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Polymerisation Practice TEPE
Polymerisation Practice TEPE
1. Bulk polymerization
2. Solution polymerization
3. Suspension polymerization
4. Emulsion polymerization
6. Etc.
1
1. Bulk Polymerization :
In the reactor:-
- Liquid monomer
- Initiator
- Inhibitors
- Chain transfer agents
Monomer
I
I
I
I
Initiator
3
Pros & Cons of Bulk Polymerization
Advantage Disadvantage
- Obtain highest polymer yield per - Cannot get high rate and high
reactor volume MW at the same time
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
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
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 )
Suspending agent
(Hydrophobic)
(Hydrophilic)
monomer
+ Water
Initiator
Monomer (hydrophobic)
Initiator (dissolved in monomer)
Monomer phase
Chain-transfer agent (dissolved in
monomer)
Initiator Water
Soap monomer (Hydrophilic)
Typical ingredient
20
Steps in Emulsion Polymeriztion
=
=
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
การดึงเส ้นใยไนลอนจากผิวสัมผัสของสารละลาย
25
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 -Need extra process in washing out suspending
- easy to control reaction temp. agent/contaminants and drying the polymer beads
- low viscosity -Polymer beads may stick together and maybe
- polymer produced may be used directly contaminated with suspending agent
as polymeric suspension -Good only for addition polymerization using
hydrophobic free radical initiator.
Emulsion -- Good heat transfer -Need extra process in washing out emulsifier/
- easy to control reaction temp. contaminants and drying
- low viscosity -Good only for addition polymerization using
- polymer produced may be used directly hydrophilic initiator.
as polymer latex
Interfacial -Reaction is fast at room temp. and -Limited to polycondensation where the two reactants
pressure. No need for high temp. like are insoluble in each other ex. Acid chloride (quite
in normal polycondensation. expensive)
-Can produce polymer in fiber form - Need extra process in recovering solvent and excess
- Good heat transfer reactants
- low viscosity
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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
27
6. Gas-Phase Olefin Polymerization :
Good Point :
- No solvent