I.

History and development:

1. History:
- In the mid-1940’s DuPont chemists searching for materials for use in textile fibers
synthesized PET.
- Film was created in the 1950’s by stretching a thin extruded sheet of PET which is found
today in photographic, video, X-ray and packaging films.
- In the 70’s blow-stretch molding of PET in shatterproof bottles was developed.
- A recycling mill in PA begins accepting residential plastics in 1972.
- In 1977 the first PET bottle was recycled.
- Major US cities in the 80’s begin establishing curbside pick-up programs.
- In 2001 major recyclers embrace single stream recycling which dramatically increases the
recycling rate of various recyclable materials
- Over 1,200 cities are reported as accepting rigid, non-bottle, plastic packaging containers
according to plasticsmakesitpossible.com.
- Today PET is the #1 most commonly recycled material with a growing number of
consumers and reclaimers recycling PET thermoformed packaging.
2. Development:
- PET has been used more widely and commonly. After its exploration, the trend using PET
instead of thermosetting plastics has been increasing thanks to its environmental
friendliness. Asia has the highest rate production and demand on PET, especially China.
Bottle drinking aim is utilized much more significant.

II. Properties:

1. Physical properties
a. Appearance:
- Depending on its processing and thermal history, polyethylene terephthalate may exist both
as an amorphous (transparent) and as a semi-crystalline polymer. The semicrystalline
material might appear transparent (particle size less than 500 nm) or opaque and white
(particle size up to a few micrometers) depending on its crystal structure and particle size.
b. Strength to weight ratio:
- PET plastic is very hard, brittle and strong. Therefore it’s very durable to use.
c. Shatterproof:
- Even without additives to increase its strength, PET is still very strong for its light weight.
This means that less material is required for uses such as plastic film for packaging. This
means less fuel is required for shipping when using PET packaging.
d. Intrinsic viscosity:
The polymer chain length in PET determines the molecular weight of the material and with
it the physical properties that make PET such a useful packaging material. Intrinsic
Viscosity (IV) is a measurement of the polymers molecular weight and has no unit due to
being extrapolated to zero concentration. The longer the polymer chains the more
entanglements between chains and therefore the higher the viscosity which reflects the
material’s melting point, crystallinity and tensile strength. The IV is used as part of the
specification to select the right grade of PET for a particular application.
 2. Chemical properties
a. Chemical resistance:
- It absorbs very little water, moreover it has a very good gas resistance and great chemical
resistance as well as a good barrier to alcohol (requires additional "barrier" treatment) and
solvents except for alkalis (which hydrolyzes it).
b. Thermoplastic:
- Polyethylene terephthalate is generally “thermoplastic” (as opposed to “thermosetas
opposed to “thermoset”) material which has to do with the way the plastic responds to heat.
That said, some variants of the material (such as certain types of polyester) are thermoset.
Thermoplastic materials become liquid at their melting point (roughly 260 degrees Celsius
in the case of PET). A major useful attribute about thermoplastics is that they can be heated
to their melting point, cooled, and reheated again without significant degradation. Instead of
burning, thermoplastics like polypropylene liquefy, which allows them to be easily injection
molded and then subsequently recycled. By contrast, thermoset plastics can only be heated
once (typically during the injection molding process). The first heating causes thermoset
materials to set (similar to a 2-part epoxy) resulting in a chemical change that cannot be
reversed. If you tried to heat a thermoset plastic to a high temperature a second time it
would simply burn. This characteristic makes thermoset materials poor candidates for
recycling.
c. Recycleable:
- PET also has good processability and can be recycled for other applications or
returned to its constituent monomers.
- Although the material is petroleum based, approximately 40% of the energy is stored
internal and is available a second time once recycled. According to American Chemistry
Council, it’s okay to reuse PET as long as we wash it before reusing.

II. Manufacture of PET:

(a) The production of the monomer

Ethane-1,2-diol is reacted with benzene-1,4-dicarboxylic acid (known as terephthalic acid), or its

dimethyl ester, in the presence of a catalyst, to produce initially the monomer and low molecular
mass oligomers (containing up to about 5 monomer units).
Using the acid provides a direct esterification reaction, while the dimethyl ester reaction involves
ester interchange. The dimethyl ester route requires the use of an acid catalyst whereas direct
esterification is self-catalysed by the carboxylic acid groups.
The dimethyl ester route was originally preferred because the ester could be purified more readily
than the acid. Very pure acid is now available in large commercial quantities; the modern processes
therefore start from the acid.

(i) Starting from the acid: Direct Esterification Reaction

The acid reacts directly with ethane-1,2-diol:

 (ii) Starting from the dimethyl ester: Ester Interchange Reaction

The acid reacts with methanol to form the dimethyl ester, with manganese(II) ethanoate being
commonly used as the catalyst.
The dimethyl ester is then reacted with ethane-1,2-diol, by a process known as transesterification,
in which one alcohol (ethane-1,2-diol) exchanges for another (methanol):

(b) Polymerization of the monomer

The monomer then undergoes polycondensation with the elimination of ethane-1,2-diol,

a condensation reaction:
 The polycondensation stage requires a catalyst, antimony(lll) oxide, and is carried out at high
temperatures (535-575 K) when the monomer and polymer are molten. Low pressures are used to
favour product formation. Ethane-1,2-diol is recycled.

Reference:

http://www.bpf.co.uk/Sustainability/pet_plastic_bottles_facts_not_myths.aspx

https://prezi.com/dyj9qnqkey8a/physical-properties-of-plastics/

https://www.ecostarplastics.com/pet-101/pet/ history

https://committee.iso.org/files/live/sites/tc61/files/The%20Plastic%20Industry%20Berlin%20Aug%2020
16%20-%20Copy.pdf