2.4 In the lab, you will make PE based on the free-radical polymerization.

What compounds
you will need and what stage of reaction occured in this polymerization reaction. [Needs
initiator, stages in their reaction]. Can we determined the rate of polymerization, the number-
average degree of polymerization?
Compound that we needs:
Ethylene(s) as monomer
Benzoyl Peroxide as Radical Molecule (Initiator)
Jawab:
Tahap tahap Polimerisasi Radikal Bebas Polietilena (PE):
1. Inisiasi: Proses aktivasi dengan Peroksida Organik (Benzoil Peroksida), Senyawa
Azo-, atau Oksigen menjadi molekul karbon dioksida dan dua radikal:

2. Chain Initiation: Radikal-radikal ini kemudian dapat bertindak sebagai elektrofil dan
menyerang ikatan rangkap etilena membentuk ikatan yang stabil:

3. Propagasi (Growth): Radikal yang baru terbentuk dengan etilena dapat menambahkan
pada dirinya sendiri dengan menyerang molekul etilena lain.

Unit Polietilena dapat tumbuh dari 4-5 monomer menjadi sangat besar yang memiliki
massa molekular 1 juta.
4. Terminasi (Kombinasi): Akhir dari reaksi adalah bertemunya dua radikal, yang
bereaksi membentuk suatu produk (Polietilena).

Keterangan:
CI Concentration of initiation, mol/L
CM Concentration of monomer mol/L
 CR Concentration of free radical 1/S
CS Concentration of solvent mol/L
Di Dead polymer or dead chains
f Efficiency of original initiation
I Initiation
kbb Rate constant of backbiting 1/S
kI Rate constant of oxygen/peroxide initiation, 1/S
kP Rate constant of propagation, 1/mol.S
ktc Rate constant of termination by combination, 1/mol.S
kth Rate constant of monomer thermal initiation, 1/S
ktrm Rate constant of chain transfer to monomer, 1/mol.L
ktrp Rate constant of chain transfer to polymer,1/mol.S
ktrs Rate constant of chain transfer to solvent,1/S
k Rate constant of -scission to secondary radical.1/S
LCB Long chain branching
M Monomer
Mwo Monomer molecular weight
Pi Live radical, radical polymer, live polymer or live chains
PDI Polydispersity Index
R Initiator radical
S Solvent
SCB Short chain branching
Live polymer moment
Dead polymer moment
0 Zeroth live polymer moment
1 First live polymer moment
2 Second live polymer moment
0 Zeroth dead polymer moment
1 First dead polymer moment
2 Second dead polymer moment
i,j Ultimate monomer unit in the radical chain

Lanjutannya ada di Emerging Issues in the Mechanisms of High Pressure Free Radical
Ethylene Polymerization. A Review

http://faculty.washington.edu/finlayso/Polyeth/Group_B/mech.html
Kehinde A. J, Usman M. A. 2012. Emerging Issues in the Mechanisms of High Pressure Free
Radical Ethylene Polymerization: A Review. American Journal of Polymer Science
2012, 2(5): 91-101.
3.3 How is the role of Biodegradable synthetic polymers in reducing the usage of Petroleum
polymers? Why PET has broad application?
Jawab:
Living green has become a popular trend in the last twenty years, and reducing oil
consumption remains an important goal for the sustainably-minded today. One of the top uses
of crude oil is the production of plastics. In 2010, 191 million barrels of liquid petroleum
gases and natural gas liquids were used to make plastic products in the United States (1).
These plastics later end up in landfills, where they take years to break down. Petroleum-based
plastics are becoming more expensive as oil prices continue to increase, and plastic
accumulation in landfills takes up valuable space and threatens the environment.
List of Advantages of Biodegradable Plastics
1. Carbon Emission Reduction
One of the advantages related to the use of biodegradable plastics is the minimal emission of
carbon in the air during the process of manufacturing bioplastics. As opposed to the normal
manufacturing of plastics that create four tons of emissions, bioplastics only emit
approximately 0.8 tons of carbon that add to the greenhouse effect and global warming.
2. Consumes Less Energy
The manufacturing process of biodegradable plastics requires less amount of energy and does
not need fossil fuels to be recycled. Conversely, traditional plastics demand more energy in
production and at the same time requires the burning of fossil fuel. Since less energy is
needed, more bioplastics can be produced while there is less pollution in the environment.
3. Less Landfill Area Needed
Plastics that are non-biodegradable are brought to landfills to discard them. Consequently,
land area that could have been used for agriculture, residence or industrial applications is
instead converted to landfills. If bioplastics are used, there is no need to add more landfills
since these plastics can be absorbed by the soil and be converted to compost or humus.
4. Recyclable
Apart from taking less time to break down when discarded, biodegradable plastics can also be
recycled and are non-toxic since they contain no chemicals or toxins compared to other types
of plastics that can emit harmful chemicals, especially if burned.
List of Disadvantages of Biodegradable Plastics
1. Need for Composters
The flipside of using biodegradable plastics is that there will be a need for industrial
composters to turn them into composts and availability of the equipment in some countries
can be a problem. Apart from the cost, not all countries have the proper equipment especially
if this is not the priority of the government. In the end, the bioplastics that need to be
processed will not be discarded properly.
2. Engineering Issues
These bioplastics are plant-based and this means that they come from organic sources from
farms such as soybeans and corn. However, these organic plants are sprayed with pesticides
which contain chemicals that can contaminate the crops and be transferred or included in the
finished product.
3. Risk of Contamination
Biodegradable plastics should not be mixed with non-biodegradable plastics when thrown in
garbage bins. The problem here is that not all people know how to segregate or distinguish
bioplastics from other plastic types. Once these two types of plastics are mixed together,
these bioplastics become contaminated and cannot be used anymore. Consequently, these
contaminated bioplastics will end in landfills and add to the volume of thrash. (2)

PET (also abbreviated PETE) is short for polyethylene terephthalate, the chemical name for
polyester.
PET is a clear, strong, and lightweight plastic that is widely used for packaging foods and
beverages, especially convenience-sized soft drinks, juices and water. Virtually all single-
serving and 2-liter bottles of carbonated soft drinks and water sold in the U.S. are made from
PET.
It is also popular for packaging salad dressings, peanut butter, cooking oils, mouthwash,
shampoo, liquid hand soap, window cleaner, even tennis balls. Special grades of PET are
used for carry-home food containers and prepared food trays that can be warmed in the oven
or microwave.
The basic building blocks of PET are ethylene glycol and terephthalic acid, which are
combined to form a polymer chain. The resulting spaghetti-like strands of PET are extruded,
quickly cooled, and cut into small pellets. The resin pellets are then heated to a molten liquid
that can be easily extruded or molded into items of practically any shape.
PET was first synthesized in North America in the mid-1940s by DuPont chemists searching
for new synthetic fibers. DuPont later branded its PET fiber as "Dacron." Today, more than
half of the world's synthetic fiber is made from PET, which is called "polyester" when used
for fiber or fabric applications. When used for containers and other purposes, it is called PET
or PET resin.
In the late 1950s, researchers found a way to stretch a thin extruded sheet of PET in two
directions to create PET film, which is now used extensively for video, photo and packaging
films. In the early 1970s, the technology was developed for blow-stretch molding PET into
bottles. The PET bottle was patented in 1973.
Global Safety Approval
PET is approved as safe for contact with foods and beverages by the FDA and health-safety
agencies throughout the world.PET is approved as safe for contact with foods and beverages
by the FDA and health-safety agencies throughout the world. The safety of PET for food,
beverage, pharmaceutical and medical applications has been repeatedly demonstrated through
extensive studies, regulatory approvals, testing, and its widespread acceptance for more than
30 years. PET does not contain bisphenol-A (BPA) or phthalates (plasticizers).
Because of PET's unique properties, it is rapidly becoming the world's preferred packaging
material for foods and beverages. Like glass, it is a very strong and inert material that does
not react with foods, is resistant to attack by micro-organisms, and will not biologically
degrade. But unlike glass, PET is extremely lightweight, easy and efficient to transport, and
shatterproof.
Fully Recyclable
PET is completely recyclable, and is the most recycled plastic in the U.S and worldwide.
More than 1.5 billion pounds of used PET bottles and containers are recovered in the United
States each year for recycling. PET can easily be identified by the #1 in the triangular
"chasing arrows" code, which is usually found molded into the bottom or side of the
container. No other plastic carries the #1 code.
PET can be commercially recycled by thorough washing and re-melting, or by chemically
breaking it down to its component materials to make new PET resin. Almost every municipal
recycling program in North America and Europe accepts PET containers.
PET can be commercially recycled by thorough washing and re-melting, or by chemically
breaking it down to its component materials to make new PET resin.Products commonly
made from recycled PET include new PET bottles and jars, carpet, clothing, industrial
strapping, rope, automotive parts, fiberfill for winter jackets and sleeping bags, construction
materials, and protective packaging.

The current U.S. recycling rate for PET is 31%. This figure continues to grow, but notably
lags behind Europe, which has a PET recycling rate of 52%.
Although recycling is the most environmentally responsible and efficient re-use of resources,
PET bottles and containers that find their way to the landfill pose no risk of harm or leaching.
Since the polymer is inert, it is resistant to attack by micro-organisms, and won't biologically
degrade. PET also takes up relatively little landfill space since it is easily crushed flat.
According to the EPA, only 1% of U.S. municipal solid waste is due to PET containers.
Sustainable
PET is a very energy-efficient packaging material. Although its raw materials are derived
from crude oil and natural gas, it enjoys a very favorable sustainability profile in comparison
to glass, aluminum and other container materials.
Its sustainability jumps even higher when recycling is introduced, since approximately 40%
of PET's energy use is attributable to its "resource energy" - the energy inherently trapped in
its raw materials that can be recaptured and reused through recycling.
The high strength of PET in comparison to its light weight is a major key to its energy
efficiency, allowing for more product to be delivered in less packaging and using less fuel for
transport. Ongoing advances in light-weighting technology continue to improve its energy
efficiency even further. Life cycle studies of PET have consistently confirmed the
environmental benefits of PET as a packaging material.
In the 60 years since PET was first synthesized, it has become one of the world's most widely
used, versatile and trusted materials.

(1) How Much Oil is Used to Make Plastic? (2012). Available at

http://www.eia.gov/tools/faqs/faq.cfm?id=34&t=6 (22 February 2017).
(2) 7 Advantages and Disadvantages of Biodegradable Plastics.
http://connectusfund.org/7-advantages-and-disadvantages-of-biodegradable-plastics
(22 February 2017)