University of Science and Technology of Hanoi

Department of Advanced Materials Science and Nanotechnology

Course:

Dr. NGUYEN DUC ANH

AMSN – USTH
Hanoi, 08/2016
Polymerization – The way to prepare a polymer
IV.1. Polymerization
IV.1.1. Introduction
IV.1.2. Classification
IV.1.3. Step growth vs chain growth polymerization
IV.2. Step-growth polymerization
IV.2.1. Step-growth
IV.2.2. Functionalities
IV.2.3. Classification
IV.2.4. Reaction process
IV.2.5. Kinetic
IV.2.6. Condensation polymerization methods
IV.2.7. Step-growth polymer
Ethylene Polyethylene

Propylene Polypropylene

+ + H2O

+ H2O
+

 POLYMERIZATION is the process of making link between MONOMER to obtain

POLYMER chains
 Polymerization
methods

Addition polymerization Condensation polymerization

(chain growth) (step growth)

Polyconde-
Polyaddition
nsation
Stereoreg Ring-
Radical Ionic
-ular opening
 Step-growth Chain-growth
•Polymer chains occur by reaction of •Polymer chains occur only by addition of
functionalities on monomers monomer to active chain end.
 Step-growth polymerization
Growth throughout matrix
Rapid loss of monomer early in the
reaction
Same mechanism throughout
Average molecular weight increases
slowly at low conversion and high
extents of reaction time are required to
obtain high chain length
Ends remain active (no termination)
No initiator necessary
Chain-growth polymerization
Growth by addition of monomer only at
one end of chain
Some monomer remains even at long
reaction times
Different mechanisms operate at
different stages of reaction (i.e.
Initiation, propagation and
termination)
Molar mass of backbone chains increase
rapidly at early stage and remain
approximately the same throughout the
polymerization
Chains not active after termination
Initiator required
+ Step-growth polymerization: a polymerization in which chain growth occurs in a
stepwise manner when a functional group from one monomer reacts with a
functional group of another monomer.

+ The chain growth normally occurs with a release of byproducts  Polycondensation

+ + H2O

+ The chain growth occurs without release of byproducts  Polyaddition

+ Functionalities should include:

Lewis Bases -NH2 , -SH , - OH

Lewis Acid

+ Monomers should have at least 2 functionalities in order to obtain condensation

polymers:

∑𝑛𝑖 .𝑓𝑖
 Average functionality number of system: f = ni : number of monomer i
∑𝑛𝑖
fi: number of functionality
on monomer i
𝑓  the ability of making crosslink in polymer system
+ Based on reaction system:
- Homogeneous condensation polymerization
- Heterogeneous condensation polymerization

+ Based on number of functionality in monomers:

- 2 dimensions polymerization or linear polymerization:
Monomers with 2 functionalities
- 3 dimensions polymerization or network polymerization:
Monomers with more than 2 reactive functionalities
Based on reaction system
+ Homogeneous condensation polymerization
Alkyd resin: A resin based on polyester, which are the most common used as paint.
Based on reaction system
+ Heterogeneous condensation polymerization
- Nylon 6,6 is polymerized on the interface of aqueous solvent and organic solvent
Based on number of functionality in monomers:
- 2 dimensions polymerization or linear polymerization:
Monomers with 2 functionalities

A–B + A–B A-b-a-B

A–A + B–B A-a-b-B

 Examples: Synthesis of PET, nylon fibres

nylon fibres

Polyethylene terephtalate
PET
Based on number of functionality in monomers:
- 3 dimensions polymerization or network polymerization:
Monomers with more than 2 functionalities

+
 Examples: Epoxy curing reaction
Propagation of polymer chains

 n-mer + m-mer (n+m)-mer

Termination of polymer chains:

- Physical termination: Decrease of flexibility of polymer chains as result of increase
viscosity or steric hindrance of network.
- Chemical termination: Deactivation of functionality
General characteristics of condensation polymerization
(1) The polymer chain forms slowly, sometimes requiring several hours to
severaldays
(2) All of the monomers are quickly converted to oligomers, thus,
the concentration of growing chains is high
(3) Since most of the chemical reactions employed have relatively high energies
of activation, the polymerization mixture is usually heated to high
temperatures
(4) Step-reaction polymerizations normally afford polymers with moderate
molecular weights, i.e., <100,000
(5) Branching or cross linking does not occur unless a monomer with three or
more functional groups is used
 + Interchange reaction
Transesterification
+ +

Intermolecular acid exchange

+ +

Intermolecular alcohol exchange

+ +

Intermolecular amine exchange

+ +
+ Intramolecular ring-closing reaction
A chain containing two mutually reactive groups can react with it self and a
ring structure forms

HO-R1 - COO - R2- COOH HO-R3 - COO - R4- COOH

Depends on: - Nature of monomers.

- Stability of resulting ring.
A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B

A—ba—B + A—B + A—ba—B + A—ba—B + A—ba—B + A—B

FA° = total number of A groups at the beginning

FA = total number of A groups at time t

total number of reacted monomer at time t Nreacted

p = conversion = =
total number of monomer at initial time No

Nt FA
Nreacted = No – Nt  p=1- = 1–
No FAo
+ Average degree of polymerization
total number of monomers
Xn = average degree of polymerization =
total number of chains

total number of molecules present initially FAo 1

DPn = = =
total number of molecules present at time t FA 1-p

Carother Equation:
The relation of Average degree of polymerization and monomer conversion

+ Molar mass: Mm
Mn = DPn x Mm = Mm: Molar mass of monomer unit
1-p
Mm x (1+p)
Mw = DPw x Mm =
1-p

+ Dispersity: Đ = Mw/Mn = 1+ p
 A+B k AB

d[A]
- = kdt
[A]2

DPn increases when: - A0 increases

- t increaces
- k increases
 Almost of condensation reactions are reversible

[ester] [H2O]
K =
[RCOOH] [ROH]

 Initial hydroxyl and carboxyl concentrations are [M]0

 Concentration of ester groups and Water at equilibrium is p[M]0
where p = conversion of reaction at equilibrium
 The concentrations of hydroxyl and carboxyl groups at equilibrium are ([M]0 – p[M]0)
 Therefore
( p [M]0)2 p2 [M]02 p2
K = = =
( [M]0 – p [M]0)2 2
[M]0 ( 1– p )2 ( 1– p )2

DPn = 1+ K1/2 Removal of byproducts out of system

Methods of condensation polymerization:
- Melt polycondensation
- Solution polycondensation
- Interfacial polycondensation
- Solid-state polycondensation

Melt polycondensation
Temperature is kept for long period of 10 – 20 0C above the melting point of polymers
- No solvent
- High temperature
- Inert environment
- Vigorous stirring because of high viscosity in the end of process

 Applied for high degraded temperature monomers and low viscosity polymers
 Quick
 High purity
+ Solution polycondensation
All monomers are dissolved in a solvent
- Low temperature
- Previously purified solvent is necessary
- Resulting polymers can be dissolved or precipitated from solvent

 Applied for high viscosity resulting polymers or low degradable temperature monomers
 Low purity  need of purification

+ Interfacial polycondensation
2 monomers are dissolved in 2 immiscible solvents, condensation polymer is obtained
on the interface of 2 phase
- Low temperature
- Quick
- Resulting polymers have high molecular weight and long chains

 Applied for high viscosity resulting polymers and obtained from 2 different nature monomers
 Low purity  need of purification
+ Solid-state polycondensation
Condensation reaction is proceeded in amorphous phase of semi-crystalline polymer.
- Temperature is in middle of Tg and Tm
- No solvent
- Need of applied vacuum

 Applied for solid monomers, especially for degraded monomer at melting point
 High purity
 Slow reaction rate
 Polyamide

Polyester
Polyurethane

Condensation
polymers Polycarbonate
Phenolic

Polyimide Epoxy resin

 Nylon 6,6

Hexanedioic (adipic) acid reacts with 1,6-hexanediamine to make Nylon 6,6

 Nylon 6,6 is used in electrical insulation, carpet fibres, clothing, airbags, zip ties, ropes,
conveyor belts, hoses, among other things.
 • Nylon 6 is synthesized from a six-carbon monomer in a novel process called
ring-opening polymerization.

• Nylon 6 is fabricated into fibers, brush bristles, high-impact moldings, and tire
cords.
 Kevlar is an aromatic polyamide (an aramid).

• Cables of Kevlar are as strong as cables of steel, but only about 20% the
weight.
• Kevlar fabric is used for bulletproof vests, jackets, and raincoats, snowboards,
drumheads, et. al.
 Poly(ethylene terephthalate), abbreviated PET or PETE, is fabricated into Dacron
fibers, Mylar films, and plastic beverage containers.

 Completely amorphous PET is formed by cooling the melt quickly.

PET with a low degree of crystallinity is used for plastic beverage bottles.
 By prolonging cooling time, high degree of crystalinity PET is formed
PET with a high degree of crystallinity can be drawn into textile fibers and tire cords.
 Lexan
 Polycarbonates, the most familiar of which is Lexan, are important engineering
plastics.
• Lexan is made from the disodium salt of bisphenol A (BPA) and phosgene.

 Lexan is a transparent polymer with high impact and tensile strengths and retains its shape
over a wide temperature range.
• It is used in sporting equipment, such as bicycle, football, and snowmobile helmets as well
as hockey and baseball catcher’s masks.
• It is also used in the manufacture of safety lenses and unbreakable windows.
 A urethane, or carbamate, is an ester of carbamic acid, H2N-CH2-COOH.
They are most commonly prepared by treating an isocyanate with an alcohol.
 Epoxy resins are prepared by a polymerization in which one monomer contains at
least two epoxy groups.
• Epoxy resins are produced in forms ranging from low viscosity liquids to high
melting solids.