:

Polymerization Reactions

( (Homopolymer
.
).(Copolymer

() Addition Polymerization

.

"" .
.
) (Vinylchloride ).(PVC
CH

Cl

Cl

Cl

Cl

n H2C

Cl

.
CH2

Ph

Ph

Ph

n HC
Ph

O
O

n H2C

CH2
O
O

() :Condensation Polymerization

"" .

) (Secondery Products
...

.
.

+
O

C6H4

OH

C6H4

HO

OH
HO


) (Linear Polymers 6,6
) (Adipic Acid ).(Hexamethylenediamine
O

n
OH

NH2

HO

+ 2nH2O
4
n

CH2

6 N
H

N
H

n NH2

 "
( )Polyfunctional
) (Cross-Linked Polymers ) (Polyester
" " "
"
O
O
OH
OH + n HO

OH

n HO

O
O

O
O
O

 .

-
. ) (Polyether
.
O

n H2C

CH2

+ H2O
n

OH
HO

 ) (Polyamide .
O

+
H

H
N

NH

.
O

H
N

+ H2O
n

H2N

OH


)(Ethyleneisocyanate

OH

HO

NCO
OCN

H
O

O
N
O

 )(Chloroformate

Cl

Cl

H2N

NH2

+2 HCl

H
N

n
O

H
N

CH2
n
.

n CH2



.
: .

CH2

H2C

n
.

2Na

+ 2NaBr
n

Br

Br

: .

 Growth Polymerization

:Chain

.
.
) (Free Radicals .
) (Initiation Step " "
.
) .(Initiator :
. .

.
:
.
( )1
.
( )2
.
( )3

 ) (Polyurethane
) (Ethyleneisocyanate
HO

OH

NCO

H
N

OCN

H
N

n
O

Cl

)(Chloroformate

Cl

H2N

NH2

+2 HCl

H
N

n
O

H
N

.1 " "
H

H
C

.1 ) (Electron Withdrawing
.
" "
H

H
C

) (Electron Donating
. "
"
H
H
H

H
C

C
X

C
H

 -
" " ).(Vinyl Polymerization
Polymerization of Vinyl Monomers

H
C
X

C
H

))((X=H; -R; Cl; -OH; -OR; -C6H5; -CO2R; -CONH2

:
.1 Initation Step
( )Initiator
.

)(Free Radical

)I (initiator

2R

O
O

Benzoyl Peroxide

Chain Propagation Steps

) (Addition Reactions
( )
1.1 .

CH

n+1

X
CH

X
H2C

CH
X

+ H2C

CH
X

R
X

 :Termination Step

:
Coupling of Free Radicals
.

H
R

n+1

n+1 X

n+1

n+1 X

 )(Disproportionation

. .
.
H
H

H
R

n+1

X
R

n+1 X

X
R

+
n+1 X

n+1

 :

. " "
.
H
CH

CH

H
R

+
n+1 X

HC

+
X

n+1 X

.
.
H
CCl 3

+
n+1 X

CCl3

+
n+1 X

n+1 X

+
n+1 X

 Chain Transfer

) (Chain Transfer .

.
" " .

H
:
H
R

( )A
( )B ( )
( )C ()A
(.)B
( )D ( )
( )A (.)B
( )E
( )A ( )D .
( )E
( )F ( )G
.

n+1

n+1 X

)(B

)(A
H
H

n+1

n+1 X

)(C

)(D
C

CH2

X
X
X

H
R

n+1 X
)(F

n+1 X

)(E

X
C

CH2

n+1 X

)(G

 )(Terminating Agents

.
) .(Inhibitors
. ) (Quinones )(Hydroquinones

.
) -6, 4,2 (Benzquinone
.
() Benzoquinone
H
O

+ O
n+1
X

X
O
H

R
O

n+1
X

 -1 Coupling of Free Radicals

-2
-3
-4
-5
Chain Transfer
-6

-7

 Polymerization of Conjugated Dienes Monomers

) (Incorporation
.
2, 1 - 4,1 - . -4,1
) (Cis ) .(Trans R
) .(Resonance Forms
.

2R + 2

H2C
1,4-cis

R
R

+
R

H2C
H
1,4-trans

 .
.
Cl
Cl2 /FeCl3

H2C

CH2

Cl

.
500

Cl

CH2 +

500oC

H2C

CH2
Cl

Cl
CH2

CH2

HC

Cl

Cl
HC

CH2

CH2

H2C

HC

Cl

Cl +

Cl

Cl

CuCl2/KCl

Cl

H2C

Cl

CH2 + Cl

H2C

+ 2HCl + 1/2O2

Cl

).(Oxychlorination Process
CH2

250-350 C
Cl

Cl
CH2

HC

-HCl
Cl

H2C

O
H3C

OH
CH3

HCN / NaOH

H3C

H2SO 4
CH3
100oC

C
CN

CH3
H2C

O
C

OH

NH3

H2C

CH3

NH2

H2SO 4
M eOH / 90oC

H2C

CH3

OCH3

n
CH3

)(PVC

n
Cl

n
CN
CH3

n
CO2CH3

n
OCOCH3

 )(Polyethylene
" "
.
. .

.1 )(LDPE) (Low Density Poly Ethylene .

.2 ) (HDPE) (High Density Poly Ethylene .
.3 ) (Linear Poly Ethylene
. "
".
)(LDPE %75
. )(LDPE 2200-1300
200-300. .
" " .
.
)(LDPE .

 ()LDPE )(Films
.

.
. .
))LDPE
.
.

 Polypropylene
-
) (HDPE .
. ) (Isotactic
.
) (HDPE
" "
.
.
.
.
.

. .

 Polyvinyl chloride
.
. :
.
.
%1-0.5
.
. .

) .(Buffers .
) (batch .

. .

.

 ( (Impact Sterngth
) (Plasticizers


. .
) (Dibutyl Phthatate
) (Tributyl Phosphate ) .(Dioctyl Phthalate
.
)(rain coat
.
).(Coating

 ((Polyacrylonitrile
.
.
.
( NaHSO3 .(Na2S2O3-K2S2O8

.
( (Dimethyl Formamide
. .
. .
.
.
.
.
.
.
.

 ((Polystyrene
.

. .
.
( (Continuous System .
.
.
.
) (High Impact Polystyrene
.0.5-1%
.
. .

 ) (Extendable Polystyrene

.
.
) (Foaming Agents
.
(
)

 )(Poly metha acrylate

.
.
" "
.
.



.
.


.
.

 ((Polyvinyl acetate

. .
.

120
.


Cationic Chain Growth Polymerization


. " "
. )(Initiator
. .

Inititiation Step

.

.
. .

 ( )
( ) " "
)(Electron Deficient .
R

_
A

R
C+

H3C

H2C

) (A
.

R
A

C
R

R
H3C

_
A

C+

+
R

H3C

 HF, HCl, HBr HI

. : ) (Perchloric Acid
. )(Lewis Acids
( )AlCl3 ( )BF3 ()SnCl4
( .)ZnCl2
( (Proton Sources
( )BF3 :

_
(BF3OH) H+

BF3 + H2O

( ) .

( )R-X .
R

_
)(BF3OH
R

R
C

CH3

C
R

CH2

_
+
+
(BF3OH) H

 2 Chain Propagation Steps

.
" " .
R

_
)(BF3OH

C+
R

R
C
H2

C
R

R
H3C

R
C

+ H2C

_
)(BF3OH
R

C+

H3C


Anionic Chain Growth Polymerization
) (Carbanions
.
. .

CH
C6H5

CH2

H2N

CH

CH2

C6H5

_
+
KNH2

CH

CH2

Li

CH

C4H9

CH2

C4H9

CH

C4H9Li + CH2

Li
CH2

CH2

CH2

)(Biphenyl )(Living Dianion
. .

Na

Na


( ) .
(.(Canonical Forms

CH
C6H5

CH2

CH

+
Na

CH2

C6H5

Na + CH2

CH
C6H5

C6H5

+
CH Na

_ +
Na HC
C6H5

_
Na+

CH

C6H5

CH2 + H C
2

+
Na HC

C6H5

 .
((THF
:

H2C

CH

CH2

CH

CH2

Na + CH2

Na+
CH2

CH2

_
+
Na H2C

CH2 Na

+
H2C

CH2

CH2 Na

Na H2C
CH2

CH2


.
.
.

CH

CH

H2N

H2N

CH

_
)(3

)(1

)(2
_
CH

H2N

H2N

CH

)(1

)(4

H2N


.
.

CH3ONa + 1/2H2

CH3OH + Na
_
CH3O

H3C

).(Polyoxymethylene
.
_
O

O
H

_
+
[R3NH] OH

HO
H

R3N + H2O


- -
.

_
CH
C6H5

H2N
C6H5

CH

_
CH + CH2

C6H5

C6H5

CH2

H2N

Termination Step

.
:

_
CH2 + NH2

CH + NH3

H2N

n+1
C6H5
OH

H2C

_
O
CH2 + OCH3
n+1

n+1

C6H5

C6H5
CH2

H2N

H3CO

CH3OH

C6H5

_
O

H2C

H2C

CH2

CH2

H3CO

H2C

n+1

O
O

OH

n+1

HO

+ H

n+1

HO

 :

-1 :

. " "
" "
.
.

.
-2

.
( )Dielectrie Constant

.
. ()Dichloromethane
( )THF
( )Dioxane .

 -3

.

( )Solvation .

.
( )THF .

-4
" " .

.

.

) :
)1 vinyl chloride
)2 )(Methyl metha acrylate