Principles of Polymer Engineering

(27-034)

Ch 1. Structure of the Molecule

Reza Bagheri
Fall 1402
 Prin. Poly. Eng. – Ch 1

Polymerization

Main polymerization methods:

• Addition Polymerization ‫پلیمریزاسیون افزایشی‬
• Condensation Polymerization ‫پلیمریزاسیون تراکمی‬

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Addition Polymerization

heat/light
1. Free radical initiation R R•

2. Active center formation

3. Chain growth

4. Termination

Monomers join to the growing chain one after another during the chain growth step. 3
 Prin. Poly. Eng. – Ch 1

Common termination processes are radical termination and

disproportionation

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Addition Polymerization
Polyvinylchloride (PVC)
Vinyl polymers

Polystyrene (PS)
Polyethylene (PE)

Polymethy metacrylate (PMMA)

Polypropylene (PP)
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Backbiting mechanism

side branch
main chain

growing chain

monomers
Catalyst controls chain branching.

catalyst
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PE Types
• Low Density Polyethylene (LDPE)
(0.917 – 0.935 g/cc) ‫پلیاتیلن سبک‬

• Linear Low Density Polyethylene (LLDPE)

(0.905 – 0.955 g/cc) ‫پلیاتیلن سبک خطی‬

• High Density Polyethylene (HDPE)

(0.955 – 0.970 g/cc) ‫پلیاتیلن سنگین‬
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Condensation Polymerization
PET, an example

• In each step of synthesis

of a condensation
polymer, a small
molecule, usually water, is
byproduct split off.

• Contrary to addition
polymerization, the
polymer here is produced
by interaction between
the two constituents.
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Condensation Polymerization
PA66, an example

byproduct

Adipic acid hexamethylenediamine Polyamide 66

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Condensation Polymerization
Polycarbonate, an example

n + n

Bis-phenol A phosgene byproduct

+ 2n HCl
n

Polycarbonate 10
 Prin. Poly. Eng. – Ch 1

Degree of Polymerization in Condensation Reactions

Carothers’ equation gives the degree of polymerization, Xn, for

a given extent of reaction, P.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑜𝑢𝑝𝑠 𝑡ℎ𝑎𝑡 ℎ𝑎𝑣𝑒 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

P= 1
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑜𝑢𝑝𝑠 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙𝑙𝑦 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 Xn =
1−𝑃

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 𝑝𝑟𝑒𝑠𝑒𝑛𝑡

Xn = P 1 Xn ∞
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡

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 Prin. Poly. Eng. – Ch 1

Relative Molecular Mass (RMM)

MW = (mass of monomer) X (degree of polymerization)

mass of molecule Y
RMM =
(1/12) mass of a mole of carbon 12

• Always, there is a
distribution of RMM in
mass of a PE molecule = [(12 X 2) + (1 X 4)] X n
polymerization process.
If n = 104, RMM = 280,000 • Thus, methods for
reporting average RMM is
needed.
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Distribution of RMM
number of moles (N)

Ni

Mi RMM (M)

Wi : mass of the ith fraction

Wi = Mi X Ni

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Example
1. Consider a blend of two paraffins, C95H192 & C105H212, each 1 g.

M95 = 95 X 12 + 192 = 1332 g/mol

M105 = 105 X 12 + 212 = 1472 g/mol
N95 = 1/1332 = 7.51 X 10-4 mol
N105 = 1/1472 = 6.79 X 10-4 mol { Mn = 1399 g/mol
Mw = 1402 g/mol

2. Consider a blend of two paraffins, C10H22 & C190H382, each 1 g.

M10 = 10 X 12 + 22 = 142 g/mol

M190 = 190 X 12 + 382 = 2662 g/mol
N10 = 1/142 = 70.42 X 10-4 mol
N190 = 1/2662 = 3.76 X 10-4 mol { Mn = 270 g/mol
Mw = 1402 g/mol

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Example
3. Consider a blend of two paraffins, C10H22 & C1000H2002, each 1 g.

M10 = 10 X 12 + 22 = 142 g/mol

M1000 = 1000 X 12 + 2002 = 14002 g/mol
N10 = 1/142 = 70.42 X 10-4 mol
N1000 = 1/14002 = 0.71 X 10-4 mol { Mn = 281 g/mol
Mw = 7072 g/mol

✓ Mn is sensitive to the presence of low molecular mass species in the mixture.

✓ Mw is sensitive to the presence of high molecular mass species in the mixture.
✓ Mw always exceeds Mn.
PDI1 = 1.00
Polydispersity Index (PDI): Mw/Mn PDI2 = 5.19
PDI3 = 22.17
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Distribution of RMM

Polydispersity Index (PDI)

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Configuration of Macromolecules
The configuration (also called microstructure) of a macromolecule is determined by
the relative positions of its constituent monomer units and their structure.

Isotactic

1- Stereoisomerism Syndiotactic
(Stereoregularity)
Atactic

Configuration:
2- Geometrical isomerism

3- Head to Head vs Head to Tail

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Steroregularity in Vinyl Polymers

high order Isotactic

limited order
Syndiotactic

no order Atactic

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Steroregularity in Polyvinylchloride (PVC)

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Geometrical isomerism

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Head to Head vs Head to Tail

Head-to-Tail
Tm= 5 ⁰C

Head-to-Head

Tm= 187 ⁰C

Polystyrene Polyisobutylene

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