1

-1

,
:

- ):(Naturel polymers

- ) :(Synthetic polymers

.

) (linear polymer ) ( branched polymer

).(cross-linked polymer

-
:
-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-

-
:
CH2-CH2-CH2-CH2-CH3
-CH2-CH-CH2-CH2-CH-CH2-CH2-CH2-
CH-CH2-CH2-CH3

-
:
-CH2-CH-CH2-CH2-CH2-CH-CH2-CH- -
-CH2-CH-CH2-CH2-CH-CH-CH2-CH2-
-CH2-CH2-CH2-CH-CH-CH2-CH-CH2-
 2

(Polymerization degree):
( ) Dp .
:
Mn
Ma ( ) Dp :
Mn
Dp
Ma

( ( ) (a
Dp:

Dp
a

-[-CH2-CH2-]n- : - ( ):

n .Dp

- ( ) -[-CH(C6H5)-CH2]n- :
- ( ) -[-CH2-CH2O-]n- :

-2

.1-2 ))Polyaddition

.

 3

1000 10000 .
) (C6H5-CH=CH2 (Insatured
) vinyl group )(CH2-CH2O
:

n (C6H5 CH CH2 )
[CH(C6H5 ) CH2 ]n
()

-CH(C6H5) CH2- :

n
.

)(Polymerization of ethylene oxide

n (CH 2 CH 2O)
[CH 2 CH 2 O]n

( )

):(general behavior of polymerization reaction

,
.

, ) (inhibitor
.

.

:
 4

( ) M
M
-

M2
M M

( ) M2 M
M3

Mi M
Mi 1

-

:
-1
-2
-3 ) (two macromolecules
-4
-5

) (macroion
" " .

:
 5

.1-2-2 ):) Free radical polymerization

) (vinylic compounds
) (electroatractive :) (styrene
) (acrylates ) (methacrylates
) (vinylchloride ) (acrylamide.

- )(initiation
:
- :
/ h
A 2 2A

UV radiation
- :
A M
A M

( ))) active center

-)(propagation

:

A M M
A M M
)(macroradical
 6

A M 2 n M
A Mn 2

( )macroradical-

- )(termination
:
-1 ) (macroradical (
)

:
R Mi H T
R Mi H T
)(transfert

( ) transfer agent - ( )
)(macromolecule
:

T M
T M


.
-2 :
CH3- CHX-[CH2-CHX]m-CH2-CHX-CH* + *CH2- CHX-[CH2-CHX]p-CH3

.2-2-2 )(anionic polymerization

) (active center
)(carbanion ) .(olefin
: ) (Bronsted
:
 7

-
( ) B-
(. (monoelectronic

B( ) CH 2 CH(A)
) B CH 2 (A)HC (

( )

.

) (B- :

- ( )OH- KOH NaOH

) (A . CH2=C(CN)2
- ) (alcoxyle ). (phenoxyle
- ) (NH2- ) (NH4OH .
- )) (R(- ) (hydrocarbon )(ether
) (organometallicR-Li , R-Mg-X :
:

) R () Li (
R Li

) R ( ) Mg(X) (
R Mg X

)(monoelectronic reduction

) (substituent group) (A .

B( ) ......Me ( ) CH 2 CH(A)
) B CH 2 (A)HC ( ) , Na (

)(Anion radical
 8

) ) dicarbanion :

2 [CH 2 (A)HC ( ) .....Na ( ) ]

) Na ( ) ....( ) CH(A) CH 2 CH 2 (A)HC ( ) ....Na (
( )dicarbanion -

-

:
B CH 2 (A)HC () ....Me () CH 2 CH(A)
) B CH 2 CH(A) CH 2 (A)HC () ....Me (

))monomer actived )) dimer actived

M :

B M()....Me() M
) B M M() ....Me(

B Mi M ( ) ....Me ( ) M
) B M i 1 M ( ) ....Me (

M ) M(- ) Me(+.

-



" ") (Live polymer
.
.
 9

.3-2-2 )(Cationic polymerization

-


.

-
) (AmH HCl, H2SO4, HClO4, CCl3CO2H :
) H(+
:
( ) ) Am() H(
AmH

)( H() CH2 CH(A) CH3 (A)HC ( -)

( )

)) (H(+ ) (A
,
) (isobutene
) (CH2=CH-O-R ) (para R
.OR
 10

-
( )III
BF3, AlCl3 :
ZnCl2, :

MeX n SH MeX nS() H () SnCl4, TiCl4,

MeX nSH
SbCl5.
) (anhydre
) (co-catalyst HX, H2O,
R-OH :
: Me

BF3 HF ) BF4() H(
BF4H

AlCl 3 H2O ) AlCl 3OH() H(

AlCl 3OH2

-
) (Alcoyle Halogenure ) (ether
:

BF3 [C2H5 ]2 O ) BF3OC2H5() C2H5(

BF3 , [C2H5 ]2 O

C2H5() CH2 CH(A)

) C2H5 CH2 (A)HC (

-

.
AmH :
 11

)H CH2 (A)HC () , Am() CH2 CH(A) H CH2 CH(A) CH2 (A)HC () , Am(

((monomer active )(Dimer actived

H M() ...Am() M
) H M M() ...Am(

H Mi M ( ) ...Am ( ) M
) M Mi 1 M ( ) ...Am (

) (AmH

.Am(-), )(+
M---

-
.

)(Coordination polymerization .2-2-4

( (Stereochemie
.

-).(Ziegler-Natta
 12

))Ziegler-Natta polymerization
- :
-1 ) (organometallic )(metalhydrure
I II III
III :
- AlH3
- AlCl3
- AlR3
- AlClR2

-2 IV V VI :
- ) (Titane Ti(4+) : ) Ti(3+ )Ti(2+
- )(Vanadium V(5+) : ) VO(3+ ) V(4+ )VO(2+
-) (Molybdane Mo(5+) :
-) (Tungesten W(6+) :
- ) ( Crome Cr(6+) : )Cr(3+

) (acetylacetonate
) (cyclopentadienyl ).(alcolate

- .

.2-2-5
:
- ) (homogenous polymerization
)(heterogenous polymerization -
 13

- 3
.1-3

.

)(Bulk polymerization -

.

.

.
)(Solution polymerization -

.



) (polyvinyl acetate (polyvinyl
)alcohol
.2-3
.
:
- ,
- ,
- .
 14

-.
:
)(Emulsion polymerization -


) (surfactant .
) (micelles ,

:

) (vinylic polymers
) (polystyrene
) (polyvinylchloride -
) ,(copolymer(styrene-butadiene.

) (Suspension polymerization -

) (dropleters .

) (Powder .

( ()
 15

)) (polymethylmethacrylate ( )) (polyvinylchloride
( ) ) (polyvinylidenechloride ()).(polyacrylonitrile

-4 )(Condensation polymerization
)two functional
. (groups

:
, HO-Si(CH3)2-OH , H2N-(CH2)4-NH2 , H2N-CH(CH3)-OH , HO-C(CO)-CH2-CH2-C(CO)-OH.
:
HO-Si(CH3)OH-OH , H2N- CH2-CH(NH2)-CH2-NH2 , HO-CH2-CH(NH2)-CH2-CO-OH , Cl-Si(OH)2-Cl

( (oligomers


. :
:1
HO-Si(CH3)2-OH + HO-Si(CH3)2-OH HO-Si(CH3)2-O Si(CH3)2-OH
+H2O
HO-Si(CH3)2-O Si(CH3)2-OH + HO-Si(CH3)2-O Si(CH3)2-OH HO-[Si(CH3)2-O -]3-OH
+H2O
.

:2
H2N-(CH2)3-OH + H2N-(CH2)3-OH H2N-(CH2)3- HN-(CH2)3-OH + H2O
H2N-(CH2)3- HN-(CH2)3-OH + H2N-(CH2)3- HN-(CH2)3-OHH2N-[-(CH2)3-HN-]3-

.
 16

HO-CO-CH2-CCOOR-OH HO-[-CO-CH2-CH(COOR)-O-]n-H Polyester )(
RO-CO-OR -[-RO-CO-O-]n-R )(
Polycarbonate
H2N-R-NH-CO-R-CCO-OH H-[-NH-R-NH-CO-R-CCO-]n-OH Polyamide )(
HO-(CH)p-OH -[-(CH2)p-O-]n- Polyether )(
NH2-CO-NH2 -[-CO-NH-]n- Polyurea )(
HO- Si(R)2-OH HO-[-Si(R)2-O-]n- )(
Polysiloxane
HO-CH2-O-CO-NH- H-[-O-CH2-O-CO-NH-(CH2)p-]n-NCO )(
(CH2)p-NCO Polyurethane
 17

-4


) (Average molecular weights .
:

)(Number Average molecular weight -

Mn
:
Ni Mi
Mn
Ni

Ni Mi ) (i .

)) (weight average molecular weight -

Mw
:
Ni Mi2
Mw
N i Mi

)(Viscosimetric average molecular weight -

Mv
:
a
Ni M ia 1
Mv
Ni Mi

a 0.5 0.9 1 = a
Mv . Mw
 18

:
Mw < Mv < Mn
Mw
( molecular weight )distribution
Mn

) ( I )( Polydispersity index
) (I ) (monodisperse

) ( polydisperse .

.5

.
.
.
.
.1-5

.


.
) (Ubelohde tube :
 19

A
t

)to
) ) ( t

. :

- )(Relative viscosity

t to
rel
t0

- )(Reduced viscosity

t t0
red rel red
C C t0

: C
:
 20

- )(Intrinsic viscosity

(red )c0 ( t t 0 )C0

C t0

Mv C1 C2 C3
C4 ) (red Ci Ci = 0
] [ Mv
) (Mark Houwink:

K Mav
ln lnk
( )
Mv e a :
K a .
:

:
0.823 0.87 0.92 1.02 )Red(dl/g
0.0025 0.05 0.1 0.2 )C(g/dl
k a 10-5 : 30 oC . 0.72
:
red

][

C
red C C=0 [] = 0.82 dl/g
 21

.2- 5 SEC
)(Exclusion by size chromatography
(gel permeation
) Chromatography
) (polymer cross-linked



.

)(GPC

 22

:
Mn
: Vl )) Elution volume
Vl = D x tr
Ma Mb : D ((Flux) )min /ml

:tr )(retention time

Vl : Ma

:Mb

(
) (standard sample) Mn s
Vs
:
V
Mn Mn s s
Vl

GPC ml 25 12.5
ml 2.3 106 .

:
25
Mn 2.3106 = 4.6106
12.5
 23

.3- 5


- ): (Vant-Hoff
RT

C Mn

: C .

: R

: T

(+
)

) ) semipermeable membrane
.25000

- ))(Poly(vinyl alcohol
- ))(Poly(isobutyral
- )(Cellophane
 24

- )(Bacterial membranes
- )(Collodian membranes

/C . C
C = 0 /C K/Mn k .

/C

K/Mn

.4-5 )(Light scattering

,


) .)polydispersity index 103
.

.


.
 25

Principe

. ,

.
)(Debye .

:
Hc 1 A
: 2 2 C
R 90 Mw RT

2 2 n 02 (dn/dc) 2
Hc
NA 4

: Hc n .C

n n0

: dn/dc .

:NA )(Avogadro

:R90 90 )(Rayleight ratio

: A2 .

Hc/R90 C
.Mw

.5-5

 26

RMN

.

.
.