مقدمه في علم البوليمر

11

______________________
11
12

History of Polymer Science

) (Polymers .

) (Natural Polymers
.
) (Oils
) (Fats
) (Natural Resins
)Gum
(Arabic
.

) (Colloids
12
13

) (
) (Raoult ) (Vant Hoff

) .(10000 40000
) .(Macromolecules

.

:
(

.
13
14

(

) (Associated Complex
) .(Secondary Forces

.Colloidal Particles

) ( ) (C5H8
): (Isoprene
) Isoprene(

) (
:
14
15

) Polystyrene( )
( ) ) (Poly(ethylene Glycol(
) ) (Isoprene Rubber(
)Staudinger
(Herman
) ( )(Macromolecules
.
:

).(Covalent

.
15
16

) (
.

.

) (Carothers ) (

) (
.(nylon 66) :
) (
).poly(hexamethylene adipamide
16
17

:
): (adipic acid
)(HOOC-(CH2)4-COOH
): (hexamethylenediamine
(H2N-(CH2)6-NH2

) (Flory ) ( .

.

.
17
18

) (

) (cyclic structure
.
) ( )(Flory

).(chain reaction
18
19

( :

)(
.
) (Goodyear ) (vulcanization
) ( .

.
) (ebonite ) (.
( :
) (
.Cellulose
) (

) (camphor
) (celluloid

19
20

) (
)(.
(
) (

) .(acetic anhydride
) (
.
(
) (

) (cuprammonium
) ( ).(viscose
(

20
21

) (Backland

) (backlite
) (
.
(
) (
) (styrene .
) (
) (.
) (
.
21
22

) (

) (
1777 1838
- )(
1838 1868
- )( ) (

1920
1856 1914
1907
)(

1922 1937
1927 1942
) (66
1929 1938
1929
) (
1931
1936
1937
1939 1954
1939
1941
1947
1957
) (
1957
1957
1962
)(Polymides
1965
22
23

( Polymer
)) (polymer
(macromolecule
" " poly " " " "mer
"" .
.

)
) (10,000 - 106

) (linear polymer ).(

) (branched polymer
) (comb form
) (ladder form ).(cruciform
) (

23
24

)) (crosslinked polymer .(
) : ( .
(
( (
( (
24
25

( Monomer

)) (monomer (
) .(polymerization

.
( Structural repeating Unit

) (structural units
) .(repeating units
) (
.
25
26

.
( Degree of Polymerization
) (DP
)(n

.
.

) (CH2 = CH2
) (polyethylene (CH2-CH2)n
) (-CH2-CH2-
) (n
).(degree of polymerization
) ( ) (
.

26
27

"

"oligomer
) (10000 1000000

.
27
28

) : (

-CH2-CH2-
CH2 = CH2
) (
) (
CH2 = CCl2
- CH2-CH=CH-CH2-
CH2 = CH CH = CH2

)(
) (
)
- CF2 CF2 -
28
CF2 = CF2
29

) : (
6 -
NH2(CH2)6-NH2
+
HOOC(CH2)4-COOH
66 -
)
(
)poly (ethylene terphthalate
Si(CH3)2Cl2 + H2O
29
30

) : (
)
(
)(
30
31

.

.
. ) (
.
) : (
31
32

) (number average molecular weight
) . ( M n
.
) (weight average molecular weight

) ( Mw
) (viscosity average molecular weight

) . ( Mv
) ( M n

Mw
. ) ( Mw

) .(molecular weight distribution
:
32
33

Mw
Mn
) .(molecular weight distribution ratio

) (1.5 50
.
33
34

Texture of Polymers
) (texture

) (stereo isomers
) (ciss ) (trans

) (conformations

.

)
(Vulcanisation
.

) (local motion
.

34
35

) .(mobile

.

) .(molding

.

)(glass transition temperature

) (Tg
.

.
35
36

) (Tg = - 50 C ) (25 C

)(- 100 C
) (brittle
.
) (glassy states
) (crystallization

) (linearity
.
) (crystalline regions

) (amorphous
.
36
37

Intermolecular Forces in Polymers
:

) ( ) (covalent bonds

.

) (secondary forces
.

.

) (entanglement .
37
38

Co-ordination Bonds
)polymers
(inorganic
) (semi organic polymers

) (co-ordination bonds

.
)(Ionic Bonds
) (ionic bonds

) (natural resins
) (crosslinked polymers

) (ionomers

) (plasters .
38
39

Metallic Bonds
) ( ) (metallic bonds

)) (organometallic
(
)(metalocene polymers

).(polyphthalocyanene
) (
) (secondary forces
)(Van der Waals
).(inter molecular forces

.
( Dipole Forces

39
40

) (dipole moment .

.
( Induction Forces

.
.
( Dispersion Forces

) .(dispersion attractive forces
40
41

.
( Hydrogen Bonds

.

) (intrmolecular hydrogen bonding

) .(interamolecular hydrogen bonding

) (-COOH
) (-CONH2 ) (-NH2- )(-OH
.

.
41
42

) (12.6 29.4 kJ/mol

).(2.4 10-8 3.2 10-8 cm
42
43

The Effect of Molecular Forces on the Polymer Properties
) (cohesive energy

) (specific cohesive energy
) .(cohesive energy density
) (heat of vaporization
)(heat of sublimation
.

.

43
44

.
.

. ) (
.

) (swelling .
) (solubility parameter
) ( :
) ( =
1/ 2
44
45

) : (

)
( ) (
)(Tg C
)(Tm C
7.9
- 125
141
8.0
- 20
165
) (
9.5
87
190
7.8
- 50
10
)(
8.1
- 72
28
8.6
100
239
) (
9.1
105
) (
10.7
69
267
66
13.6
50
265
) (
15.4
120
317
): (
) (elastic polymers
.

.

.
45
46

.

.
46
47

Nomenclature of Polymers
47
48

Nomenclature of Polymers

.
.
:
Nomenclature Based on Sources

.
.

)linking
(cross ) .(branching
) (poly
.

48
49

.

) (

) (polyethylene oxide
:
49
50

poly styrene
) (
)poly (alpha-methylstyrene
) (
)poly (vinyl alcohol

:
-
)(6- aminocaproic acid
:
) - (
).(poly (6- aminocaproic acid

.

50
51
(co-) -
.

) (ethylene glycol )(terphthalic acid
:
) (
)poly (ethyleneglycol-co-terphthalic acid
:
( .
(

. .

) ) (poly (vinyl alcohol

) ) (poly(vinylacetate
) (.
51
52

.

:
-(O-CH2-CH2) n :

)(ring opening polymerization
:

)(Polyoxirane
) (
)poly(ethylene oxide
52
53

) (ethylene glycol :
)poly(ethylene glycol
)poly (1,2-ethylene diol
:
) (
)poly (ethylene glycol
) - (
)poly (1,2- ethylenediol
53
54

Nomenclature of Condensation Polymers
:

. :
) (.
poly-- caprolactam

:

caprolactam
54
55
) (.
)poly(ethylene terphthalate

)( :

ethylene terphthalate
55
56
:

) (
(co-) - :
) (
poly (hexamethylenediamine) co-adipylchloride
56
57

Nomenclature of Copolymers
(
Nomenclature of Random Copolymer
) (

) (Co
:
-
)poly (styrene-co-butadiene

:
) (
Poly(methyl Methacrylate)-co-styrene

57
58

ABS :
) (
)poly (styrene-co-butadiene-co-acrylonitrile
(
Nomenclature of Alternating Copolymer

) (-co- ) (alt
) (alternative ) (

) (ceresa

:
) (
)poly(ethylene-alt-carbonmonoxide
58
59
(
Nomenclature of Grafted Copolymers

:
) (co )(g
) (graft ) (
:
) (
)poly(styrene-g-acrylonitrile
59
60
( )(
Block Copolymers
) (

:
) (-co-
) (b ) (block

:
:
) (
)poly(butadiene-b-acrylonitrile
60
61

)Nomenclature Based on the Structure of Repeating Unit

.
.

:
)(hexamethylene diamine
)acid
(sebasic
:
) (
)poly(hexamethylene sebasamide
61
62
:
) (
)poly(ethylene terphthalate

.
62
63
:
Trade and Known Names

.

) (diamines
) (nylon
) (Carothers

)
(.
:

: 6
: 66 ) ( :
( ): (adipic acid
)(HOOC-(CH2)4-COOH
63
64
( )(hexamethylene diamine
(H2N-(CH2)6-NH2
106 -
) (
)poly (hexamethylene ebasamide
: Teflon
) ( (CF2-CF2)-
)poly (tetrafluroethylene
-(CH2-CH2)-Cl : PVC
) (
)poly (vinyl chloride
:
caprolactam 6
) (6- aminocaproic
) (repeating unit
) ( . (Nylon-6) 6-

.

64
65

)resins
(phenolic ) .(phenoplast
.
) ( )(polytetrafluroethylene
) ( )(polyacrylonitrile
).(prespex

.
65
66
:
Nomenclature Based on IUPA

.
)(IUPAC Macromolecular Nomenclature Commission
-
.

) (journals .
:

Constitutional Repeating Unit

66
67
67
68
68
69
)(
) (bivalent

:
-CH=CH
= = CH - CH
:
69
70
:
-CH = CHCH2CH2
= = CH-CH2-CH2-CH
70
71
)(

. ) (
) ( :
) ( - O - CH 2CH 2 -
)
) ( - CH 2 -
)Poly (Oxyethylene
Polymethylene
71
72
)(

.

:
- CH = CH - CH 2 CH 2 -
) -(
)poly(1- butenylene
) -(
)(poly (2 - butenylene

:
) (
)poly (vinyl ethylene

72
73
)(
)poly(ethylidine
) (
)poly (methyl methylene
.
73
74
)(

. .

:
:
) -3 2- (4'',4-
)poly (3- bromo -2'-chloro- p- terphenyl -4, 4'' ylene
74
75
)(

): (
:
)poly (1- phenylethylene
:
)poly (benzylidinemethylene
:
)poly (1 phenyldimethylene
75
76
): (
:
:
) - (
)poly (1, 2 dioxo tetramethylene
:
)(
)poly (Succinyl

) (1, 4- ) (1,2-
.
76
77
:
) (
)poly (oxy succinyl
:
) (.
.
77
78
)(

:
( ) - (
)poly(2,4 pyridinediyl
( ) - (
)poly (2,7- naphthalene
( ) ] [ ( -
)poly (tricycle[2.2.1] heptylene-3.5
78
79
)(

) (subunit

.

) (A, B, D :
)poly (A. B. D
:
79
80
) (
)poly (oxo terphthaloyl hydrazo terphthaloyl
:
) - (.

:
( .
( )(hetro atom
( .
( .

.
80
81
) - - (
)poly(4,2-pyridine diylamino-1,4- cyclohexylene benzylidene
81
82
)(

) .(hetro atom

.
:
O, S, Se, Te, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, B. Hg
.

:
] ) - ( [
]poly [imino (1- oxyethylene) silylene trimethylene
82
83
.( - )
poly (oxy methylene amino carbonyl) thio-1,3- phenylene ethylene
83
84
)(

:

.
:
84
85
) - - - (.
)Poly(2,7 naphthalene- 1, 4- phenylene -1,3 cyclohexylene
) - (
)poly (2,6 biphenylene ethylene
85
86
( - -) ( - -)
Poly (3-chloro - 4,4' biphenylene) methylene

(3- chloro -1, 4- phenylene) methylene]
86
87
)(

:
(
.
:
) ) - ( ) - (
)poly (oxy (1,1- dichloroethylene) amino (1- oxoethylene
(
.
87
88
) ) -( - - ) - (
])poly [thio (1- chloroethylene) 1,3 phenylene (1- chloroethylene
( ) (alphabetical
] - ) - ( - ) - ([
poly[1,3- phenylene (1- bromo ethylene)-1,3-cyclohexylene (2-butyl ethylene
88
89
)(

:
(

.
:
) (
)poly (oxybenzylidene
:
) ) (
)poly (oxyphenylmethylene
89
90
(
.

.
:
) - -- - -( ) - (.
])poly [(6-chloro-1-cyclohexene-1,3-ylene) (1-bromoethylene
] ) - ( [
]poly [oxy 2-(methoxycarbonyl) ethylidine
90
91
(

.
:
] ) - (
])[poly [oxy (2- chlorosuccinyl

. ) (

)) (IUPAC(.
91
92
) : ( )) (IUPAC(.
IUPAC

(-CH2CH2-)n

(-CH(CH)3CH2-)n

)(- CH = CH CH2 CH2-
) -(
) - (
) (

) - (
92
) - (
) - (
IUPAC
93
) (
)Poly (vinyl alcohol
) - (
)poly (1- hydroxyl ethylene
) (
)poly (vinyl acetate
) - (
)poly (1- acetoxy ethylene
) (
)poly (vinyl chloride
) (
)poly (vinylidene fluoride
-(CF2CF2)n
) (
)poly (tetraflouro ethylene
) (
)poly(methyl acrylate
93
) - (
)poly (1- chloroethylene
) (
)poly (1,1-diflouroethylene
) (
)poly (difluoromethylene
]) ( -[
]poly [1-(methoxy carbonyl)ethylene
IUPAC
94
) (
)poly(methyl Methacrylate
)(-O-CH2-
)(-OCH2-CH2-

) (
) (
) (
) (
66 -
)( 6 -
94
]) ( - [
poly[1-(methoxycarbonyl)-1]methylethylene
) (
) (.
) - (
)poly (oxy-1,4-phynylene
) ([
)poly (oxyethylene oxy terephthalate
) (
)poly (amino methylene amino adipoil
])- ([
)poly (amino -1- oxohexmethylene
95
IUPAC
(repeating
) unit
:
( ) ( .
(

:
... Bi, B, As, P, N, Te, Se, S, O.

:
) (
)poly(1-methylethylene
:
) (
95
96
)poly(ethyleneterphthalate
:
poly (oxy-ethylene-oxy-terphthaloyl
) (.
})poly{2,4-pyridinyl-[4-(2-chloroethyl)-(1,3-phenylene]-(2,4-dioxo-hexamethylene
) - ] -) - - )-[ -]- -(.

:
)(-CH2-CH2-O
96
97

polyethyleneoxide
:
) (
)poly(ethyleneoxide
) (polyethyleneoxide

:

) (PS
) (PS
) ...(PS) ( polysiloxanes
.
97
98

Types of Polymers and

their Classification
98
99

Types of Polymers and their Classification
:
Classification Based on Sources
:
( )(Natural Polymers
:
( )(Organic

:

.
.
99
100

( )(Inorganic
: .
( ) (
Synthetic Polymers

.
.
:
(

.
(
.
100
101

(
Modified Natural Polymers

.
:
)acetate
(cellulose
) (cellulose nitrate ) (
.

.

.

) (
101
102

) (Films .
102
103

:
Classification Based on the Chemical Nature of Polymer

:
( Organic Polymers
)
( .
.
( ) (
Pure Inorganic Polymers
.
) (-Si-
) (-N- ) (-P-N-
).(-B-N-

.
.
) (
.
103
104

) (silicon polymers
)fibers
) )silicates
(glass
(poly
)( .
104
105

) (

polysulphide
) (
)poly (sulphure oxide

)poly (sylphonitide
) (
)poly (oxyphosphohalide
) (
)poly(phosphonitrilic chloride
350 C

1000 C

polyphosphazene
) (
polyphospho-oxonitride
) (
)poly (silicon disulphide

)(1200 C

.
)(
poly borazole
300 C

105
106

(
)(Organic Inorganic Polymers

.
.
.Silicon Polymers
:
)' (R, R .

) (co-ordination polymers
) (metal chelate polymers
) (metal ion

) .(co-ordination bond

106
107

) (ferrocine :
) ( .
107
108

) (

Polysulphone

Polysiloxane
) (
)Poly (Metalosiloxane
)(M = Al, B
M = Sn, Ge
M'' = Ti
M''' = P, AS
) (
)Poly (Vinylferrocene
108
109

:
Classification of Polymers Based on Technological Aspects

:
( Thermoplastics
) (hard
) (soften

)
) (thermoplastic

.

) .(thermoplastics
:
109
110

) (polyethylene ) (polystyrene
) (polycarbonates ) (
) (poly(vinylChloride
) (polypropylene.

.

.
.

.
:
) ( .
( ) (
Thermosetting Polymers

)

110
111

).(thermosetting

.

.
:

.
) (
:
) (crosslinked.
) (hard
.
)
(.
111
112

) (

.
)(Thermoplastics

) (Thermoplastics
.
:

) (crosslinking agents

).(crosslinked polymer

) (high energy radiation

.
112
113

( Elastomers

)elongation
or
(extensibility
).(resilience or resiliency

.

.

). (Tg

) (
.
113
114

) ( ) (

) - (.
1931
) (

nitrile rubber
.
)(S. B. Rubber

butyl rubber

)(butadiene rubber
1937
1937
)
)(0.6 3.5 %
1934
) (
1961
1960

1961
1962
114
1963
115

( Fibers

) (crystalline polymer
.
:
.
.

.
) (Tg
.

.
.

.
115
116

.
)
(
) (Static Charges
.
.
:
) (.
.
) ( ) (.
.
( Adhesive and Coatings
.

116
117

.

.
:
)(arabic gum
.

.
) (
.

films .
117
118

) (
acrylic adhesives
cellulose acetate, butyrate, nitrate
epoxides
) (
synthetic rubber
polyisocyanates
melanoplast
phenolplast
uroplast
polyamides
polyesters
polyurethanes
polyvinyles
polysilicones
118
119

:
Classification Based on the Structural Shape of Molecules

:
( Linear Polymers

.

.
:
)(high density polythylene
-
) .(Ziegler-Natta catalyst
)(.
119
120

) : (
(
( (
( Branched Polymers

) ( .
120
121

) (Tm
) (Tg .

) (

.
:
)(Low Density Polyethylene
121
122

( )(crosslinked polymers

) .(
) (degree of crosslinking
.
:
.
.

.
:
)(thermosetting resins
:
.
.
122
123

:
Classification Based on the Homogeneity of Polymers
( Homopolymers

. ) (
.

) (CH2-CH2-

:
( )( Copolymers

.

.
123
124

.

) (co-polymerization

.
): (SB
)
)(styrene butadiene copolymers

:
124
125

( Composite Polymers

.
)(heterogeneous
.

.

:
( ) (stiffness )(strength
).(dimensional stability
( ).(impact strength
( )(distortion temperature
.
( ).(mechanical damping
( .
( .
125
126

( .
) (
).(glass fibers
) (

)(%
30
20
10
0
69.8
60. 41.8 25.5

-6
9
Tensile Strength 10 N/m2

84.7
67. 44.2 20.7
2
Flexural Strength 10-6 N/m2
54.9
40. 24.3 8.6

Flexural Modulus 10-8 N/m2
3

130
129 116
71
4.6 105 N/m2
Impact Strength
1.7
2.8 4.0 18.1
) ( N/m
126
127

.

.
) (additives :
( : Fillers

. ) (
.
( Plasticisers
.
.

.
(

.
127
128

) ( ) (Fillers
Composites
polystyrene
Fillers

styrene acrylonitrile - copolymer
polyethylene
polypropylene
) (
)poly vinyl chloride (PVC
epoxy resins
Polyurethane
butyl rubber

ethylene propylene rubber
( Polymer Blends

.

.
.

.
128
129

Classification of Polymers Based on
"the "Polymerization Reaction

.
:

.
:
: :
(
) )(condensation polymers
(
) )(addition polymers
129
130

Classification Based on the Mechanism of Chain Growth
:
(
chain growth polymerization
( )(
step growth polymerization
: :
(
) )(Condensation Polymers

) (
.

:
)(Ester
) (Amide
130
131

.

.

:
:
)poly (hexamethylene adipamide
:
(C12H22N2O2)n
:
)(C6H10O4 + C6H16N2
131
132

:
: C6H16N2
)(H2N-(CH2)6NH2
: C6H10O4
).(HOOC (CH2)4-COOH
:
)(C6H10O4 + C6H16N2) = (C12H26N2O4

.

.
132
133

(
Addition Polymers

)( .

.
:
) (polystyrene
:
133
134

Classification Based on the Mechanism of Chain Growth

.

)) (chain growth mechanism
(.
:
(
Chain Growth Polymerization

Chain Growth Polymers

) (Initiation
) (active center
134
135

.
:
( Initiation
( Propagation
( Termination

.

(Chain
) Reaction ) (

.
) (unsaturated

.
) (AdditionPolymerization
) .(AdditionPolymers
:
(
( .
135
136

Mechanism of Free Radical

Polymerization of Vinyl Monomers

) (CH2 = CH x ) (-H ) (-R
) (-CH=CH2 Cl )...(-OH .

) (initiators

).(I

( Initiation Step
) (I
) (free radicals
) ( :
136
137

( Propagation Step

:
( Termination Step

.
). (termination reaction
137
138

(
Coupling Reaction
(
Chain Transfer

:
( :
138
139

(
Chain Transfer to Solvent
( :

.
)(primary radical termination

.
(
Chain Transfer to Polymer Molecules
139
140

(
.

.
Disproportionation

:
140
141

(
Termination Agents

) (growing active center
) ) (inhibiting agents
) (inhibitors
(retarding
)agents
) .(retardants

.
141
142

)(
Cationic Polymerization of Vinyl Polymers

) (CH2 = CHX
X )(electron donating group
) (-OR) (-C2H5) (-CH3) (-OH

:
( Initiation Step
)(initiator
)
(cation
) (bronsted acid ).(Lewis acid

HCl H2SO4
:
142
143

( Propagation Step

:
( Termination
:
(
:
143
144

(
) (chain transfer

:
144
145

Anionic Polymerization of Vinyl Monomers

) (electron withdrawing
CH2=CHX X
CN ) (CH=CH2 C6H5
.Cl :
( Initiation

)( .
) (Lewis base
OH-
:
Y- .
145
146

( Propagation Step
( Termination Step

(
:
( (-
) H :
146
147

Coordination Polymerization or Sterioregular Polymerization

.

) (heterogeneous catalyst

) (conserted mechanism

.
( ) (
Step-Growth Polymerization
) (
) (active center

) (
) (dimer
147
148

) (trimer
:

M1 + M1
M2
M 2 + M1
M3
M 2 + M 2
M4
M 3 + M1
M4
M 3 + M 2
M5
M 3 + M 3
M6
M 3 + M 4
M7
M n + M x
Mn + x

) (functional group
.

.

) (
) (

) (poly(thioglycolate
148
149

) (chain growth
:
6 - :
( )(Caprolactam
(2-oxohexamethylene amine) :
( :
149
150

) - Aminocaproic Acid
:
150
151

) (step-growth
.

)polymerization
(condensation
) .(condensation polymers

) (functional groups .

.
.
151
152

152
153

:
(
Molecular Weight of Polymer

! Brittle

.
) (Branched
) (Crosslinked

.
153
154

(

.

C-O-C
) (ether linkage )(elasticity
) (flexibility
.

).(Crystalline Structures
154
155

( Molecular Forces :
:
:

).(intermolecular forces
:

:
( Dipole Effect

CH3 -CH 2+Cl-

)charges
(partial
155
156

.

.

.

.
156
157

( Hydrogen Bonding

) (OH ) (NH .HF

:

.
.
) (5
:
157
158

( Induced Dipole

.
.

.

).(induction
158
159

( Vander Waals Forces

:
(
Vander Waals Attraction Forces
) (London forces
) .(dispersion forces

.

.

:
159
160

(
Vander Waals Repulsion Forces

.

) .(Vander Waals's radius

) (.
160
161
161
PDF created with FinePrint pdfFactory Pro trial version http://www.pdffactory.com
162
:
Monomer
) (

) ( .
:

) (bi-functional :
( :
(
)(dicarboxylic
( )(glycols
( ).(diamines
162
163
(
:
(
)(hydroxy acides
(
).(amino acids
:
(

) (

:
163
164
) (n
:

) (
:
) (n
:
(
:
164
165
( )acid
(hydroxy
) (amino acid
:
)(n

:
165
166
(
:
( )(Direct Esterification

)( :
166
167
(
)(Trans Esterification

) (diacid
.
(
) (diacid chloride :

) (Shottan-Bauman
HCl
167
168
): (diamine
) (amino acids
) (6
:
(CH2)5 = R :
168
169
( :
) (
:
( Poly Urethane

): (diisocyanate
( )(Poly Carbonate

) (phosgene ) (A
): (bisphenol A
169
170
) (
)adioamide
(polyhexamethylene
) (Nylon 66) (66

) (adipic acid
) (hexamethylene diamine
:
:
) (66

) (66 ) (6
170
171
)(6
)(
. 6 ) (11
) (610
.
171
172
: Addition Polymers
Monomer Reactivity :

:
(
) (double bond

) (CH2 = CH2 ) (CH2 = CH - CH3
:
(
) (lactones ) (lactams
).(cyclic ether
172
173
(
): (double bond
)
.(vinyl compounds
X= (Cl, CN, OH...etc).
CH 2 = CH-X
vinyl compound
CH 2 = CH 2
ethylene
:
( : Free Radicals

) (peroxides
).(benzoyl peroxide
PH-CO-O - O- OC- PH
2PHCOO
Benzoyl Peroxide
Free Radical
173
174
( Cations
) (HCl
) (Lewis acids AlCl3 ) BF3
( :
BF3 + H 2 O
[ BF3OH ] H +
-
( Anions

) (NH2-
:
KNH 2
K + + NH 2 -
174
175
(
)(Heterogeneous

) (Zeigler Nata
:
( Al(C2H5)3
( TiCl4
(
)(Heterocyclic
) (lactone ) (lactam
:
175
176

) ( .

.

.
176
177
) : (
.
CH2 = CH2
CH2 = CH-CH3
CH2 = CH-CH2-CH3
CH2 = CH-CH=CH2
CH2 = CHCl
CF2 = CF2
CH2 = CH-O-R
CH2 = CHCOOCH3
CH2 = CH-CN
*) (+ (-)
177
178
:
Three-Dimensions Network Polymers
( )( Linear Polymers

.
.
)
( .

) (
.Covalent
178
179

)
) (Covalent

) .(linear

) (thermoplastic

.
(
Three Dimensional Network

) (multifunctional

.
179
180

.Thermoset
:
( phenol-formaldehyde
( urea-formaldehyde
( divinyl benzene
( vulcanized rubber
( .
180
181
: Copolymerization

Copolymer .

(
:
( :
) (A, B
)(alternate
:
-(A-B-A-B-A-B-A-B-A-B)-
( :

) (block copolymer :
)-(A-A-A-A-A-B-B-B-B-B181
182
( :

).(random polymer
)-(A-B-A-A-B-B-B-A
( ) (
Two-dimensions
) (graft copolymer

. :
182
183
(
Ladder Copolymer

.
:
183
184
) : ( Thermoplastics
-CH2CH2CH2 = CH2
-CH2-CH2-CH3
CH2 = CH-CH3
styrene
CH2 = CH-Cl
vinyl chloride
CH2 = CH-COOCH3
methyl acrylate
methyl methaacrylate
184
185
) : ( Thermoplastics
CH2 = CH-CN
acrylonitrile
-
CF2 = CF2
)(
Tetrafluoroethylene
) (
CH2O
-CF2-CF2-
formaldehyde
-CH2-O-
185
186
) : ( :

) (66

H2N(CH2)6NH2

HOOC(CH2)4COOH
[OC(CH2)4CONH(CH2)6NH]n
HO(CH2)2OH
186
187
) : ( :
[HN-(CH2)5CO]n
) (6
187
188
) : ( :
Cl-CO-Cl
A
H2O

O=C=N-R'-N=C=O

HO-R-OH
[O-R-O-CO-NH-R'-NH-CO]n
188
189
) : ( Thermoset

CH2O
) (
CH2O
H2N-CO-NH2
) (
Urea
189
190
) : ( Thermoset

) (
CH2O
) (
190
191
: ) : ( Thermoset

) (
191
192

Condensation
Polymerization
192
193

Condensation Polymerization

Functional Groups
Linear Polymers
).(crosslinked polymers

) (dimer )(trimer
)...(tetramer

) (oligomers

.

) (interlinkage groups
193
194

) ( .
) : (

Polyester

Interlinkage Group

polycarbonate

polyamide

polyether
(R O)n
-O-

polyacetal

polyurethane

polyurea
cellulose
-C-O-C-

pheno-formaldehyde resin

Polysulphide
-CH2-
(R S)n
-S-

Polysiloxane
- Si O -

Urea-Formaldehyde Resin
-N-CH2-
194
195

) (kinetics

).(chain transfer

)
(.

:
195
196

196
197

Classification of Condensation Polymerization Reactions

Reactions Involving Addition-Elimination to the Carbonyl Group
197
198

:

Polyamides

.

.
:

R-ONa :
PbO Mg(OR)2 Zn(BO3)2 .
) (alcoholysis
) ( )
( . :
198
199

:

) (R-CO :
:
Reactions of Acid Chlorides and Anhydrides
) (acid chlorides
) (anhydrides

:
199
200

) .(alkyde resins
) (phthalic anhydride :
200
201

(

Reactions Involving the Formation of Cyclic
Compounds Versus Polymeric Chains

)acids
(amino
)acids
(hydroxycarboxylic
) (lactam
) (lactone
:
201
202

.

6-
:
202
203

Carbonyl Addition Substitution Reactions

).(substitution

-
) (melamine-formaldehyde
) (phenol phormaldehyde resin

) . (urea formaldehyde resin

:
203
204

(
Nucleophilic Substitution Reactions

)resins
(epoxy
204
205

(
Double Bond Addition Reactions

)group
(urethane

) (diisocyanate
) (dihydroxy compounds :

) (
-
205
206

(
Reactions Involving Free Radical Coupling Mechanism

) (

) (
:
206
207

(
Aromatic Electrophilic-Substitution Reactions

.
) (polybenzyl )
( ) (poly (arylene - alkylene ) (
) (poly(p-phenylene :
207
208

208
209

Kinetic of Condensation Polymerization

) .(1 %

:
(

.
(

.
( .

.
209
210

:

:
)~~~(
.
) (esterfication
) (equilibrium

.

210
211

.

.

:
= k 3 ~~C + (OH)2 [ ~~OH ] ......
)(D
] ~~C + (OH) 2 , [ ~~OH ] , [ ~~COOH
] - d [ COOH
dt
= Rp

/ .

C + (OH) 2
C + (OH) 2
:
211
) (A
212

+
k1 ~~C (OH) 2 A
=
.................................(F)
k2
~~COOH
HA
[
][ ]
~~C + (OH) 2 =
Rp =
Rp =
C + (OH) 2
dt
k 2 A -
= k 3 ~~C+ (OH) 2 [ ~~OH ]
= k3
- d [ COOH ]
dt
...............(G)
k1 [ ~~COOH ][ HA ]
- d [ COOH ]
dt
- d [ COOH ]
k 2 A -
- d [ COOH ]
= k 3 ~~C+ (OH) 2 [ ~~OH ]
Rp =
dt
~~C+ (OH) 2 =
Rp =
k1 [ ~~COOH ][ HA ]
k1 [ ~~COOH ][ HA ]
k 2 A -
[ ~~OH ]
k 3k1 [ COOH ][ HA ][ OH ]
k 2 A -
...........(H)
[ A-]
:
212
213

HA H + + A H + A -
K HA =
[ HA ]
A - =
K HA [ HA ]
H +
..................(J)
[ A-]
:
A - =
Rp =
Rp =
Rp =
K HA [ HA ]
H +
(J )
K HA [ HA ]
H +
- d [ COOH ]
dt
- d [ COOH ]
dt
- d [ COOH ]
Rp =
A - =
dt
- d [ COOH ]
dt
=
=
k 3 k1 [ COOH ][ HA ][ OH ]
k 2 A -
k 3k1 [ COOH ][ HA ][ OH ]
K [ HA ]
k 2 HA +
H
k 3 k1 [ COOH ] HA [ OH ] H +
k 2 K HA HA
=
k 3 k1 [ COOH ][ OH ] H +
k 2 k HA
213
...............(K)
214

): (K, H
] - d [ COOH ] k 3k1 [ COOH ][ HA ][ OH

= Rp
dt
k
A
2
- d [ COOH ] k 3 k1 [ COOH ][ OH ] H
= Rp
dt
k 2 k HA
:
Kinetics of Polymerization without External Catalyst

) (self catalyzed .
) (HA )(COOH
:
)= k [ COOH ] [ OH ]........(A
2
214
] -d [ COOH
dt
215

k ) (k3, k2, k1 ]. [A

] - d [ COOH
2
] = k [ COOH ] [ OH
dt

) (third order reaction
] [COOH
2
.

] [OH
] [COOH ) (A :
)= k [ C] .[ C] = k [ C] ........(B
2
]- d [C
dt
= Rp
C .
) Integration (B :
1
)+ X......................(C
c2
215
= 2kt
216

:
: X
: T . ) (t = 0
) (c = co :
1
co 2
=X
): (C
2kt = 2 + X
c
.

) (t = P
) t = (1 P
t
:
)c = co (1 - P ) ..................(D
c ): (C
:
216
2kt = 2 + X
c
217

) c = co (1 - P
1
+X
c2
1
+X
) (1 - P
) ) ( co (1 - P
1
+X
)+ X..................(F
) ( co ) (1 - P
2
1
2
= 2kt
= 2kt
= 2kt
= 2 ( co ) kt
2
) (1 - P
) (Dp = degree of polymerization

) .(Xn ) (1/1-P ): (F
1
2
+ X
= 2 ( co ) kt
2
) (1 - P
+X
:
1
2
= 2 ( co ) kt
2
) (1 - P
1
) (1 - P
= Dp
) 2 ( co ) kt = ( Dp ) + X.................(G
2
217
218

) (1/1-P Dp ) (t
).(
) : ( ) (DE ) (A
Dp
218
219

:
Kinetics of Externally Catalysed Condensation Polymerization
][HA
] [H+
:
k1 k 3
)[ COOH][OH]...........(A
k 2 k HA
] d [ COOH
dt
Rp = -
) (c )(A
:
dc
)= k C2 ...........................(B
dt
Rp = -

.

) (B :
1
)+ X .....................(C
1-p
219
= co kt
220

) (1/1-p Dp
:
)co kt = Dp + X .....................(D
Dp
) (t ).(
) : ( Dp
) % 0.4 ) (p-toluenesulfonic
( .
220
221

221
222

Polymerization
by Addition
222
223

Polymerization by Addition
:
( .
( :
.

) .(steric hindrance

) (electron withdrawing
.

.
) (anionic polymerization

) (electron donating groups

.
223
224

. ) (
.
) (

CH2=CH2

CH2=CH-CH=CH2

CH2 = CH-CN
H2C = CH O -R
224
225

Type of Initiators Used in Free Radical

Polymerization

.

.
: Thermal Initiators

.

) (peroxides
)(hydroperoxide
) (azo-compounds
) (diazo-compounds
) (
225
226

) (Thermal Catalysts

)(benzoyl peroxide
)peroxide
(cumene
) (AIBN) azoisobuteronitrile
:
226
227

: Photoinitiators

) (organometallics :
227
228

228
229

: Redox Initiators

) (0 - 50 C

) .(emulsion polymerization

:
229
230

Kinetic of Free Radical Addition Polymerization

.
M : I

( :

:
kd
I
2R
ka
R + M1
R-M1
:
: kd )(decomposition constant
: ka .
230
231

( Propagation Step

:
k
p
R-M1 + M
RM 2
p
RM 2 + M
RM 3
p
RM x + M
RM x + I
:
: kp

.
( Termination
:
( )(coupling
k tc
Mx + My
Mx + y
231
232

( Disproportionation

:
k td
Mx + My
Mx + My
(
Chain Transfer Reactions

:
k tr M
M x + M
M x + M
k tr S
)M x + S (solvent
M x + S
k tr P
)M x + P (polymer
M x + P
k tr I
)M x + I (Initiator
M x + I
:
- d M
]R i = = 2 f k d [ I
dt
:
232
233

: F .

.
] : [I
: Ri

:
- d M
2
R t = = 2 k t M
dt

:
] R t = 2 k t M + k td M x M y + k tm M x [ M ] + k tr M x [S] + k tp M x P + k tr.I M x [ I
2
233
234

).(steady state
Ri = R t
Ri Rt :
- d M
]R i = = 2 f k d [ I
dt
i
- d M
2
R t = = 2 k t M
dt
t
at steady state : R i = R t
2
2 f k d [ I] = 2 k t M
]2 f k d [ I
2 kt
]f k d [ I
kt
]f k d [ I
kt
= M
2
= M
= M
] f k d [ I
= M
kt
1/ 2
:
] - d [M
= RP
= k p [ M ] M
dt
234
235

] - d [M
= R P
= k p [ M ] M
dt
1/ 2
] f k d [ I
= M

k
t
:
] - d [M
= RP
= k p [ M ] M
dt
] f k d [ I
= M
kt
1/ 2
] - d [M
] f k d [ I
= RP
=
k
M
[
]
p
dt
kt
1/ 2
] [ I .
1/ 2
) (f

) (f
).(
235
236

) : (
) (AIBN 0.20
1.00 0.50/ .
] [ M
3/ 2
) ( ) (Rp
]. [ I
1/ 2
236
237

) : ( Rp ) (I1/2
) (50 C :
) (AIBN ).(O) (60 C
) ( Rp ].[M
) : ( Rp

) (.
237
238

) ( Dp :
Rp
Rt
= Dp
:
: Rt
Rp
. R
t
) (kinetic chain length

) ( Dp :
] k p [ M ] M k p [ M
= Dp
=
2
k t M
k t M
] f k d [ I
= M
k
t
1/ 2
238
]kp [M
= Dp
k
M
t
239

]k p [M
k t M
= Dp
] f k d [ I
= M
kt
]k p [M
= Dp
1/ 2
] f k d [ I
kt
kt
1/ 2
][M
1/ 2
][ I
kp
) (f kdkt
1/ 2
= Dp
) ( Dp

) . ( Dp

) ( Dp :
R p

Rp
f k d [ I] + k tr.m [ M ] M + k tr.s [S] M + k tr.I [ I] M
239
= Dp
= Dp
240

Rp
= Dp
f k d [ I] + k tr.m [ M ] M + k tr.s [S] M + k tr.I [ I] M

.
)(c
Chain Transfer Constant :
)= (c
k tr
k p
C
:
k tr . M
kp
= CM
k tr . S
kp
= Cs
k tr .I
kp
= CI
ktRp
k t R 2p
]S
[
1
= 2
+ C M + Cs
+C
2
Dp
[ M ] I k 2p f k d [ M ]3
]k p [M
240
241

ktRp
k t R 2p
]S
[
= 2
+
C
+
C
+
C
M
s
I
2
3
2
Dp
M
] [
]k p [M
] k p f k d [ M
) (chain transfer agents S

Rp :
kt Rp
][ I
1
= 2
+ CM + CI
Rp
]k p [M
][M
1
kt Rp
][ I
= 2
+ CM + CI
R
k
M
M
[
]
[
]
p
p
.Rp
) (
Rp

.
241
242

)(
242
243

:
)Low Density Polyethylene (LDPE

.
) (branched
.

)Manufacture of (LDPE

.
) (1000 3000 atm
) .(250 C
) (heat of polymerization ) (800 cal/g
).(164 cal/g
243
244

) (exothermic
) (34000 cal/mol

.

:
)
(autoclave .

)(batch system
).(tubular reactors

.
).(continuous system

) (initiators : :
244
245

.

) (190 C
) .(1500 atm
).(10 15 %

.

.

).(0.91 0.94 g/cm3
) (crystallinity ).(50 60 %
.
).(120 130 C

) (tertiary carbon atom
245
246

) (stabilizers
) .(antioxidants
.
: ) (Polystyrene

) (glass polymers .
) .(thermoplastics
) (80 C

) (rigid foam.

:
246
247

) (dehydrogenation
)(600 C
.

.

:
(
(
(
( .
.

.
247
248

:
Styrene Copolymers

) (styrene butadiene rubber) (SBR
) (25 % . ) (SBR
:
Nitrile Rubber

)styrene
butadiene
(ABS) (acry

.

248
249

.
) (18 %
) (40 %
.
) (emulsion polymerization
).(SBR
:
)Poly(Vinyl Chloride (PVC

) (vinyl chloride
) (suspension polymerization
) (50 C ) (9 atm

) .(- 14 C ).(88 %

.PVC
249
250

Vinyl Chloride
PVC
)(two stage process

:

1, 2 dichloroethane
:

:
250
251

)(PVC

.
)(20 30 %
)(plasticizer
) (PVC

) (extrusion
30 %
) (5 % )(fillers
. )(PVC

. ) (PVC
.
PVC
Coating
.
251
253

) (

Plasticized
Nonplasticized
*
87
)(Tg
*
212
)(Tm

5
5
(10 25) 10 (35 63) 10
tensile strength kg/m2
200 450
2 - 40
)elongation (%
1.16 1.35
1.35 1.45
g/cm3
11 25
1.52 1.55
D

48
3 3.3
dielectric constant D
- 120
12 - 130
ABS
SBR
100
240
*
*
*
*
(42 161) 104

90 800
0.91 0.94
1.51
(35 84) 105

1.0 2.5
1.04 1.09
1.59 1.60
(245 434) 104

5 60
1.02 1.04
-
(42 210) 104

300 1000
0.93 1.10
1.52 1.55
2.25 2.3
2.4 2.65
2.4 4.5
3.4 2.5
253
254

Ionic Chain
Growth Polymerization
254
255

Ionic Chain Growth Polymerization
)(active centers
) ( ) (cationic ) ( ).(anionic

)ions
(carbonium )(carbonion
.

): (ion pair

)(growing ion
) (ion counter
.
.
255
256

) (insertion

.

) (coupling
.
: Cationic Polymerization

.

:
256
257

) (delocalization

) (alkoxy (-OR
.

) (C6H5-
) (CH2-CH- ) (-R :
257
258

258
259

) (initiators
:
( Protonic Acids

.

)(weak nucleophile

:
259
260

) (A-
:

.

) (perchloric acid )(sulphuric acid
)acid
(phosphoric

.
( Lewis Acids

:
( )(AlCl3
( BF3
260
261

( SnCl4
( ZnCl2
( TiBr4

) (butyl rubber
).(polyisoprene
(
) (carbonium ion

:
-
RCl + SnCl4
) R + ( SnCl5

) (I2 ) (Cu2+
)ion
(oxonium
261
262

) .(high energy radiation

:
262
263

C ) (RH
. ).(M

:
k
) H+ ( CR C + RH
:
ki
+
) H + ( CR
HM
CR
(
)
:
kP
) HM n -M + ( CR HM + ( CR ) + nM
:
kt
) M n + 1 + H + ( CR ) HM n - M + ( CR

:
) R i = k [ M ] H + ( CR
263
264

H + ( CR )-
] R i = k k i [ C][ RH ][ M
:
: k
HM + ( CR )-
) (ion pair .
) (steady state

:
Ri = R t
] k t HM + ( CR ) = k k i [ C][ RH ][ M
] HM + ( CR )- = k k i [ C][ RH ][ M
k
t
HM + ( CR )-
] [ C][ RH ][ M
k kik p
264
kt
= Rp
265

) ( Dp :
][ M

kp
kt
Rp
Rt
= Dp
k kik p
2
] [C][ RH ][ M
= Rp
kt
] [ M
2
] [ C ]. [ RH
] [ M
kp
kt
Rp
Rt
= Dp
] [ M ]. [ C

:
) (polyisoprene

).(butyl rubber
265
266

) (isobutene

.AlCl3
:

.

) (0 50 C
) (3000
.

) (- 100 C

.
266
267

:
Anionic Polymerization

.
.

( )(ion pair

.
(
) (
.
( .

267
268

) (induction

.
:
)(CN

.
:
)(CN-CH2=CH
:
268
269

269
270

Anionic Initiators
: Alkali Metals
)(Na
.

) (biphenyl

) (aromatic free radical anion :
)) (sodium naphthalene (
)) (sodium biphenyl .(
(
270
271

K + NH3
KNH 2 + H +
) ( NH -2
:
) (
.
271
272

: Metal Alkyls

) (butyl lithium
).(triphenylmethyl sodium
: Metals Amides

) (sodium amide
).(liquid ammonia
272
273

Kinetic of Anionic Polymerization

) (free ion
.

) (
.

:
:
] R i = k i H 2 N:- [ M
) ( H N:
-
] [ KNH 2 ][ M
K +
273
R i = kik
274

:
R p = k p M - [ M ]
:
R t = k tr. S M - [ NH 3 ]

: ( steady state)
R i = kik
[ KNH 2 ][ M ]
K +
R t = k tr. S M - [ NH 3 ]
Ri = Rt
kik
at steady state
[ KNH 2 ][ M ]
M - =
K +
= k tr. S M - [ NH 3 ]
k i k [ KNH 2 ][ M ]
K +
k tr. S [ NH 3 ]
k k [ KNH 2 ][ M ]
M - = i
k tr. S [ NH 3 ] K +
274
275

(R
= k p M - [ M ]
) M
R p = k p M - [ M ]
Rp
M - =
M - =
Rp
k p [M]
k p [M]
k i k [ KNH 2 ][ M ]
k tr. S [ NH 3 ] K +
k i k [ KNH 2 ][ M ]
k tr. S [ NH 3 ] K +
k i k k p [ KNH 2 ][ M ]
Rp =
k tr. S [ NH 3 ] K +
Rp =
k i k [ KNH 2 ][ M ]
k tr. S [ NH 3 ] K +
:
R p = k p M - [ M ]
R t = k tr. S M - [ NH 3 ]
Dp =
Rp
Rt
Dp =
Dp =
=
Rp
Rt
k p M - [ M ]
k tr. S M - [ NH 3 ]
=
k p [M]
k tr.s [ NH 3 ]
[M]
Cs [ NH 3 ]
275
276

1
] . [ NH
3

)(
)(polyisoprene

) (acetal resin
)(dilrine
) .(celcon

).(engineering plastics

) (formaldehyde ) (trioxane

276
277

.
) (nucleophilic

) (tertiary aliphatic amines )(phosphines
) (arsines.

Factors Affecting Anionic Polymerization

) (Rp
:
( The Effect of Temperature

.

) (activation energy
.

277
278

.

.

).(stereo regularity
( The Effect of Solvent

) (ion pair
.
.
278
279

( the Effect of Counter Ion

:

) (1,2 dichloroethane ) (25 C

0.003 17
.
:

I3

.
.

. ) (
279
280

) (25 C
) (THF .
kp
) (dissociation constant
) (solvation ) (Li
) (Cs

.
.
) : (
25 C ) (THF .

Counterion
)(kp
k 107
160
2.2
Li+
80
1.5
Na+
60 80
0.8
K+
50 80
0.1
Rb+
22
0.02
Cs+
280
281

Ring Opening
Polymerization
281
282

Ring Opening Polymerization
:

:
.

) (interlinkage group .
.

( :

.
282
283

(

.
( :

) .(8 11 atoms

. )(
:
283
284

) : (

:
(
.
( )(ring opening polymerization

.

). (105.5
284
285

Mechanism of Ring Opening Polymerization

) (ionic initiators )(molecular initiator

:
285
286

: (BF3) (H+) (OH-) (OR-)
.

.

.

) (chain growth
)( )(step growth

.

.
286
287

Polymerization of Cyclic Ethers

.

.

:
- ) (.

.

287
288

:
)) (tetrahydropyran )(
- )) (1, 4 dioxane (.
288
289

Anionic Polymerization of Cyclic Ethers

:
)(ethylene oxide
) )(propylene - oxide
:

) (Na+--OCH3 :
289
290

) (aprotic solvent
) (terminating agents

) .(living anionic polymerization
) (unsymmetrical

:
290
291

.

) (2
.

)(KOH

.

.
291
292

)(t

) (t

:
)= ( D p )t = (t
)(t

) (5000
) .(10,000

:
292
293

293
294

Cationic Polymerization of Cyclic Ethers

) (oxonium ion

.

( Protonic Acids

).(triflouroacetic acid
): (secondary oxonium ion
294
295

) (tertiary oxonium ion

.
( Lewis Acids

SnCl4 BF3 :

:
BF3 + H 2 O
) ( + H ) F3 B ( OH -
295
296

(
Organometallic Compounds

Zn(C2H5)2 .Al(C2H5)3

.
296
297

) (

:
C 2 H 5 -Zn-O-Zn-C 2 H 5
( C 2 H 5 )2 -Al-O-Al- ( C 2 H 5 )2 ,
( Carbonium Ions

.
) (H+ ). (R+

:
297
298

Polymerization of Cyclic Amides

.
) (lactam

.
:

).(beta propiolactam

).(gamma-butyrolactam
298
299

). (delta-valerolactam

6-hexa-caprolactam
299
300

Anionic Polymerization of Cyclic Amides

:
-
-
-
-

:
M
:
300
301

) (1 :
) (II
) (I

:
301
302

) (III

) (III ): (I
) (IV
:
302
303

:
(
Cationic Polymerization by Protonic Acids
:
(
(
(
(
:
303
304

) (acidity
) (nucleophilic
.
(
) (Lewis Acid

) (SnCl4
.
2Caprolactam + SnCl4
( Capprolactam )2 SnCl4
Complex Compound
( Capprolactam )2 SnCl4
304
305

) (Infrared

.
(
Cationic Polymerization of Lactams by Amines

) (aniline ) (benzyl amine

) (ammonium salt
:
305
306

Polymerization of Cyclic Amide by Water Analysis

)(hydrolysis
:
306
307

Polymerization of Cyclosiloxanes

)(octamethylcyclotetrasiloxane
(
Anionic Polymerization of Cyclic Siloxanes

(CH3)2SiOK .
:
307
308

).(neocleophilic
(
Cationic Polymerization of Cyclic Siloxanes

)acids
(protonic
308
309

309
310

Copolymerization
310
311

Copolymerization
) (copolymerization

).(structure unit

).(homopolymer

.

.
:

.
311
312

.

.

:

)acrylonitrile-butadiene-styrene copolymer (ABS

.

.
) (SBR

ABS .
312
313

Types of Copolymers
: Random Copolymers

) (randomly
.
A B
:

A
B .
313
314

: Alternative Copolymers

.

. :
: Block Copolymers

) (blocks .

:
314
315

: Graft Copolymer

:
315
316

Condensation Copolymers

) (

) (polyethylene terphthalate
.

[-CH2-CH2-
] .OCO-C6H4-COO-

:
( -CH2-CH2-OCO-C6H4-COO-
( CH2-CH2-CH2-OCOC6H4COO-
316
317

Preparation of Condensation Copolymers
.
:
( copolyamides
( copolyesters
( copolycarbonates
( copolyurethanes

.

) (hydroquinone
) (random copolycarbonates :
317
318

)(Alternative Copolymer

) (alternative copolymer )(copolyamide
)(HOOC-R-COOH
) (diamine :
NH2-R'-NH2 (I H2N-R''-NH2 (II
)(I

: ) (trimer
:
318
319

2HOOCRCOOH + H 2 NR'-NH 2
HOOCRCONH-R'-NHCO-R-COOH + 2H 2O
III
) (III) ( HOOCRCONH-R'-NHCO-R-COOH
) (II
) (I, II :
HOOCRCONH-R'-NHCO-R-COOH + nH 2 N-R''-NH 2
HO- ( -CO-R-CONH-R' -NH-CO-R-CONH-R'' NH- )n - H + ( 2n-1) H 2 O
319
320

)(Block Copolymers
) (block copolymers
) (block

.

Applications of Condensation Copolymers

)(crystalline melting point
) (Tm ) (Tg )(elasticity

) (Tg
) (Tm
.
320
321

Addition Copolymers
) (

) (ABS )(SBR
) (.

:
(
free radical copolymerization
(
cationic copolymerization
(
anionic copolymerization
321
322

Composition of Addition Copolymers

.

): (homopolymerization

:
( )(maleic anhydride
( )(stilbene
( )(fumaric acid ester

.

.
322
323

) (M1, M2

) (Active Center
M1 :
~~~M1
M2 :
~~~M2

:
k11
~~~M1 + M1
~~~M1
)1
k12
2) ~~~M1 + M 2
~~~M 2
k 21
3) ~~~M 2 + M1
~~~M1
k 22
4) ~~~M 2 + M 2
~~~M1
k22 k21 k12 k11

.
323
324

M1
M2
:
- dM1
] = k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1
dt
- dM 2
] = k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2
dt

:
- dM1
] = k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1
dt
- dM 2
] = k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2
dt
- dM1
] dt = k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1
] - dM 2 k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2
dt
] - dM1 k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1
=
] - dM 2 k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2
] dM1 k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1
=
] dM 2 k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2
] [ ~~~M 2 ] , [ ~~~M1

] [~~~M ] [ ~~~M :
1
324
325

k 21 [ ~~~M 2 ][ M1 ] = k12 [ ~~~M1 ][ M 2 ]

[ ~~~M1 ] =
k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
~~~ [ M ]
k 21 [ ~~~M 2 ][ M1 ]
~~~M
=
[
]
k
M
[
]
12
2
dM1 k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1 ]

: dM = k [ ~~~M ][ M ] + k [ ~~~M ][ M ]
2
21
1
2
22
2
2
dM1 k11 [ ~~~M1 ][ M1 ] + k 21 [ ~~~M 2 ][ M1 ]

=
dM 2 k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2 ]
[ ~~~M1 ] =
dM1
=
dM 2
k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
k11k 21 [ ~~~M 2 ][ M1 ][ M1 ]
+ k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2 ]
k11k 21 [ ~~~M 2 ][ M1 ]
+ k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
2
dM1
=
dM 2
k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2 ]
( k [ ~~~M ][ M ])
21
k11k 21 [ ~~~M 2 ][ M1 ]
+ k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
dM1
=
dM
k
~~~M
M
+
k
~~~M
M
2
21 [
1 ][
2]
22 [
2 ][
2]
k11
= r1 ,
k
12
k 22
= r2 :
k 21
325
326

k11k 21 [ ~~~M 2 ][ M1 ]
+ k 21 [ ~~~M 2 ][ M1 ]
k12 [ M 2 ]
2
dM1
=
dM 2
k 21 [ ~~~M1 ][ M 2 ] + k 22 [ ~~~M 2 ][ M 2 ]
k11k 21 [ ~~~M 2 ][ M1 ]
k [ ~~~M 2 ][ M1 ]
+ 21
dM1 k 21k12 [ M 2 ][ ~~~M 2 ][ M 2 ] k 21 [ ~~~M 2 ][ M 2 ]
=
k 21 [ ~~~M1 ][ M 2 ] k 22 [ ~~~M 2 ][ M 2 ]
dM 2
+
k 21 [ ~~~M 2 ][ M 2 ] k 21 [ ~~~M 2 ][ M 2 ]
2
k11 k 21 ~~~M 2
M1
k 21 ~~~M 2 [ M1 ]
dM1 k 21k12 M 2
~~~M 2
M 2 k 21 ~~~M 2 [ M 2 ]
=
k 21 [ ~~~M1 ] M 2 k 22 ~~~M 2
dM 2
M 2
+
k 21 [ ~~~M 2 ] M 2 k 21 ~~~M 2
M 2
k11 [ M1 ]
+
k12 [ M 2 ]
dM1
=
dM 2 [ ~~~M1 ] k 22
+
[ ~~~M 2 ] k 21
k11
k
= r1 and 22 = r2
k12
k 21
k11 [ M1 ]
+
k12 [ M 2 ]
dM1
=
dM 2 [ ~~~M1 ] k 22
+
[ ~~~M 2 ] k 21
[ M1 ]
[M2 ]
dM1
=
dM 2 [ ~~~M1 ]
+r
[ ~~~M 2 ] 2
r1 [ M 2 ] [ M1 ]
+
M2 ]
[
[M2 ]
dM1
=
dM 2 [ ~~~M1 ] [ ~~~M 2 ] r2
+
[ ~~~M 2 ] [ ~~~M 2 ]
r1 [ M 2 ] + [ M1 ]
[M2 ]
dM1
=
dM 2 [ ~~~M1 ] + [ ~~~M 2 ] r2
[ ~~~M 2 ]
r1 +
326
divided by ( k 21 [ ~~~M 2 ][ M 2 ])
327

] r1 [ M 2 ] + [ M1
] [M2
= dM1
dM 2 [ ~~~M1 ] + [ ~~~M 2 ] r2
] [ ~~~M 2
:
] r1 [ M 2 ] + [ M1
] [M2
dM1
=
dM 2 [ ~~~M1 ] + [ ~~~M 2 ] r2
] [ ~~~M 2
] [ ~~~M 2
] dM1 r1 [ M 2 ] + [ M1
=
dM 2
] [M2
[ ~~~M1 ] + [ ~~~M 2 ] r2
] [ ~~~M 2
] dM1 r1 [ M 2 ] + [ M1
=
dM 2
] [M2
[ ~~~M1 ] + [ ~~~M 2 ] r2
)] dM1 [ M1 ] ( r1 [ M1 ] + [ M 2
=
)] dM 2 [ M 2 ] ([ M1 ] + r2 [ M 2
:
dM
)] [ M1 ] ( r1 [ M1 ] + [ M 2
1
=
)] dM 2 [ M 2 ] ([ M1 ] + r2 [ M 2
)(copolymerization equation

.
327
328

: r1, r2 ) (reactivity ratio

r
.
r1
) ( ~~~M1
M1 M1
.
r1
M2
) (r1 = 0 M1
).(homopolymer
r2 r1 Reactivity Ratio :
(
1
= r1
r2
) (r1 r2 = 1
.
( ) r1 = 0 (r2 = 0
.
328
329

.

( r1 r2
) ( r1 < 1) , ( r2 < 1 .
( ) (r1 = r2 = 1
.
:
M1- M1-M2- M1- M2- M2- M2
( r1 r2
) ( r1 > 1) , ( r2 > 1

.
( r1 ) ( r1 > 1 r2
) : ( r2 < 1
M1
M2 .
329
330

) (mole fraction
f1 f2
M1 M2
F1 F2 M1 M2
:
] [ M1
] [ M1 ] + [ M 2
] d [ M1
= F1 =1- F2
] d [ M1 ] + d [ M 2
= f1 = 1- f 2
] d [ M1
F
=1F
=
1
2
d
M
+
d
M
[
]
[
]
1
2
] [ M1
= f1 = 1- f 2
M
+
M
[
]
[
]
1
2
dM
)] [ M1 ] ( r1 [ M1 ] + [ M 2
1
=
)] dM 2 [ M 2 ] ([ M1 ] + r2 [ M 2
r1f12 + f1f 2
F1 = 2
r1f1 + 2f1f 2 + r2f 22
330
331

r1f12 + f1f 2
F
=
1 r f 2 + 2f f + r f 2
1 1
1 2
2 2
. r1 r2
. r1 r2

) (Initiation M1 M2
) (Methyl Methacrylate r1 r2
:
)(
r1
0.52
10
0.1
r2
0.46
0.1
6
) (

.

1 : 1

.

331
332

) : ( . F1 F2
2
1
3 SnCl4 /Na
.
332
333

)(inhibitors
) (chain transferring agents

.

) (initiator

.

) (AIBN

.
333
334

)(monomer reactivity
.

) (r1r2

:
( Ideal Copolymerization
)(r1.r2 = 1

:
k 22
k
= 12
k 21
k11
:
1
r1
= r2
334
335

] [ M1
] [M2
= r1
] d [ M1
] d [M2
:
r1 f1
r1f1 + f 2
= F1
) (r1 = r2 = 1
) ( ~~~M1 ) ( ~~~M 2

.
:
r2 < 1
r1 > 1,
r2 > 1
r1 < 1,

) ( F1 M1
f1
335
336

) (
M1 r1 1
M1 r1 1
) : ( ) M1 ( ) f1
Mi ( r1
).(r1 r2 = 1

)(r1 = 10
) (r2 = 0
.M2 M2
336
337

(f2 = 0.80) 80
) (71 % M2
).(F2 = 0.71
(
Alternative Copolymerization
Alternative r2 = r1

) (F1 = 0.5 ) (dM1/dM2 = 1
M1 M2
M2 M1

.

.
:
=1
] d [ M1
] d [M2
337
338

:
0 < r1 r2 < 1
) (r1. r2
)(r1 = r2 = 0
.

r2 r1
) (0-2
. ) (r1 = 2
r1
r1r2
) ( F1 f1
r1
F1 f1
) .(azeotropic copolymerization

:
338
339

M1
M2
] d [ M1
] d [M2
:
M1 r2 - 1
=
M 2 r1 - 1
:
1 - r2
2 - r1 - r2
= f1

( r2 << 1, r1 >> 1) :

) (homopolymers

) (vinyl acetate
55
).(0.01
339
340

) : ( ) (F1
) (f1 r1 r2 0.5
340
341

(
Block Copolymerization
r1 r2 ) (1 < r2 , 1 < r1

)( r1r2 > 1
) (block copolymer
.

.

. r1 r2

) (homopolymerization .
341
342

Variation of Copolymer Composition with Conversion

) (conversion ratio
.
M

)(M1

) < F1
( f
) (dM ) (M1 (M-

) dM)(f1-df1 M1
) (M1 :
Mf1 - ( M - dM )( f1 - df1 ) = F1dM
342
343

df1dM

:
f1
df1
dM
M
=
ln
=
Mo M
) M o ( f1 )o ( F1 - f1
M
Mo (f1)o m f
.
) (1 M/Mo
F1
:
y
f f ( f1 )o
M
1 =1- 1 2
Mo
f
f
f
(
)
(
)
1 o 2 o 1
:
r2
1 - r2
r1
,
1- r1
1 - r2
) ( 2 - r1 - r2
1 - r1r2
,
) (1 - r1 )(1 - r2
343
344

Determination of Monomer Reactivity Ratio
Copolymerization

) (elemental analysis
) (spectroscopic methods
) (ultraviolet )(infra-red
)(nuclear magnetic resonance
344
345

:
) f12 ( F1 - 1
) f1 (1 - 2F1
= r2 +
r
2 1
) F1 (1 - f1
) F1 (1 - f1

r1 r1
.r2 ) (
) (activity ratio
.
M1
M2
)(
r1
0.02
0.15
0.04
4.2
2.7
0.75
1.35
8.8
0.46
20
10
55
17
0.23
345
r2
0.3
1.22
0.40
0.05
0.04
0.25
0.58
0.035
0.52
0.015
0.1
0.01
0.02
1.68

)(C
40
80
60
50
60
90
50
50
60
60
68
60
60
60
346

Factors Affecting Free Radical Copolymerization

r

.

.
346
347

:
( Effect of Temperature

r1 r2
0.52 0.46 )(60 C
0.59 0.54
).(131 C
( Effect of Pressure

r

r2 r1 )(0.16

) (0.54 ) (100 atm ) (0.91
).(1000 atm
347
348

:

.

.
:
C6 H5 - > -CH=CH 2 > -CN, OCR > COOH, COOR > Cl > OCOR > OR, OH
: Effect of Steric Hindrance

.
348
349

) (

.
.
) : (
78
- .
0.6
3.9
0.7
349
350

.

.

Ionic Copolymerization

) (
:
( ) (comonomers
:

.

.
350
351

(
) (ideal copolymerization )(r1 r2 1

.
( ) (r

.

Anionic Copolymerization

) (carbanion .
:
-CN > COOR > -C6 H5 -CH=CH 2 > -H

.
351
352

.

Cationic Copolymerization

:

) (Electron Density

.

.

:
< Vinyl Ethers < =
352
353

.

.
353
354

Polymerization Conditions and
Molecular Weights of Polymers
354
355

Polymerization Conditions and

Molecular Weights of Polymers
:
( )(homogeneous polymerization
( )(heterogeneous polymerization
:
Homogeneous Polymerization

) (
.
:
.
( )(bulk polymerization

) (initiators

355
356

.

) ( :
) ( ) (
) ( ) (
.

) (exothermic
) (condensation reactions
.
( Solution Polymerization

) (cooling medium

356
357

) (adhesives ) (coatings
) (dye additives
) (
) (poly(vinyl acetate )
().poly (viny alcohol
:

.
.

).(initiator
357
358

:
Heterogeneous Polymerization

.

( Suspension Polymerization
.

) (droplets
) .(suspension
.

.

358
359

.

) ( ) ( )
( )chloride
(vinylidine
(poly
)( )(poly (acrylonitrile
( Emulsion Polymerization

) (dispersion medium
.

:
) (ammonium persulphate

.
) (emulsifying-agent

) (micelles .
) (hydrophilic
)( ) (hydrophobic .
359
360

(
( )(alkyl aryl sulphate
(.

.
360
361

) : (
361
362

) (vinyl polymers
) (

).(styrene-butadiene rubber (SBR
(
Interfacial Polymerization

.

) (halides

.
362
363

:

) (immiscible

. .
(
Gas Phase Polymerization

.

.
363
364

(
Precipitation Polymerization
.

.

.

.
364
365

:

) (average molecular weights
.
)(mass-spectrometry

) (volatile

.
365
366

:
)(osmometers

)(light scattering
)(viscometry

).(ultracentrifugation

.
366
367

)(number average (molecular weight

) . ( M n
.

.
( M ) weight average molecular

w

)(viscosity average molecular weight
) ( M n
) . ( M
367
368

): (colligative properties
(
(
(
) ( M n

) ( M n
:
W
Ni Mi
=
Ni Ni
= Mn
:
: Ni Mi

)scattering
(light
) (ultracentrifugation
368
369

) ( M .
w
M w = Wi Mi
:
: Wi ) (weight fraction
Mi .

Mw
Wi :
Ni Mi
Ni Mi
= Wi
) : ( M w
Ni Mi
Ni Mi
= Wi
W M
N M M = N M
=
N M
N M
i
= Mw
369
Mw
370

) ( M
:
) ( W N
a 1/a
i
= M
:
: Wi .
: a ).(0.5 0.9
) (W )
1/a
Ni Mi
N
M
i i
) ( Wi Nia
= M
= Wi :
Ni Mi
Ni Mi
= Wi
) ( Wi Nia
= M
1/a
Ni Mi
= M
N M
i
i
1/a
) (a = 1 ) ( M
) . ( M w
370
371

) ( M
) . ( M w

. ( M n < M < M w ) :
M n
.

Mw
Mn
).molecular weight distribution ratio (MWDR
) (narrow distribution
Mw
M
n
) ( M n < M < M w .
371
372

End Group Analysis

) ( M n

) (25,000

.

) (titration :

)(standard solution

.
) (milliequivalents
.
372
373

Acetylation :

.

) ( M n :
= number of moles of Polymers/garm
number of mequivalents of carboxyl + number of mequivalents of hydroxyl
Weight of Polymer in grams 2 1000
) ( M :
n
1
Number of moles of Polymers / gram
= Mn

)(epoxy groups
) (epoxy resin .

373
374

) (spectroscopy

) (elemental analysis
.
374
375

) ( M
w
Determination Weight Average Molecular Weight
Determination of ( M w ) by Light Scattering

) (absorption

.
) (amplitude of electron vibration.
375
376

) (amplitude factor

) (amplitude :
t = Hc Mw
:
: H ) (n
) (c :
2
) 32 3n o2 ( dn/dc
=H
3 4 No
:
: T ) (turbidity .
:
: No )(Avogadros' number
: dn/dc .
376
377

: ) ( M w

Determination of ( M n ) by Ultracentrifugation

) (brownianmotion

) (sedimentation
.

.
) ( M w
) (centrifuge )
70,000 (

) .(sedimentation velocity method
377
378

) (S
:
) 1 dr m (1 -
=
W 2 r dt
f
=S
:
: M
: f ).(frictional coefficient
) (coiled polymers
f )(diffusion coefficient
): (infinite dilution
KT
f
=D
) ( M w :
D
RT
=
S
) Mw (1 -

) ( M
w
.
378
379

) ( M
Determination of Viscosity Average Molecular Weight

) (flow resistance .

.
. ( M w ) viscosity average molecular weight

) (relative

)(capillary tube) (t

) (to .
:
379
380

( ) : ( rel
t
t
tt
t
=- 1
t
( ) t : ( sp
t - t
( ) t c : ( red
sp
c
ln rel
( :
c
= inh
t - t
t
c
( c 0 :
:
: to
: t
c

.
380
381

) . ( 0.01 C
) (
red
. ) (c = 0

)(Mark Huink
a
= K M
:
A : K
:
= K M
) log = log ( K M

a
log = log K + log M a

log = log K + a log M

381
382

) ( a K
.
) : ( K : a
)(
6-
)(
)
(

) (

)(C
)(DMF

382
K 104
25
2.4
0.75
25
30
25
25
20
25
25
25
32
0.62
0.75
0.55
0.60
0.20
1.7
2.1
2.6
0.70
0.70
0.76
0.79
0.74
0.69
0.68
383

383
384

.

:
( Homogeneous

) (one phase
:
( Bulk Polymerization
)

(
.
384
385


.
( Heterogeneous

:
( )(gas phase polymerization
(
).(bulk polymerization
( ).(suspension polymerization
( ).(emulsion polymerization
: Homogeneous
( Bulk Polymerization

.

.
385
386

)(exothermic

.

/

.

.
)) (106 Poise
. ).(10 21 kcal

386
387

.
).(
) : (
387
388

<f< ^< < ]]< hi< < < gj]< l]]qc

]< <^]<
<<
( ) (
) .(

) (.
( : )(
.(

)
(.
( )
( ) (viscous
.

.

.
(
) (continuous process
.
388
389

) (
.
).(
) : (
389
390

) (40 %
.

.
.

.
)
95 % (

.
)

1
1
inch
8
8
390
. 18
391

:
(
.

.
(

)(cross-links
.
(
.
:
( .
(
.
(
.
391
392

(

.

.

) (
.

).(ionic initiator

-.
) (isobutylene
) (Lewis )(- 150 F
) (.
392
393

) (
.
) : (
) (

.

.
393
394

.
.
.

.

( .
(
.

(
.
( .
( .
(
.

394
395

(

) (chain transfer .
(
(

.
.

.
.

.
395
396

(
:

.
:
.
(

)(0.01 0.1 mm

) (
) (stabilizer

396
397

. :
) (polyvinyl chloride
.
.

.

.

.
.

) (polysterene
).(polymethyl methacrylate
:
397
398

)(polyvinyl chloride
)(polyvinylidine chloride
).(polyacrylonitile
:

) (.

(
(
(

. .
-
- .
- .
) (
.
398
399

) : (
399
400

) (
.
) : (

.

.

-

400
401

.

.

) (
.
.
) (ion-exchange resins
.

( .
(
.
401
402

( .
(

.
( .
( Emulsion Polymerization

:
(
.
(
) (1 10-3 mm

.
.
402
403

.
:

.
) (
) (micells - ).
.(
) : (
403
404

.

.

) / (
.

. .
-

.
.

.
404
405

-

.

.

) .(butadiene
) (SBR
. )(
) (SBR
).(
405
406

) : ( ) (SBR
) : ( SBR

-
.
.
) (
) (

)( ) (latex :
406
407

:

.
:
)(spray drying
.
:

.

.

.
407
408

.

.

( .
(
.
( .

)
(
) (benzoyl peroxide
.
408
409

)(potassium or ammonium persulfate

.
Redox Systems

KHSO3
) (ferrous sulfate
:
S2 O82- + HSO3-
SO 42- + SO 42- + HSO3 S2 O82- + Fe 2+
SO 42- + Fe3+ + SO 42 HSO3- + Fe3+
HSO3- + Fe 2+
409
410

Interfacial Polymerization

.

.

)( - .
) (610
) (hexamethylene diamine

) (sebacic dichloried
.
) (

)
( ) (610

410
411

) : ( ) (
411
412

412
413

: :
First Order Transition
:

) (Tm
.

.
.

) (enthalpy
.

413
414

) ( :
)(vibrational
)(rotational
)(transitional

.

.
)
(
) (

) (
414
415

).(isothermally
) : (

) (Tb
.
) (
) (Tm

)) (Tf (
415
416

.

.

.
:
Second Order Transition

) ( )(quenching

.
) (
) (glass transition temperature ).(Tg

) (second order transition
416
417

) (100 %

) .(100 %

.

.

.

417
418

.

)( ) (

)

.(Tg
:
): (Tg
)(.

:
.
418
419

): (Tm
) (.

:
:

).(Tg
:

).(Tm

(

.
(

419
420

) (
.
) (hysteresis
).(
) : (
420
421

Glass Transition
)
(
.

.
.

) (density ) .(specific volume

) .(

.
421
422

) : (
422
423

.

)(
423
424

( Kinetics

) (segmental motion
.
.
.
(
Thermodynamics
) (Tg

.
.
424
425

) (Tm )(Tg

)(empirical
.
Tg = k Tm
) (k .
)1/2
(k
) (symmetrical .
= 1/2 .
1
Tm
2
= Tg
) (k = 2/3
.
2
Tm
3
= Tg
425
426

:
1 Tg 2
<
<
2 Tm 3
426
427

( .
( .
( ).(Symmetry
:

.

) (cohesive energy density
) . (
)
(

.
) ( ) (
) (Tg ) .(Tm
427
428

) : ( ) ( ) (Tg
.Tm
)Tm (C
)Tg (C
)(
3 1/2
) (cal/cm
165
- 10
8

190
82
9.5

317
120
15.4

:

).(
) : (
)(Tg
)Tg (C

- 20

- 100

428
429

)(Symmetry

) Tg

(.
) : ( Tg
)Tg (C
105
- 30
- 50
429
430

) (Gibbs Helmholts
:
G m = Hm - Tm Sm
:
: G m
: H m )(.
: Sm .
) ( G m = H m - Tm Sm
) (Tm :
G m = H m - Tm Sm
Tm Sm = H m G m
H m G m
Sm
= Tm
at equilibrium G m = 0
H m
Sm
430
= Tm
431

) (
) : (
H m
)(Tm
Sm
)(C
Cal/mol
Cal/mol
0.17
69
138
) (
0.138
62
176

0.037
19.2
239

0.038
23
317

0.042
14.6
327
0.5
15.3
28
)(
1.30
45
74
)(
0.052
28
267

) (
) ( H m
) ( H m
.

) ( Sm
) ) ( Sm ( ) ( H m
) (.
431
432

) ( Sm
) (stiffness

.
432
433

)(Tm
: :
) (CH2

).(
) : (
)(Tm

)Tm (C
- (CH2)4265
66
- (CH2)8228
610
- (CH2)18189
620
:

.
433
434

)( )(CH2
:
)(
)Tm (C
240
190
215
150
170
X
2
3
4
5
6
:

) (

. :
434
435

)(
)Tm (C
265
355
X
1
2
:

) (Tm ) (
:
)(
)Tm (C
108
86
40
R
-H
-CH3
-C2H5
435
436

) (.
)(
:
)(
)Tm (C
265
190
R
-CH2-CH2-CH2-CH2-CH2-
140
436
437

)(

= .(130 C

) = : (70 C
437
438

438
439

:
( )(tensile strength
(
( )(impact strength
( )(elasticity
( )(elongation
(
(
(
( )(thermal stability
( ).(durability
.

.

.
439
440

Physical Properties of Polymers
:
( )(crystalline polymers
( )(amorphous polymers
( )(semicrystalline polymers
) (
.
) (
) (frozen liquids .

.
440
441

Crystallinity and Crystalline Melting Point

.

) ( .
) (
).(degree of crystallinity
:
)(X-ray diffraction

).(enthalpy measurements
441
442

) (
.
) (

) (microscopy
).(fringed micelle theory
) (

) (single crystal

) (folds

).(folded chain theory
442
443

) (degree of crystallinity
:
( .
( .
( .
( .
( ) (stereoregularity .
(
) (quenching
.

:
( .
( .
( ).(hot precipitation
443
444

): (crystalline polymers

.

)(crystalline melting point
) (Tm
.
) (Tm :
:
)(polarizing microscope

) (enthalpy :

))(differential scanning calorimetry (DSC

))(differential thermal analysis (DTA

444
445

) (
)(100 C
.

:
( .
( .
( ) (.
( .

:

66 )(Tm = 265 C
445
446

) (
).(Tm = 60 C
) (.

) (66- )
(.
) (
).(Tm = 220 C
446
447

)
(
.
) ( ).(Tm = 50 C
447
448

Glassy State and Glass Transition Temperature

) (supercooling
) (glass state

) (glass-transition temperature
).(Tg
)(Tg

)
( .
448
449

. ) (
.
) ( ) (coefficient of expansion

.

)index
(refractive
)conductivity
(thermal
) (heat (capacity ).(enthalpy

Tg

)(DSC
) (DTA.
449
450

) : (
) ( ).(C
450
451

Mechanical Properties of Polymers

.
:

).(additives

Tensile Strength
) (tensile strength
) (stretching rate
451
452

.

) (elongation
.
)) (stress strain curves .(
452
453

) : ( (Stress-
) Elongation :
(
( Brittle
(
(
( .
( .
453
454

Polymer Analysis

) (qualitative analysis
)analysis
)stability
(thermal
(thermal
) (photostabilizer )(antioxidants
) (thermogravimetric
.

( )(Thermal Analysis

:
( .
( .
( )(degree of crystallinity
454
455

:
)) DTA ( differential thermal analysis
(
)) DSC (differential scanning calorimetry
(.
.
:
)(enthalpy
)(heat capacity
). (specific heat
.
) ( ) .(DTA
) ( ) (Tg
) (Tm 120 C 260 C .
455
456

) : ( DTA ) (
.
) (60 C .
(
)(Thermogravimetric Analysis

.

.
456
457

) (thermostabilizers
.
) (
.

) (chromatography

.
) : (
.
457
458

) (isothermal decomposition
)(activation energy
. ) (

).(410 C
) : ( (410
) C .
458
459

(
Spectroscopic Analysis of Polymers
) (spectroscopic methods

.
:
(
.
( ) (branching
(
( .
(
.

.
459
460

(
Analysis by Infra-red Spectra

) ) .(tacticity ) (
) (
.
) : ( ) (.
460
461

( Ultraviolet Spectra

.
:
( .
( .
(
.
461
462

(
)Nuclear Magnetic Resonance (NMR

) (NMR
NMR :
(
(
.
:
(
(

( .
) (
.
462
463

) : (

463
464

Testing and Characterization
of Polymers
464
465

Testing and Characterization of Polymers

.

.

.

.
465
466
:
Spectroscopic Methods
(
Infrared Spectroscopy

.
) ( .
.

).(KBr disc
466

467

) (

).(absorption spectra
467
468

) : ( ) (IR
468
469

) (
.
) : (

)( cm-1

) (C-H
) . (
)(CH2
) (C-H
) . (

)(CH2
) . (
) (C-H
)(CH3
) . (
) (C-H- ) . (
)(CH2
)(CH2
) . (
)-(C = C
) . (
)(C = O

) . (
)(-O-

) . . (

)-(-CH-Cl
)(
)(C-F
469
) . . (
) . (
) . . (.
470

:

.
:

.
:
) (-O-CH2-CH2-O-
) (

Trans

) (gaushe .
470
471

.

).(
) : (

cm-1
10.1 , 11
RCH = CH2

10.4
RCH = CHR

14.2
RCH = CHR

11.3
RRC = CH2

12.0
RCC = CHR

(
)Nuclear Magnetic Resonance Spectroscope (NMR
) (NMR

) (chain configurations
.
471
472

) (NMR
) (proton ) (spin

:

.

) (19F) (17O) (13C
) (NMR
.

.

) (
472
473

.

).(chemical shift
( Scale
) (
.
( Scale
) (10
:
= 10 -
) (
.
) ( ) (NMR
.
473
474

) : (
474
475

) : ( NMR
) (NMR
.

:

) 22,000 60,000 ( )(10,000
.
) ( ) (NMR
.
475
476

) (double resonance

) (multiplet
).(
) : ( NMR
476
477

) : (
477
478

)Electron Paramagnetic Resonance Spectroscopy (EPR
)(NMR
) (free radicals

.

. ) (NMR
) (EPR

.
478
479

:
X-Rays Diffraction Analysis

.

.

.
479
480

) (X

.

).(monochromatic X-Rays
) (X

.

.
480
481

) (X

) (fiber

.

) (
.

).(layer lines

) (unoriented

) (

)
(
481
482

) (

) (arcs )(distribution
.
) : ( ) (X )( )(

.

.

) (repeat distances
482
483

.

)(2.55 A

)) (zig-zag 109
(.

.

) (unit cell
.

.

) (bond length
483
484

484
485

:
Microscopic Method
(
Light Microscope
(
Reflected Light Microscope

.
(
Transmitted Light Microscope

) (polarized light

485
486

).(Hot Stage
( Interference
.
.
( Electron Microscope

.
:

.
:

).(accelerating voltage
486
487

) (scanning electron microscope

.
) (
.
) : (
.
487
488

) : ( ) (

) : (

488
489

) : (
489
490

:
Thermal Analysis

.

) (Du Pont-Perkin Elmer
:
( )(DSC
differential scanning calorimeter
( DTA
differential thermal analysis
( )(TGA
thermogravimetric analysis
( )(TMA
thermomechanical analysis
490
491

(
)(DSC Differential Scanning Calorimeter
)(DTA : differential thermal analysis

.
) (Perkin Elmer

.

.

.

) ( T

).(
491
492

) : ( )(DSC), (DTA
) ( :

) (endotherm
) (Tm ).(Tg

) (exotherm

) .(crystallization ) ( T

)(.
492
493

) : ( )(DSC
(
DTA : Differential Thermal Analysis

DSC
) (DTA
) (
).(
493
494

)(
) : ( )(DTA
) (

).(adiabatic calorimeter
)
(
) (60 80 C

) (
494
495

) (Tm .
) : (

).(Adiabatic Calorimeter
495
496

) (
) (DSC
.
) : ( ) (DSC
.
496
497

(
)(TGA : Thermogravimetric Analysis

.

) (
).(TGA
497
498

) : ( ) (TGA .
) 5 C/min
.
(.
) .(HCl
) (PVC

) (C=C PVC
).(400 C
)) (PMMA (
) (HDPE ) (PTFE
.
) (PI : poly imide
).(580 C
498
499

(
)(TMA : Thermomechanical Analysis

:
)) (modulus (.
:
Degradation Products

:
( )(mass spectroscopy
( )(gas chromatography
( Mass Spectroscopy

.
) ( .

499
500

.

.
( Gas Chromatography

.

.
500
501

:
Chemical Analysis

:

.

).(endgroup analysis
501
502

.

) (stress-strain curve
) .(tensile tester
.
).(
) : (
502
503

:
( Stiffness
) (modulus
) (slope )

).(yield point
( Yield Stress
)
(
.

.
( Ultimate Strength

)(kg/cm2
).(dyne/cm2
503
504

( Ultimate Elongation

.
( Toughness

) (.

:
) (
:
) : ( .
504
505

) : (
) : (
) : (
505
506

) : (
:

) ( ) (regular rate
% .
) % (

.
506
507

) ( .
:
( Fatigue

Cyclic

.

) (cycles ).(
)(

) (

.
507
508

( Impact Strength

.
.
:
) (brittle breaking
.
)(ductile breaking

.
.
( Tear Resistance

.

.

. .
508
509

.
( Hardness Test

.

.
( Abrasion Resistance

.

.

.
( Stress Relaxation

) (Extension
509
510

.

) (

.
) (

) (
.
)(
510
511

: :

) (high modulus
) (
) .(yield point

.

.
:

.

)(cords-links
511
512

:

)
(
.

) (

) (Tm :
:
.

.
.
512
513

) ( :
) (

.

.

) (
.
513
514

514
515

:

) (transparency ) (strength
) .(elasticity
.

) (cracking
.
.

.

.
515
516

.

.

Crystallinity and Crystalline Polymers

.

)structure
(regular
) .(crystalline regions

)%
(100
) (crystalline polymer
516
517

).(degree of crystallinity
517
518

Crystallisability Requirements

).(thermal history

:
(
)(Regularity of Molecular Structure

) (interchain forces rage
.

:
-CH2-CH2CH2-CH2-
518
519

: 6
).(linear polymers

.
) (branching

.
)(degree of branching
.
) (
.
) ( .

.
519
520

).(amorphous

:
520
521

) ) (

.
) ) ((

.

.

) (Isotactic
) (atactic polymers
.
.
521
522

). (amorphous

.
) (random copolymer

.
) (polymer lattice

.
.
) (block copolymers

.
522
523

( )(Interchain Forces

.

) (polar groups
)interaction
(dipole
) (dispersion forces .

. .

.
(
Local Mobility Freedom of Chains

523
524

) (symmetric

.

.

) (stiff .

.
524
525

Crystalline Melting Point

: ) (specific volume
)capacity
(heat
) .(polymer viscosity

.
).(
525
526

) : (
) (.
) (Tm
.

).(heating rate

.
526
527

)Factors Affecting (Tm

.

.
:
( )(Molecular Weight

.

).(
527
528

: ()
.
Hydrocarbon
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Terradecane
Pentadecane
Hexadecane
Octadecane
Eicosane
Pentacosane
Triacontane
Pentatriacontane
Tetracontane
Pentacontane
Hexacontane
Heptacontane
Hectane
Formula
CH4
C2H6
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
C16H34
C18H38
C20H42
C25H52
C30H62
C35H72
C40H82
C50H102
C60H122
C70H142
C100H102

(C)
Tm, C
- 182
- 183
- 187
- 138
- 130
- 95
- 91
- 57
- 54
- 30
- 26
- 10
-6
6
10
18
28
36
53
66
75
81
93
99
105
115
528
(g/cm3)
Tm, C
1
4
49
8
35
4
34
3
24
4
16
4
12
8
8
10
8
17
13
9
6
12
6
6
10
Density
0.424*
0.546*
0.585*
0.579
0.626
0.659
0.684
0.703
0.718
0.730
0.740
0.749
0.757
0.764
0.769
0.775**
0.777**
0.778
0.780
0.781
0.942
-
529

) ( :
.

.

.

:
1
17.1 10-3
-3
= 2.39 10 +
Tm
n
) (n .

).(
529
530

) : ( .
( ][(CnH2n - 1)2CO
( )(CnH2n-1
( .
(.
) (

.
530
531

) (Flory
:
2 E Mo
1
1
=
+
Tm
Tm
H M n
:
: Tm
: Tm
: R
: H
: Mn
: Mo .

.
( )(Co-Polymerization

.
)copolymers
(random
531
532

) (homopolymer
:
1
1
-R
=
ln x A
Tm Tm 0
H
:
: xA

Tm 0
: .
( )(Solvents and Plasticizers

) (plasticizers .

:
1
1
R Vu
=
Tm Tm 0
H V1
532
533

:
: Vu ) (Molar Volume .
: V1 .
( )(Interchain Forces

.
) (

Tm
)(C

135

176

265

280
_ 66

300

327

533
534

) (
:

) (linear polyethylene
) (dispersion forces ).(135 C

66-

).(280 C

) (300 C

). (327 C
:

.
534
535

.
) (300 C

) (115 C
.

.

) (
) (135 C ) (
).(120 C

) (265 C
535
536

)C
(55
.
(
)(Flexibility of Polymer Chains

.

)(

) .(dispersion forces
) )(
) ( .
) (327 C ).(135 C
) (CH2

) ).((
536
537

) : (
.
(
(
(
( (
) (
) (linear aliphatic polymers

.

:
) .(-COO-, -O-CH2-
.
537
538

) (Rigid

.

:

H ( O - CH 2CH 2 - OCO ( CH 2 )6 - CO - ) OH
n
) (45 C
(-CH2)6
).(265 C

.
) (polyurethane

.
538
539

) (poly urea

).(

.
539
540

)(Crystallinity Determination
) (degree of crystallinity

.
.
:
(
)(X-ray Diffraction Crystallography

) .(electromagnetic
.

).(Bragg distance
540
541

) : ( .
) ) (
( :
= 2d sin
:
: .
) (intensity
). ( = 1

.
541
542

) (sharp ) )(
) : (
) (.

) (
.
542
543

) : (
) (.
543
544

( )
.
. : ()
Polymer
Polyethylene
st-Polyvinyl Chloride
Poly (isobutene)
n-Poly (propylene) ( form)
st- Poly (Propylene)
n- Poly (styrene)
n- Poly (vinyl cyclohexane)
n-Poly (o-methyl styrene)
n- Poly (butene-1) (mod. 1)
n- Poly (butane-1) (mod. 2)
n- Poly (butane -1) (mod 3).
Number
of Base
Units in
the Unit
Cell
2
4
16
12
?
3
8
18
16
16
18
44
?
Lattice Constants A
a
7.36
10.40
6.94
6.65
6.47
6.38
14.50
22.08
21.9
19.01
17.69
14.85
12.49
Crystal System
4.92 2.534 Orthorhombic

20.96 6.50 Monoclinic
10.71
?
Pseudohexgonal
6.38 6.33 Triclinic
5.81
7.3 Orthorhombic
22.08 6.63 Triclinic
21.9 6.50 Tetragonal
17.69 6.50 Triclinic
8.96
?
Orthorhombic
) (

.() )
544
545

) : ( ) (I
) ( )
(.

. ) (I
. ) ( .

.
545
546

(

) (Packed
) (amorphous

) (specific volume .

:
Vam - V
Vam - Vcry
= % Crystallinity
:
d - d am
d cry. - d am
= % Crystallinity
) (flotation
. ) (
.
546
547

: ()
Polymer
Poly (ethylene)
it Poly (propylene)
It Poly (styrene)
Poly (vinyl alcohol)
Poly (ethylene terephthalate)
Bisphenol A-polycarbonate
Nylon 6.6 ( modification)
trans-1.4 Poly (butadiene)
dcry.
1.00
0.937
1.111
1.345
1.455
1.30
1.220
1.020
547
(g/cm3)
dcry - dam
dam.
0.852
0.148
0.854
0.083
1.054
0.057
1.269
0.076
1.335
0.120
1.20
0.10
1.069
0.151
0.926
0.094
548

(
)(Enthalpy Changes

) (specific heat

) (enthalpy :
H am - H
H m
=
100
H am - H cry.
H f
= % Crys.
:
: Ham )( .
: Hcry. .
: H m
: H f .
548
549

(
)(Infrared Spectroscopy

) (bands
. ) (
.
) : (

1-

IR Bands

1894.719
1298
894.975
4274
922.815
4274
) (
.
) (650 1500 cm-1
) (absorption bands

) (intermolecular interaction

.
549
550

) (absorbance
) 100 % (
.

:
A am = (1 - IR ) A am
A am =A am - IR
:
A cry.
A am
=D
Acry Aam :
D
A cry
D +
A am
= % = . 100
:
: Acry
: Aam
550
551

.

. )
(

.
.
551
552

Crystallinity Theories of Polymers

. .
(
)(Fringed Micelle Theory

.
.

.

.

.
552
553

) .(unit cell

. ) (

.
) : (
)(Fringed Micelle Theory
553
554

(
Chain Folded Theory
) (single crystal
) (1957
) (0.1 %

).(
) : (
.
554
555

) (folds

.

.
3- -

66 .

)temperature
(crystallization
) (thermal history.
555
556

Crystallisation of Polymers

.
).(films
:
(
Crystallisation by Annealing

.
.
)) (annealing time (
(.
556
557

) : (
.

.
.

) (Nucleation
) (spherulite
) .(lamellae
) ( .
557
558

) : (
.

.
) (
.

558
559

) : (
.
(
)(Cold Drawing Crystallization

.

559
560

.

.
) .(orientation ) (
.
) : (
.
560
561

Crystallisation by the Effect of Stress Cracking Solvents
.

) (cracking solvents

.

.

.
) (

.
.
561
562

:
.
) : ( 48
.
562
563

Mechanism and Kinetic of Crystallisation

) (nucleation
.
:

.
.

.

.

563
564

) (glass polymer

.

.
.

) (lamellae
) .(homogeneous crystallization

564
565

.

) (avrami

.

.
) (specific volume

) (spherulite
) (

) (instantaneous
565
566

) .(
) : (
.

.

.

. .
566
567

).(dilatometer
) (avrami
:
ln (1 - ) = K t n
:
:
: K
: T
: n ) (exponent
) .(nucleation
:
1 2
V - Vt
=-
Kt
V - V0
W
c
ln
:
: V ,V0 .
: Wc ) (Weight Fraction
567
568

Glassy State and Amorphous Polymers

) .(cellulose esters

.

) .(amorphous

) (

.
.
:

.
.
.
568
569

) (

.

.
) (semicrystalline polymers

.
.

) (1011 1015 Poise
) (

) (flexible
569
570

)temperature
(glass-transition

) (elastic modulus . )(

.
.
) (

.
570
571

) : (
) (Tg ) (Tm
.

) .(Tg

) .(free volume theory

571
572

) (conversion

.
) ( Vam
) ( V1
) (
(Free
) Volumes
.
:
Vam - V1
=f
Vam
) (f
).(2.5 %
572
573

) ( Vam .T

) (van der Waals Radii :
Vam - Vvdw
=
Vam
vacant volume

) .(thermal expansion
.
( Vam ) - ( Vcr. )
( Vam )
= Fexp

)scattering
(neutron
) (X-ray scattering

573
574

) (physical entanglement
.
574
575

Glass Transition Temperature

) (
.

) (Tg

) (Soft ) .(flexible
) (rubbery state

.
) (elastic modulus ) (1000

.
575
576

. :
) (thermal expansion
)capacity
)index
)damping
(heat
(refractive
(mechanical
) (nuclear magnetic resonance behaviour

) (electrical properties .
) ( .Tg
576
577

)(
)(
)(
) : ( .
( ( (
.
577
578

) (elastomers
) (Tg

) (brittle
) (rigid .

) (first order transition
.

.
578
579

Factors Affecting Tg
.Tg

:
- :
(
Rigidity and Flexibility of Polymer Chain

.

) (ether linkage :
579
580

Tg
.Tg
:
) (

) .(acrylates
) : (
)(Methacrylate Esters
)Tg (C
105

65

35
-
21
-
-5
-
- 20
-
- 65

580
581

( )(Rigid Groups

Tg.
:

Tg
).(
) : (
)Tg (C
- 120

- 10

100

167

208

581
582

Tg

Tg.
( Polymer Polarity

) (cohesive energy ) (Tg )(Tg

:

).(
582
583

) : ( Tg
)Tg (C
- 10

85
) (
101

.

).(
) : ( Tg
)Tg (C
3

106
) (
400
) (

Tg

.Tg
583
584

(
)(Symmetry of Polymer Chains
Tg
Tg .
:

) ( ): (
)(
)Tg (C
- 10
- 70

)(
)Tg (C
85
- 19
( )(Free Volume
Tg
:
- g ) Tg = 0.113 0.0003
584
585

( 1 - g ) Tg = 0.113 0.0003
Tg
.
:
: 1
.
: g
.
Tg
.
:
): (
Tg ) (
) (0.022 C/atm .
) ( )(0.014 C/atm
) .(0.018 C/atm
) (0.017 C/atm
).(0.2 C/atm
585
586

Tg :
) : (compressibility
.
) : ( Tg .
Tg

)(C/atm
0.022 C/atm
) (
0.014 C/atm
) (
0.018 C/atm

0.2 C/atm

( )(Stearic Hindrance

.
:
) (

) (Tg = 101 C Tg
) (Tg = 125 C

586
587

) (

) (Tg = 3 C Tg )
(Tg = 105 C
.
(
Structural Factors Affecting Tg

:
( )(Molecular Weight
Tg
:
k
Mn
Tg = Tg -
: k .
587
588

)(
k
1.75 105 mol K
1.45 105 mol K
Tg ) (104
) (Tg = 83 C ) (Tg = 100 C
) .(
)(

104
104
)Tg (C
83
100

) (
588
589

) : (
.
( Crosslinking
Tg
. Tg
) (curing
) ( ) (vulcanisation Tg

)(epoxy resin
Tg Tg
) .(decomposition
589
590

:
3.9 104
= Tg - Tg
Mc
o
: Mc
) (crosslinking points Tg
.
Tg :
k x c 2k
1 - x nc
Tg - Tg o
Tg o
:
: xc .
: nc
.
Tg k
) (1-1.2
) (segmental mobilities
.
590
591

( Co-Polymerization
Tg
) (homopolymers
.
:
Tg = V1Tg 1 + V2 Tg 2
W W
1
= 1+ 2
Tg
Tg 1 Tg 2
:
: Tg2 Tg1

: V2 V1 .
W1 : W2 .
) ( .
591
592

) : (

( Degree of Branching
.

) (chain ends
.

) (linear
. .
Tg :
592
593

K .W
2M
Tg = Tg -
:
: W
: M .
( )( Plasticizers :

.
.

) .(extrusion
.

) .(50 150 C Tg
Tg
.
) (Tm .
593
594

) (
Tg Tm .
) : (
.
)fraction
(volume
) (Components
Tg :
594
595

Tg = TgA VA + TgB VB
W
W
1
= A + B
Tg Tg A
Tg B
:
: TgA
: TgB
VA
: VB .
: WA
: WB .
595
596

Determination of Tg

.

:
(

) (dillatometers
. Tg
. ) (

))(co-efficient thermal expansion
) (

) (.
596
597

) (
) (
597
598

) (refractive index

. ) (
)
( ).(poly (vinyl acetate
) (
598
599

(
Specific Heat

. ) (
.

:
).( differential scanning calorimetry
) : (
599
600

(
) ( Enthalpy

.
Tm Tg
) (crystallinity
) (calorimetry .
)(
) : (
.
) ( H
Tg

)(
600
601

) : (
DSC .
(

.
- ) (visco elastic

)modulus
(elastic
) .(loss factor ) (
.
.
601
602

) : (
)(Rheovibron
602
683

Industry Polymers
683
684

Industry Polymers

) (films
)(alkyd paints
:
Linear Aliphatic Polyesters

) (functional group : ) (

:
684
685

.

.
:
( Plasticizers
) (plasticizer

)temperature
transition
(glass
)
(

.
685
686

( Adhesives
) (coating .
(

)(crosslinks

) (anhydrides )anhydride
(maleic
).(fumaric acid

) (sebacic acid

).(paraplex rubber
(

) (HO/COOH

686
687

) (poly urethane

) (di-isocyanates
) (tri-isocyanate :
687
688

:
Aromatic Linear Polyesters

:
.

) .(crystallizable

.
) (diol.

) (
) .(
688
689

) : (

)(Tm) (C

-
225 230
225 260

110
220
689
70
330
120
690

) : ( ) (diol
)(Tm
)(C
500
180
360
330
300
224
690
691

: ) (
)Poly (Ethylene Terphthalate
) (
) ( )terphthalate
(dimethyl

) (
.

). (Crystallization

)terphthalate
(dimethyle
) (P-xylene )(terphthalic acid

:
691
692

692
693

693
694

:
Poly Carbonate

) (biphenols
:

.

.
694
695

) .(polycarbonate bisphenol A ).(
695
696

)(

)(Tg
(Tm) C
150
240 260
180
250 260
147
223 225
120
200 215
112
696
200 - 220
697

)( :
) - (

" "A :
697
698

:
Branched and Crosslinked Polyesters

). (network polymer

:

) (Tm )(Tg
.
698
699

) (maleic acid anhydride

.
:
699
700

.

).(alkyde resin
700
701

Polyester Derived from non Carboxylic Acids

) (polysulphonate )(polyphosphate
:
701
702

:
Polyamides
) .(nylon

.

) (natural polymers
.

)(amide linkages
702
703

) (films .

) (308 C 64 ) (65
) .(223 C
.

66
) (

.

.
703
704

) (

)(C
320 330
265
250 270
215
233
195 200
200
10
188
11
185 190
12
180
64
308
65
223
66
265
104
236
105
186
106
228
704
705

) ( :

) (NH
10 -

4 .5

) ( 66 -
) (265 C )
( ) (260 C.

:
705
706

) ( :
) : (
.
)(C

455
399
436
353
371
341
66
) ( .
706
707

6
) ( :
707
708

:
Poly Urea

:
:
( :

.
(
708
709

( :
709
710

:
Poly Ureathane

) .(H2N-COOH

.

.
) (
(

) (diols :
710
711

.
) (softening
.
( :
711
712

( :

:

) (copolymerization
.

.
) (

712
713

) (allophanate :
713
714

)(
Polyurethane Foam

Foam
:
- ).(flexible foam
- ).(rigid foam

.

.

.
714
715

:
Mechanical Foaming

.

).(polystyrene foam
:

) .(foaming agents

" "AIBN ) (45 C
:
715
716

) (emulsifire ) (stabilizers
.

.

) (-NH-CO-
.

:
716
717

) (amide linkage :
:
-
toluenediisocyanate
:
-
4,4'- diphenylmethane diisocyanate
:
-
stannous-2-ethyl hexoate
) (tertiary amines :
.Diazabicyclo-2-2-2-Octane
717
718

Phenol-Formaldehyde Resins

"
. "phenolplast

:
:

" "resole
.
:

" "novolac
:
718
719

719
720

Melamine-Formaldehyde Resin

) (cyanamide :
2000 C
CaO + 3C
CaC 2 + CO
720
721

721
722

:
( ) (latex
.
( ).(synthetic fibers
( ) (plastics
).(resins

:
( )(paints
( )(adhesives

.
.
722
723

: :
) (
) (700 %
.

:

.
) (
.

)
( .
) (Tg

.
723
724

.

.

)
(
) (tensile strength
. )
( )(reinforcing agents

.
724
725

.

) (

.
725
726

:

.

:
( ) (200 C

.
(

.

.
726
727

(

) (oriented

.

).(hot drawing
(
) (

.
) (covalent

.

727
728

) (covalent

.
728
729

:

.

.

)(

.

) (
.

.
729
730

) : (

) (
.
.
)C

)(200 C
730
).(300 C
(120
731

:

.

)(moldable

) (waterproof

.

.
731
732

. )(thikol
).(neoprene

.
(styrene butadiene rubber) SBR

) (gr-s
) (government
) (10,700 kg .
) (
)
( .

.
732
733

)(
.
) : (
:
(
( .
733
734

:

) (Hyatt
) (camphor

.

.
.

.SBR
)(PVC

.
.
:

734
735

.

.
735
736

: Fibers
)
(
) (synthetic

.
)
) (rayon

(.

.

.
.

736
737

.

.
737
738

: Paints

)(linseed oil

.

) (alkyd resins
) (SBR
.
) (
) (latex paints
.

.
.
738
739

Feed Stock

.

.

)(
).(
739
740

) : (
.
740
741

) : (
741
742

).(16.6 106 kg

) (5000 106 kg/year
.
.

.

.

.
) (

742
743

.

) ) (850 C/s
(
) .(cracking furnace

.

.
743
744

744
745

:
)Low Density Polyethylene (LDPE

.
.

:
:
( :
CH3 -CH 2 -OH
CH 2 =CH 2 + H 2 O
745
746

( :
CH CH + H 2
CH 2 =CH 2

) (cracking
) (naphtha
.
: ) (

) (Tubular Reactor

746
747

) : (
) (
) (demethanized
) (deethanized
) ( ) .(0.5 % O2
)( (1000
) 3000 atm
) .(175 200 C
) (5 cm
) (15 cm
747
748

) .(100 106 kg/year

) (Pilot Plant )(20 m
) (5 mm
) .(3 kg/hour

.
) (
.
748
749

) : ( .
749
750

( (50 60 % ) %
( . . /(0.91 0.94 g/cm3)
( ) (100 C

.
(
.
(
)( .
(
.

.

750
751

:
.

( :
) .(0.001 to 0.005 inch
) (70 %
.

.
) (green house
.
751
752

(
)(Injection Molding
) (
) (13 % .
( :
) (1 %

.
( Coatings

.

.
) (3 % .
752
753

(

) (blow molding ) (2 %

.
753
754

:
)High Density Polyethylene (HDPE

) (linear
.

.

(

)(heterogeneous
) (
) (slurry reactor ) (
.

) .(slurry
) (120 C ) (90 C
) .(5 30 atm
754
755

.
.
) : ( -
755
756

( Philip's Method
) (
) (CrO3
) .(Al2O3

).(
) : (
756
757

:
(
Fixed Bed Reactor
) (
) ( ) (isooctane
) .(2 4 %
) (
) (150 180 C )(20 40 atm
) -/ ( .

.
.
757
758

) : (
(
Slurry Reactor
) (
) ( .
) (
)
( ) (150 C
)
(
758
759

.
) .(20 40 atm
.

.
.
) : (
759
760

)(90 %

.
)C
(127
) (135 C
)(0.95 0.97 g/cm3

)(100,000
) (20,000
.
.

.
760
761

(
) (40 %
.
( . (20
) % ) .(HDPE

.
( .
(

.
761
762

:
)Linear Low Density Polyethylene (LLDPE

) (LDPE
) (HDPE
).(LDPE
) (
) (fluidized bed (gas phase
) ( .

) (fluidized bed ) (30 atm
) (100 C .
) (2 5 hours
) (500
.
762
763

) : (

)(600,000 kg

) (

.
-.
763
764

:
Polypropylene
:

.

) (

.

).(0.905 g/cm3
764
765

)) (165 C
(.
.

.

.

.

(

) (50 %
.
(
) ( )(staple
.
765
766

:
Polystyrene
:
) (MgO .
766
767

) (emulsion
) (solution
) (suspension
).(bulk

) (atactic
.

.
) (240 C ).(80 C

.

) (90 C
.
767
768

.
) (
).(1.65
.
) / (.

.

.
) (
) (240 C

) .(82 88 C
.
768
769

769
770

(

)(60 %
(40 %)
)( .

.

) (
.
.
(
) (76 %
)%
(24 ) (CH2=CH-CN

.
770
771

) .(90 92 C

.
(

) (dispersion

)(toughness
.
( ABS

) (
) (ABS
) (A )(B
) (S .
).(
771
772

) : ( )(ABS
ABS

ABS

).(electroplating
772
773

(

.
) (ABS
) (24 %
.
773
774

Ionic Exchange Resins
: )(
Cationic Exchange Resins

) (divinyl benzene
)polymerization
.(suspension

) (
) (SO3H .

.
: )(
Anionic Exchange
) (

.

774
775

Cl-CH2-O-CH3
.
) : ).((
775
776

) : (
776
777

(
)Polystyrene Foam (Styrofoam
) (250 300
.

.

(20
) C .
:
:
)
( ) .(
777
778

) : (

) .(
) : ( ) (.
778
779

: Acrylic Plastics
( ) (
)Poly Methyl Methacrylate (PMMA

.
: )(MMA
)
(
.
.
779
780

:
) (Bulk
) (suspension
) . .(
) (
) (
.
) (bulk
.
780
781

) : (
781
782

)(PMMA

) (70 75 %
) (syndiotactic
) (-OOCH3
.

.
) (PMMA

. ) (PMMA
.
) (10,000 .

.
).(90 C
.
.
782
783

(
)
) (50 %
.

.

) (plexiglass
)(lucite

(
Polyethyl Cyano Acrylate
) (ethyl cyano acrylate

.

.
783
784

784
785

:
Poly Vinyl Acetate

CH2 = CH-O-OC-CH3
:
CH CH + CH3 - COOH
CH3 - COO - CH = CH 2
.
:
:
( ): (Bulk

.
785
786

( Suspension

.
( Emulsion

.

.

) (28 C
.

.
786
787

.

).(chewing gum

.

.
)
(
)( ).(latex paints

:
( ) (polyviny alcohol
) (
787
788

. "
".
) (

)(.
( ) (polyvinyl acetal
)
(.

) (
.
788
789

) (safety glass .

)) (cellulose nitrate (

.

.
789
790

)) (plasticizer
) (dibutyl sebacate ) (40 45 %

.

)) (autoclave (
.
790
791

: )
( Polyvinyl Alcohol
791
792

).(drawing

) (150 C

.

) .(90 C

.

.
792
793

) (
.

:

) (30 % .
793
794

:
)Polyvinyl Chloride (PVC
: )(CH2 = CH-Cl
) (- 14 C
:

) .(suspension
.

) .(plastisol and organosol

.
794
795

.

) (HCl
) (.

.
) (HCl
.

.

) (PMMA, ABS
.
795
796

) % (

.

.
) (PVC
) ( :
) (tricresyl phosphate
.
.

" " " ".
)

.
)
( .
796
797

) (
.

) (calendering

) (20 30 % ) (
.

.
% + % +
+ .

.
).(180 C
PVC .

.
797
798

798
799

: Fluorocarbon
) )(Teflon
)(Polytetrafluoro Ethylene
) (CF2 = CF2
) (- 76 C
.
)
(

) (.

799
800

)) (93 98 %
(.
) (237 C
) (2.3 g/cm3
.

.
.

.
)(250 C
.
.

)
800
801

( )
(
.

.

)dispersion
(aqueous
. .
)(

.

)
( .

801
802

802
803

: Polyurethane

) (diisocynate
).(ethylene glycol

) .(-NH-C-O-
.
:
( ) (.
( )(.
( .
( .
( .
803
804

) : (
( ) (Foamed Rubber
:

:
( )
(
.

.
.
804
805

( ) (B

)) .(prepolymer
) ( ) (
) ( (
) ( :

) (B :
(

.

805
806

) (-NCO
.
R-NCO + H 2 O
R-NH 2 + CO 2
)
(.

) (
.
Synthetic Fibers

) (
) (
).(spandex
806
807

( Coating Materials

.

) .(magnetic stirrers

.
( )( Poromerics

) (
.

.
.
807
808

: Polycarbonate
:
)(phosgene
) - ) (bis phenol
-(.
808
809

) (

) (
.

.
) (140 C
.

.
.
) (

.
.
809
810

: Epoxy Resins

.
(epichlorohydrin
.
( )(epichlorohydrin
) (bis phenol

)
(.
810
811

) (A

A .

.

.
811
812

.

.

BF3
) .
) : (
812
813

.

.
.

.
813
814

:
Thermosetting Resins
(
(
Phenol Phormaldehyde

.

.

) (.
:
(
.
814
815

:
( Novolac
) (
) (
.

815
816

. )(1000
) (10
.

.
( Resols

.
816
817

:
( .
(
)(.
(
.
( ) (
.

) .(
817
818

) : (
818
819

) : (
819
820

:
)
(
) ( : .
.
:
:
.
) .( .

) .(hexamethylene tetramine

.
Hexamethylene Tetramine
6CH 2 O + NH3

820
821

.Vacuum

)
(
.
).(A

)( : .

) (B
.
) (

821
822

.
).(C

.

.

.
822
823

:

) (10 15 %
) (
) (

.

.
.

) (ion exchange
.
823
824

( Amino Resins
:
( )(urea formaldehyde
(
).(melamine formaldehyde

.
:
( .
: ).( : .
824
825

(

:
(
)( :
) ( .

.
:

825
826

.
Molding Resin

. .

.
) (.
826
827

.

.

.

.

.

.
827
828

.

) (Alky Resins ) (enamel
) ( ) (baking

:
Butyl or Substituted Monomethylol Urea Formalehyde
828
829

( ) ( :
Reinforced Polyesters Resins

.
)
(

.

.

.
.
.
.
.
829
/
.
.
.
.
.
830

( ) (

) (
) (

.

.
.
(

) (accelerators ) (promoters

. :
(
).(gel
(

830
831

.

) (contact
) (laminating
.

.

.

.
.
.
.
831
832

( Allyl Resins

.

.
:
832
833

( Diallyl Phthalate
)
( .
- .

.

.

.
(
Allyl Diglycol Carbonate

-
)-(CH = CH - CH2 OCOO - CH2 - CH2 - O

.
833
834

( Furan Resins

.

.
.
( Lignin
) (%
.

) (n-propyl benzene

.
834
835

835
836

: )(
)(

.

.
) (
) (

)( ) (Grigrand

)
) .((
) ( ) .(

) .(
) (

.
836
837

( )(PET

) (PET .

)(stretch blow
............. ).(PET
837
838

.

.
( )(PET

)(polybutylene terephalate
) (
) ( ) (PET )(PBT
. ) (PBT

.
( )(Aromatic Polyester
838
839

) (
.
)) (PTFE(
) (
) ( .
) (PTFE .
)
( .
.
839
840

:
)polyimide : (poly benzimidazole

:

) .(amide
.

) (imide
) (.
840
841

)

) .(k
.
.
841
842

)
(

.
.

) (liquid crystals
)
( .

.
)(

.
842

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11

( Structural repeating Unit

)poly (ethylene terphthalate

) (weight average molecular weight

) (viscosity average molecular weight

) .(molecular weight distribution ratio

) (semi organic polymers

) (12.6 29.4 kJ/mol

Poly (3-chloro - 4,4' biphenylene) methylene

) - ] -) - - )-[ -]- -(.

Types of Polymers and

) (high energy radiation

cellulose acetate, butyrate, nitrate

)(styrene butadiene copolymers

Classification Based on the Mechanism of Chain Growth

Classification Based on the Mechanism of Chain Growth

Mechanism of Free Radical

Chain Transfer to Polymer Molecules

) (-OR) (-C2H5) (-CH3) (-OH

CH3 -CH 2+Cl-

( Vander Waals Forces

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) (Nylon 66) (66

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Carbonyl Addition Substitution Reactions

) (phenol phormaldehyde resin

] ~~C + (OH) 2 , [ ~~OH ] , [ ~~COOH

] - d [ COOH ] k 3k1 [ COOH ][ HA ][ OH

) (Dp = degree of polymerization

Type of Initiators Used in Free Radical

) (kinetic chain length

f k d [ I] + k tr.m [ M ] M + k tr.s [S] M + k tr.I [ I] M

f k d [ I] + k tr.m [ M ] M + k tr.s [S] M + k tr.I [ I] M

) (chain transfer agents S

(42 161) 104

] C + (OH) 2 , [ OH ] , [ ~~COOH

k 21 [ ~M 2 ][ M1 ] = k12 [ ~M1 ][ M 2 ]

dM1 k11 [ ~M1 ][ M1 ] + k 21 [ ~M 2 ][ M1 ]

dM1 k11 [ ~M1 ][ M1 ] + k 21 [ ~M 2 ][ M1 ]