Chapter 5:Polymerization Techniques

1. Bulk polymerization

2. Solution polymerization

3. Suspension polymerization

4. Emulsion polymerization

5. Interfacial condensation polymerization

6. Etc.
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 1. Bulk Polymerization :
In the reactor:-
- Liquid monomer
- Initiator
- Inhibitors
- Chain transfer agents

Homogeneous : polymer remains dissolved in monomers.

Ex. PMMA
Heterogeneous : aka. Precipitation polymerization
polymer is insoluble in its monomers.
Ex. Polyacrylonitrile, PVC

Problem : heat transfer not good

Make objects with a desirable shape by polymerization in a mold.

2
Model of Batch Polymerization

Monomer

I
I

I
I
Initiator

3
 Pros & Cons of Bulk Polymerization

Advantage Disadvantage

- Obtain purest possible polymer - Difficult to control

- Conveniently cast to shape - Reaction has to be run slowly

- Obtain highest polymer yield per - Cannot get high rate and high
reactor volume MW at the same time

- Difficult to remove last traces

of unreacted monomer

4
5
Ex. 1 The maximum possible temperature rise
in a polymerizing batch may be calculated
by assuming that no heat is transferred
from the system. Estimate the adiabatic
temperature rise for the bulk
polymerization of styrene, Hp = -16.4
kcal/mol, molecular weight = 104
• Solution Hp for polymerization of
styrene = 16,400 cal/mol (assuming complete
conversion)  meaning that polymerization
of 1 mol styrene release heat in the amount
of 16,400 calories.
cal 1mol g oC
 Tmax 
•In the absense ofmolheat
16, 400 x x 
transfer,315o
all this
C (!)
104 g 0.5cal
energy heats up the reaction mass.
(Note that- Boiling point of styrene = 146 oC)
• To a reasonable approximation, the heat 6
 2. Solution Polymerization
Solution Polymerization : Monomer dissolved into inert-
solvent / inhibitor
- Monomer
- Initiator
- CTA
- Inert solvent
Solvent helps controlling heat transfer from reaction.

Use for :
- Thermosetting condensation polymer (stop before gel point)

- Ionic polymerization

- Ziegler-Natta solution process

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Model of Solution Polymerization

Monomer
I

I
I Initiator
I

I
Solvent

8
 The effect of solvent solubility on
the molecular weight of polyurethane
produced by solution method
Solvent V iscosity of polym er Precipitation of polym er
solution out of the solution

Precipitate immediately
Xylene 0.06
C hlorobenzene 0.17 Precipitate immediately

N itrobenzene 0.36 Precipitate within 0.5 hr.

D im ethylsulfoxide 0.69 Polymer remain dissolved in solution

Viscosity of polymer  MWpolymer

 High viscosity = high molecular weight !

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 Pros & Cons of Solution Polymerization

Advantage Disadvantage
solvent
- Reduces the tendency toward - Rate [M]  reduce rate,
autoacceleration chain length xn
- Solvent waste
- Increases heat capacity/heat- - Need solvent separation &
transfer recovery
- Have traces of solvent, monomer
- Reduces viscosity
- Lower yield
- Minimize runaway reaction -Solvent may not be really inert
(May interfere w/ rxn.-act as CTA)

10
Ref: S.L. Rosen, John Wiley & Sons 1993
11
Ex. 2 Estimate the adiabatic temperature rise for the
polymerization of a 20% (by weight) solution of styrene
in an inert organic solvent
Solution In 100 g of the reaction mass, there are 20 g of styrene,
so the energy liberated on its complete conversion to polymer is

(1mol ) (16400cal )
(20 g )  3150 cal
(104 g ) (mol )

• Temperature rise is calculated from Q =

mc T
o
( g
Therefore, the adiabatic temperatureC ) rise1is then
Tmax  (3150cal )  63o C
(0.5cal ) (100 g )
12
Ref: S.L. Rosen, John Wiley & Sons 1993
13
Ref: S.L. Rosen, John Wiley & Sons 1993
14
 3. Suspension Polymerization :
Model of suspension polymerization

Suspending agent

(Hydrophobic)
(Hydrophilic)
monomer
+ Water
Initiator

Monomer into water,

suspending agents (Ex.Ionic detergent, barium sulfate)
- Ex. Polyvinyl alcohol
- Beads of polymer ( 10-1000 m)
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 Typical Composition:

Monomer (hydrophobic)
Initiator (dissolved in monomer)
Monomer phase
Chain-transfer agent (dissolved in
monomer)

Water – suspending medium

Protective Colloid
Suspending agent
Insoluble inorganic
salt
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Pros & Cons of Suspension Polymerization
Advantage Disadvantage
1. Easy heat removal 1. Low yield / reactor volume
and control
2. Traces of suspending agent
2. Obtain polymer in a on particle surfaces
directly useful from
3. Cannot run continuously
4. Cannot be used for
-condensation polymers
-ionic or Ziegler-Natta
polymerization
17
Ref: S.L. Rosen, John Wiley & Sons 1993
18
 4. Emulsion Polymerization
Emulsion Polymerization : Use emulsifier / soap

Initiator Water
Soap monomer (Hydrophilic)

-Reaction occurs in water phase until polymer gets very

hydrophobic and then dissolve back in the monomer region.

Ex. Latex - very very small particle stable in solution

- particle size << 1 m
- can generate very high MW. polymer 19
Emulsion Polymerization (cont.):

Typical ingredient

100 part (by wt.) monomer (water insoluble)

180 part water
2-5 parts acid soap
0.1-0.5 part water-soluble initiator
0-1 part CTA (monomer soluble)

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 Steps in Emulsion Polymeriztion

Water-soluble initiator Monomer swollen micelle

Polymer born in water Polymer moves to micelle

-growing polymer particle

-Monomers inside the micelle decrease

Unreacted monomers in other

micelles and in droplets diffuse
through water to the growing particles

Reaction terminates when 2nd radical gets in

reaction starts again for the 2nd chain when 3rd particle gets in. 21
Ref: S.L. Rosen, John Wiley & Sons 1993 22
Ref: S.L. Rosen, John Wiley & Sons 1993
23
 5. Interfacial Polycondensation

Interfacial Polycondensation of Nylon 6/11

water
H 2N CH2 6 NH2 Monomer1 : Hexamethlyene diamine H 2N CH2 6 NH2

Polymer formed at interface

CCl4
o o o o
Monomer2 : Sebacoyl chloride Cl  C CH2 8C  Cl

=
=
Cl  C CH2 8C  Cl
=

o o H H o o
=

=
H 2N CH2 6 NH2  Cl  C CH2 8C  Cl  N CH2 6 N  C CH2 8C   HCl

=
Commercial scale  easier to stir the phases together

Advantage : - Reaction  rapid at room temperature

(no need for high T., vacuum P.)
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 Experiment on
Interfacial Polycondensation of Nylon 6/11

การดึงเส ้นใยไนลอนจากผิวสัมผัสของสารละลาย

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 Pros & Cons of some polymerization techniques
Pros Cons
Bulk - easy - Difficult to control temp. and heat transfer
- No contamination - High viscosity
Solution -good heat transfer - Need to use solvent –adding cost
-easy to control reaction temp. -Difficult to eliminate solvent entirely
-low viscosity -Solvents sometimes act as chain transfer agent 
-polymer produced may be used directly leading to lower MW polymer
in the solution form

Suspension - Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used directly
as polymeric suspension
Emulsion -- Good heat transfer
- easy to control reaction temp.
- low viscosity
- polymer produced may be used directly
as polymer latex
Interfacial -Reaction is fast at room temp. and
pressure.  No need for high temp. like
in normal polycondensation.
-Can produce polymer in fiber form
- Good heat transfer
- low viscosity
-Need extra process in washing out suspending
agent/contaminants and drying the polymer beads
-Polymer beads may stick together and maybe
contaminated with suspending agent
-Good only for addition polymerization using
hydrophobic free radical initiator.
-Need extra process in washing out emulsifier/
contaminants and drying
-Good only for addition polymerization using
hydrophilic initiator.
-Limited to polycondensation where the two reactants
are insoluble in each other ex. Acid chloride (quite
expensive)
- Need extra process in recovering solvent and excess
reactants
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 Comparing different techniques for Polycondensation
conditions บัลค ์ สารละลาย ระหว่างผิว
(bulk) (solution) (interfacial)
Temp สูง จากัดอยู่ทจุี่ ดหลอมเหลวและจุดเดือด
ของตัวทาละลายโดยทัวไปท่ าที่
อุณหภูมห ิ ้อง
Heat stabilization จาเป็ น ไม่จาเป็ น ไม่จาเป็ น

Kinetic of ้
สมดุล เป็ นขัน ้
สมดุล เป็ นขัน ้ั สมดุล
บ่อยครงไม่
Reaction คล ้ายปฏิก ิรยิ าลูก
โซ๋
Reaction time ่ั
1 ชวโมงถึ
งหลาย หลายนาทีถงึ 1 หลายนาทีถงึ 1
วัน ่ั
ชวโมง ่ั
ชวโมง
Productivity สูง ่ งสูง
ตาถึ ่ งสูง
ตาถึ
Equality of จาเป็ น ไม่คอ
่ ยจาเป็ น ไม่จาเป็ น
reactants
Purity of จาเป็ น ไม่จาเป็ น ไม่จาเป็ น
reactants
Equipment พิเศษ ระบบปิ ด ง่ายๆ ระบบเปิ ด ง่ายๆ ระบบเปิ ด
Pressure สูง, ตา่ บรรยากาศ บรรยากาศ
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 6. Gas-Phase Olefin Polymerization :

- Use Zieler-Natta catalyst

- Moderate P (7-20 atm)

- Low temperature ( < 100 oC)

- Use fluidized bed reactor

Good Point :
- No solvent

- Monomer separation is easy

- Low capital + operating cost 28

Ref: S.L. Rosen, John Wiley & Sons 1993
29
Ref: S.L. Rosen, John Wiley & Sons 1993 30