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Polyethylene is a polymer with ethylene as its monomer. There are several types of polyethylene including high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE). LDPE has a high degree of branching and is produced via free radical polymerization, while HDPE has little branching and is produced via Ziegler-Natta or metallocene catalysts. The free radical polymerization of ethylene to produce LDPE was first developed in the 1930s, while Ziegler-Natta catalysts allowed the production of HDPE in the 1950s and metallocene catalysts provided improved control of polymer structure in the 1970s.

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201 views

Pe PDF

Polyethylene is a polymer with ethylene as its monomer. There are several types of polyethylene including high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE). LDPE has a high degree of branching and is produced via free radical polymerization, while HDPE has little branching and is produced via Ziegler-Natta or metallocene catalysts. The free radical polymerization of ethylene to produce LDPE was first developed in the 1930s, while Ziegler-Natta catalysts allowed the production of HDPE in the 1950s and metallocene catalysts provided improved control of polymer structure in the 1970s.

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Tai Xin Yee
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Polyethylene

Monomer:
Ethylene

High Density Polyethylene (HDPE)


Low Density Polyethylene (LDPE)
Linear Low Density Polyethylene (LLDPE)
1
Low Density Polyethylene (LDPE) High Density Polyethylene (HDPE)
High degree of short and long chain Low degrees of branching (essentially
branching linear)
Density - 0.9100.940 g/cm3 Density > 0.940 g/cm3
Lower tensile strength and increased High tensile strength
ductility Various catalysts (ZN, Metallocene)
Free radical polymerization Milk jugs, detergent bottles, garbage
Plastic bags and film wrap containers and water pipes

Long chain branching Short chain branching Hyperbranched


(HDPE) (LLDPE) (LDPE)
2
Timeline of Polyethylene

1898
Synthesized by accident while heating diazomethane (Called
Poly-methylene due to repeating CH2 group)

1930-35
First polymerization of ethylene at Imperial Chemical
Industries.
Advent of the free radical process to produce LDPE

3
Free Radical Polymerization
1. INITIATION (You need Initiators)

AIBN

Benzoyl Peroxide

4
Free Radical Polymerization
2. PROPAGATION
High pressure is needed during the propagation step in order to bring
the ethylene monomer closer to the free radicals

5
Free Radical Polymerization
3. TERMINATION (Many ways)

a. COUPLING

6
Free Radical Polymerization
3. TERMINATION (Many ways)
b. DISPROPORTIONATION

7
Free Radical Polymerization
3. TERMINATION (Many ways)
c. CHAIN TRANSFER (Hydrogen Abstraction)

8
Free Radical Polymerization

SIDE REACTIONS
(Causes Branching)

9
Disadvantages

1. Uncontrolled Process
Structure,
Molecular weight
2. Requires high pressure
3. Reactions are highly
exothermic
4. Inefficient process (20%
ethylene polymerized)

10
Timeline of Polyethylene

1898
Synthesized by accident while heating diazomethane (Called
Poly-methylene due to repeating CH2 group)

1930-35
First polymerization of ethylene at Imperial Chemical
Industries.
Advent of the free radical process to produce LDPE

1950s
Ziegler-Natta Catalyst (Inorganic Catalyst for HDPE)

11
Zieglar-Natta Catalyst

12
Zieglar-Natta Catalyst

Mechanism

13
Timeline of Polyethylene

1898
Synthesized by accident while heating diazomethane (Called
Poly-methylene due to repeating CH2 group)

1930-35
First polymerization of ethylene at Imperial Chemical
Industries.
Advent of the free radical process to produce LDPE
1950s
Ziegler-Natta Catalyst (Inorganic Catalyst for HDPE)
1970s
Metallocene Catalyst (Organic-Inorganic Hybrid Catalyst for
HDPE)

14
Metallocene Catalyst

Zirconium Sandwich
The Bread is Cyclopentadiene
The Filling is Zr bonded to Chlorine

15
Timeline of Polyethylene

1898
Synthesized by accident while heating diazomethane (Called
Poly-methylene due to repeating CH2 group)
1930-35
First polymerization of ethylene at Imperial Chemical
Industries.
Advent of the free radical process to produce LDPE
1950s
Ziegler-Natta Catalyst (Inorganic Catalyst for HDPE)
1970s
Metallocene Catalyst (Organic-Inorganic Hybrid Catalyst for
HDPE)

What is next ?
Organic Routes (biological enzymatic reactions) 16
Zieglar-Natta Catalyst

Mechanism

17

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