
How do you explain the condensation step-growth polymerization in 18

general?

A polymerization reaction involving two monomers whose reaction results can cause the loss of simple molecules such
as water or methanol.

Each molecule must be symmetrical. have two equivalent groups, one on each end.

Water

Water
 3rd Assignment No 3 19

Table 1. The definition and different between number average

Question :
molecular weight and weight average molecular weight
● How do you describe
number-average molecular Number-Average Weight-Average
weight and weight-average Molecular Weight Molecular Weight
molecular weight.? Definition The mole fraction of The weight Fraction
● What the difference molecules in a of molecules in
between each other? polymer sample polymer sample
Equation σ(𝑁𝑖 𝑀𝑖 ) σ(𝑁𝑖 𝑀𝑖2)
𝑀𝑛 = 𝑀𝑤 =
σ 𝑁𝑖 σ(𝑁𝑖 𝑀𝑖 )
Value Always lesser than Always greater than
weight average the number average
molecular weight molecular weight
Determination By using gel By using static light
permeation scattering. Small
chromatography. angle neutron
Figure 1 Mw is always greater than Mn Viscometry and scattering. X-ray
Source: colligative methods scattering and
https://www.differencebetween.com/difference- such as vapor sedimentation
between-number-average-and-weight-average-
molecular-weight
pressure osmometry velocity
 3rd Assignment No 4 22

Given : Objective : To obtain N1 & N2 we

Question : M1 : 10,000 Find N1 & N2 need solver help in Excel :
M2 : 200,000
In a polymer plant, mixture of Mn : 50,000
polymers with specific molecular
As we know,
weight will have certain physical
Number - Average Molecular Because
properties as well. In the plant,
the polymers available are those Weight : N1 + N2 need to be 1
σ(𝑁𝑖 𝑀𝑖 )
with molecular weights of 10,000 𝑀𝑛 =
σ 𝑁𝑖 We need to put
and 200,000. How do you mix
them so the polymer obtained The equation for this question : constrain in solver to
has number - average molecular 𝑁1 𝑀1 +(𝑁2𝑀2 ) meet the requirement
weight 50,000? Will you use 𝑀𝑛 = condition
(𝑁1 +𝑁2 )
different ways to obtain the We obtained :
weight-average molecular Using the given variables we got :
weight? Find
𝑁1 10,000 +(𝑁2 200,000)
50,000= N1 0.789473
(𝑁1+𝑁2 ) N2 0.210526
 No 4 Cont… 21

Objective : As we know, Will you use different

Find 𝑀𝑤 Weight - Average Molecular ways to obtain the
Weight : weight-average
Given : molecular weight?
M1 : 10,000 σ(𝑁𝑖 𝑀𝑖2)
𝑀𝑤 =
M2 : 200,000 σ(𝑁𝑖 𝑀𝑖 ) Answer :
Mn : 50,000
The equation for this question : Yes, since number-
From previous calculation we average molecular weight
obtained : is different from weight
𝑁1 𝑀12 +(𝑁2 𝑀22)
𝑀𝑤 = average molecular weight
Find 𝑁1𝑀1 +(𝑁2𝑀2 )
N1 0.789473
N2 0.210526 Using the given variables we got :
We obtained :
0.789473 . 10,0002
+ 0.210526 . 200,0002
MW =
0.789473 . 10,000 + (0.210526 . 200,000) MW = 170000
 3rd Assignment NO 5 22

Given:
Question NDMT = 2 mol t = 75 s
NEG = 2 mol NDMT = 0.0002
You conduct an experiment in the lab to synthesize PET. You use
ethylene glycol and
dimethylterephthalate as much as 2 moles each. Time required to a) Objective : Write the equation
form PET is 75 seconds and
after that you seperate immediately the product and the remaining
reactants. Gas +
chromatography analysis on the remaining reactants showed the
amount of
dimethylterephthalate is as much as 0.0002 moles.
+
a) How do you write the equation reaction of this
polymerization?
b) How do you calculate degree of reaction (p), average degree
of polymerization (Xn), Dimethylterephthalate + ethylene glycol
c) and average number molecular weight of PET (Mn) (2 mol) (2 mol)
d) How do you determine the rate constant of polymerization (k),
if assuming that Polymerization reaction is stoichiometric and PET + Methanol
no catalyst used.
 3rd Assignment NO 5 Cont… 23

Molecular weight Source : pubchem.ncbi.nlm.nih.gov

b) Objective :
Find (p), (𝑋𝑛 ) and (Mn) of PET Dimethylterephthalate : 62.07 g/mol
Ethylene glycol : 194.18 g/mol

We can find p using : We can find 𝑋𝑛 using : We can find 𝑀𝑛 using :

𝑁𝑜 − 𝑁 1 σ(𝑁𝑖 𝑀𝑖 )
𝑝= 𝑋𝑛 = 𝑀𝑛 =
𝑁𝑜 1−𝑝 σ 𝑁𝑖

Using the given variable, we get : Using the given variable, we get : Using the given variable, we get :

4 − 0.0002 1
𝑝= 𝑋𝑛 =
4 1 − 0.99995
𝑝 = 0.99995 𝑋𝑛 = 20000 128.125 𝑔
𝑀𝑛 =
𝑚𝑜𝑙
 3rd Assignment NO 5 Cont… 24

c) Objective :
Find (k), if assuming that Polymerization reaction is stoichiometric, and no catalyst
used.

Where :
The general reaction is : Using the given variable, we get :
𝐴0 : 2 𝑚𝑜𝑙
𝐴 ∶ 0.0002 𝑚𝑜𝑙
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 T : 75 s
a : 1 (since A coefficient is 1)
Using this formula :

Where :
𝑚𝑜𝑙
𝐴0 = 𝑜𝑓 𝐴 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡 = 0 We obtained :
𝐿
𝑚𝑜𝑙
𝐴= 𝑜𝑓 𝐴 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡 0.122804538
𝐿
𝑎 = 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝐴 𝑘=
𝑠
𝑡 = 𝑡𝑖𝑚𝑒 𝑒𝑙𝑎𝑝𝑠𝑒𝑑
𝑘 = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
 25

Conclusion

• Polymer has gained huge development in the last 100 years. Currently, behavioral shift
in the society makes bio-based polymer in trend.
• PLA is the most popular type of bio-based polymer since it has the best mechanical,
and barrier properties compared to the other bio-based polymer. It is made from corn
starch and synthesized using three different method, with ring opening polymerization
as the best option to synthesize polymer to become food packaging.
• There are two types of polymerization, chain growth and step growth. One of the
polymerization type is growth polymerization, used in PET. Some important
parameters in reaction kinetics are Stoichiometric coefficient, time elapsed and
concentration.

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