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Polymer Center- HUTS 1

Monome
Polyme
Trng hp
Chng 2: CC PHNG PHP TNG HP POLYME
n M ( - M - )
n
Polymerization mechanisms
Chui
Ch cduynht mt phn ng cng
hp ca monome vo mch ang
phttrin vi monomehot ng
Hn hp phn ng baogm c
polymevccmonomekhngphn
ng vi rt t ccmch ang pht
trin
Nng ca monomegim u n
theothi gian
Tng Bc
Phn ng cth xy ramt cchc
lp gia bt k ccphn t thamgia
phn ng
Hn hp phn ng baogm rt nhiu
ccoligomevi nhiu kchc khc
nhau
Nng ca monomegim rt nhanh
to thnhccoligome
Chui
Phnt polymec hnh
thnhto thnhrt nhanh,
khi lng phnt trung
bnhkhngthayi nhiu
trongsut qutrnhphn ng
Hiu sut sn phm tng theo
thi gianphn ng nhng
khi lng phnt trung
bnhca polymekhngthay
i nhiu
Tng Bc
Kchthc ca oligometng
u n, khi lng phnt
trungbnhca polymetng
dn theoqutrnhphn ng
Thi gianphn ng di v
bn cht s to thnhpolyme
vi khi lng phnt trung
bnhcao
Polymerization mechanisms
Polymer Center- HUTS 4
2.1. Phn ng trng hp (addition polymerization)
monome
C C
R
3
R
4
R
1
R
2
R : H, Halogen, - CH
3,
-C
2
H
5 .
5
Polymerization mechanisms
Trng hp chui
Trng hp chui
c imca phn ng trng hp chui:
1- S pht trin c tin hnh bng cch gn cc monome ln phn cui ca mch
ang pht trin
2- Lun lun cn li cc monome cha phn ng trong hn hp phn ng
3- Khi lng phn t ca polyme tng rt nhanh
4- C nhiu c ch phn ng xy ra cc giai on khc nhau ca phn ng
5- Tc phn ng trng hp lc u tng v sau tin dn n khng i
6- i hi phi c cht khi mo phn ng
Phn ng trng hp chui bao gm 3 giai on chnh
1- Khi mo
2- Pht trin mch
3-Ngt mch
S phn ng
Khi mo (initiation)
I R*
R* + M R M*
Pht trin mch (propagation)
R M* + M R MM*
R MM* + n M R M
n+1
- M*
t mch (termination)
C C
H
X
C C
H
X
n
n
H
H
H
H
Vinyl monome
I : cht khi mo
R
*
: gc t do hoc ion
R M
*
n
R M
+
*
m
R M
n
R M
m
R M
n
R M
+
m
Kt hp (coupling)
Phn ly (Dispropotionation)
Ha hc phn ng trng hp gc t do
Radical Generation
Initiator Radicals
R R 2 R
Initiation
Monomers
R
+
C C R C C
Propagation
R C C
+
C C C C C R
Termination
R C C
+
C C C R
R C C C C C R
Polymer
Chain polymerization
Trng hp gc
Lin kt i C=C
thng tham gia phn
ng trng hp gc t
do v cng c dng
nh cn tr hnh hc
ca cc nhm th
Ionic polym.
Trng hp anion Trng hp cation.
X X
X
radical cationic
anionic
cc nhm th a
electron lm gim mt
electron trn lin
kt i v tip nhn
s tn cng ca cc
nhm anion nh
cyano v cacbonyl
+ -
CH
2
=CH Y
Cc nhm th cho electron
lm tng mt electron
trn ni i v d dng tip
nhn s tn cng ca cc
nhm cation nh alkoxy,
alkyl v phenyl
- +
CH
2
=CH Y
Trng hp gc
1. Overview Free radical polymerization processes
involve at least three mechanistic steps.
A. Khi mo
1. Cu thnh gc t do
In In In
+
In
2. Khi mo
In M
In
+
M
hv , etc.
B. Pht trin mch
In-M
1
.
+ M
2
In-M
1
M
2
.
In-M
1
M
2
.
+ M
3
In-M
1
M
2
M
3
.
In-M
1
M
2
M
3
M
X
.
+ M
Y
In-M
1
M
2
M
3
M
X
M
Y
.
C. Ngt mch

1) Kt Hp (Combination)
In
+
In In In
2) Phn ly ( -hydrogen transfer)
H
In M
x
C
H
C
H
H H
+
In M
y
C
H
C
H H
H
3
C CH
2
M
y
In
CH
2
CH In M
x
+
In-M
X
.
+
.
M
Y
-In In-M
X
-M
Y
-In
D. Chuyn Mch (sometimes) Mt nguyn t chuyn
ln mch ang pht trin v ngt mch phn ng ng
thi pht trn mt mch mi
P
x
R
P
x
+
R H
+
P
x
+
P
y
H
P
x
P
y
+
Chain Transfer to Chain Transfer Agent:
Chain Transfer to Polymer:
Chain Transfer to Monomer:
P
x
.
+ H
2
C=CH-(C=O)OR
Causes Branching
E. S c ch v ngn cn phn ng Mt cht c ch l mt hp cht c th
phn ng mt gc t do to thnh sn phm m khng c kh nng phn
ng vi monome. Mt cht c ch c gi l cht lm kt thc phn ng trng
hp
2. Cc monome thng dng cho phn ng trng hp gc
A. Vinyl Monomers
H
2
C CHX H
2
C CH Cl
Vinyl chloride
H
H
Y
X
F
F H
H
Vinylidene fluoride
B. Allyl Monomers
C. Ester Monomers
OH
O
OR
O
Acrylic Acid Acrylate Esters
X Cl
Allyl Chloride
1) Acrylates
2) Methacrylates
OH
O
OR
O
Methacrylate Esters
3) Vinyl Esters
O
O
Vinyl Acetate
D. Amide Monomers
NH
2
O
NH
2
O
Acrylamide Methacrylamide
Methacrylic Acid
3. Cc monome khng tham gia phn ng trng hp gc
A. 1,2 olefins (Polymerize to oils only)
B. Vinyl ethers
O
R
O
methyl vinyl ether
x
C. 1,2-disubstituted Ethylenes
H
Cl
H
Cl
1,2-dichloroethylene
Initiation free radical polymerization
Thermal initiators
Photochemical
Redox initiators
Ionizing radiation
4. Initiation Getting the thing started!
A. To gc t do (Initiators)
1. Benzoyl Peroxide
C
O
O O C
O
80-90
0
C
C
O
O
2
+
2 CO
2
(continued)
+
Ph
Ph
New Active Site
Initiator End-Group
2) t-Butyl Peroxide
H
3
C C
CH
3
CH
3
O O C
CH
3
CH
3
CH
3
120
0
-140
0
C
H
3
C C
CH
3
CH
3
2
(continued)
H
3
C C
CH
3
CH
3
+
O
O
O
O
3) Azobisisobutyronitrile (AIBN)
(continued)
CH
3
CH
3
H
3
C C N=N C CH
3
CN CN
~60
o
C
or h
H
3
C C
CH
3
CN
+ N
2
H
3
C C
CH
3
CN
C
H
2
CH
Ph
4) Cumyl Hydroperoxide
Ph O
+
OH
C
CH
3
CH
3
O OH
(continued)
Ph O
+
O
O
Ph O
O
O
(continued)
Photochemical initiators:
One or two component.
Used for thin films.
Peroxides
Azo compounds Disulfides
Ketones
S S S 2
h
Redox initiators:
Thng bao gm 2 thnh phn.
t c s dng.
Bc x ion:
X-ray, gamma-ray.
Cu trc b ph v ngu nhin to thnh
gc t do.
c s dng trong mt s trng hp
c bit.
Cht hot ng Fenton
6) Photoinitiators (Photocleavage Norrish I)
O
HO
h v
C
OH
H
+
C
O
C
OH
H
+
Ph
Ph Ph
OH
H
benzoin
(continued)
OR
C C
O O
hv
C
O
2
benzil
7) Photoinitiators (Photo-Abstraction)
O
hv
Ph Ph
O*
benzophenone
excited state
C
R
R
H N
R
R
Ph Ph
OH
+
C
R
R
N
R
R
Photosensitizer
Coinitiator
5. Propagation - Keeping the thing going!
A. The addition of monomer to an active center (free radical)
to generate a new active center.
R C
H
2
CH
2
X
X
R C
H
2
H
C
X
C
H
2
CH
X
X X
etc. etc.
R C
H
2
H
C
X
C
H
2
CH
X
n
(continued)
Examples:
R C
H
2
CH
2
Ph
Ph
R C
H
2
H
C
Ph
C
H
2
CH
Ph
n
R C
H
2
C
H
2
CH
C
O
CH
3
O
O
CH
3
O
R C
H
2
C
H
2
H
C
C
O
CH
3
O
C
H
2
CH
C
O
CH
3
O
Polystyrene
Polymethyl
Acrylate
6. Termination - Stopping the thing!
A. Kt Hp (thng xy ra)
P
x
C
H
2
C
H
X
+
P
y
C
H
2
C
X
H
P
y
C
H
2
C
X
H
P
x
C
H
2
C
H
X
- Thng xy ra u ni u
- To thnh hai mch khi mo (nhm cui)
trn mt chui.
B. Phn Ly
In M
x
C
H
C
H
H H
+
In M
y
C
H
C
H
H H
H
3
C CH
2
M
y
In
CH
2
CH In M
x
+
- To ra sn phm ch c mt mch ca mch khi mo
- To ra mt sn phm c mch khng no v mt
mch no khi kt thc phn ng
D. Ngt mch gc t do s cp kt hp vi cht
khi mo
~~~P
X
CH
2
-CH
.
+
.
In
X
~~~P
X
CH
2
-CH-In
X
More Likely at
High [In
.
]
So molecular mass can be controlled using chain-transfer
agents, hydroperoxide initiators, OR higher levels of
initiator!
7. Chain-Transfer - Rerouting the thing!
A. Definition The transfer of reactivity from the growing polymer
chain to another species. An atom is transferred to the growing
chain, terminating the chain and starting a new one.
~~~P
X
CH
2
-CH
.
+ X-R ~~~P
X
CH
2
-CHX + R
.
Y Y
~~~P
X
CH
2
-CH
.
+ CCl
4
~~~P
X
CH
2
-CHCl + Cl
3
C
.
Y Y
B. Chain-transfer to solvent:
C. Chain-transfer to monomer:
~~~P
X
CH
2
-CH
.
+ H
2
C =CH
~~~P
X
CH
2
-CH
2
+ H
2
C =C
.
OR
H H
~~~P
X
CH - C
.
+ H
2
C =CH
~~~P
X
CH
2
=CH + H
3
C - C
.
Propylene Why wont it polymerize with Free Radicals?
~~~P
X
CH
2
-CH
.
+ HCH=CH
CH
3
CH
3
~~~P
X
CH
2
-CH
2
-CH
3
+ CH
2
=CH-CH
2
.
H
2
C-CH-CH
2

Chain-transfer occurs so readily that propylene wont polymerize


with free radicals.
D. Chain-transfer to polymer:
~~~P
X
CH
2
-CH
2
-CH
2
.
+ ~~~CH
2
-CH
2
-CH
2
~~~
~~~P
X
CH
2
-CH
2
-CH
3
+ ~~~CH
2
-CH-CH
2
~~~

Increases branching and broadens MWD!


E. Chain-transfer to Initiator (Primary Radical
Termination):
~~~P
X
CH
2
.
+ R-O-O-R ~~~P
X
CH
2
-OR +
.
OR
Definition The transfer of reactivity from the growing polymer chain to
another species. An atom is transferred to the growing chain, terminating the
chain and starting a new one.
F. Chain-transfer to Chain-transfer Agent:
Examples: R-OH; R-SH; R-Cl; R-Br
~~~P
X
CH
2
-CH
2
.
+ HS-(CH
2
)
7
CH
3
~~~P
X
CH
2
-CH
3
+
.
S-(CH
2
)
7
CH
3
H
2
C CHX
.
CXH-CH
2
- S-(CH
2
)
7
CH
3
etc., etc., etc.
H
2
C CHX
8. Inhibition and Retardation - Preventing the thing or slowing it down!
Definition Compounds that slow down or stop poly-
merization by forming radicals that are either too
stable or too sterically hindered to initiate poly-
merization OR they prefer coupling (termination)
reactions to initiation reactions.
~~~P
X
CH
2
-CH
.
+ O= =O
para-Benzoquinone
~~~P
X
CH
2
-CH
2
-O- -O
.
Will Not
Propagate
~~~P
X
CH
2
-CH
.
+ O=O ~~~P
X
CH
2
-CH-O-O
.
2.2. Phn ng trng ngng (condensation polymerization)
Phn ng trng ngng l phn ng tng hp polyme xy ra theo
c ch phn ng th vi s thot ra sn phm ph l hp cht
phn t thp v mi giai on pht trin mch cc trung tm
hot ng b tiu hao.
S phn ng trng ngng
A a a
+ B b b A a
B b A a a
+
A a
B
A a
+ B b b
- ab
- ab
- ab
A a
B
A
B b
(a, b l hai nhm chc khc nhau)
Khi cc nhm chc tc dng vi nhau, hp cht phn t thp c tch ra vi s to thnh lin kt mi ni
nhng phn cn li ca cc cht tham gia phn ng vi nhau.
HO CH
2
CH
2
OH
C
O
C
O
O
CH
2
COOH HOOC
4
CH
2
NH
2
H
2
N
6
O C N R N C O
CH
2
CH CH
2
OH OH OH
C
CH
2
OH
CH
2
OH
HOH
2
C
HOH
2
C
etylenglycol
anhydrit phtalic
axit adipic
hecxa metylendiamin
di izoxyanat
glyxerin
penta eritrit
Monome ca phn ng trng ngng
Phn ng trng ngng Big Idea
Phn ng trng ngng Big Idea
Phn ng trng ngng Big Idea
Polymerization mechanisms
- Step-growth polymerization
Stepwise (Condensation) polymerization Reaction
Cc yu cu i vi trng hp tng bc
chuyn ha ca monome cao
Monome phi c tinh khit cao
Hiu sut phn ng cao
H s cn bng ca cc nhm chc cao
c im ca trng hp tng bc
1-S pht trin mch xy ra trong ton b qu trnh phn ng
2-Nng monome gim rt nhanh
3-Khi lng phn t ca polyme tng chm dn trong sut qu trnh phn ng
4- Cng mt c ch phn ng xy ra trong sut qu trnh phn ng
5-Tc ca phn ng trng hp gim theo s gim i ca nhm chc phn ng
6-Khng cn s c mt ca cht khi mo
Stage 1
Consumption
of monomer
n n
Stage 2
Combination
of small fragments
Stage 3
Reaction of
oligomers to give
high molecular
weight polymer
Step-Growth Polymerization
Chc v nhm chc
Nhm chc: l nhm quyt nh tnh cht ca mt loi hp
cht ho hc. V d: - OH, - COOH, - NH
2
, Cl,
Chc: ca mt phn t l s lin kt ng ho tr c th to
thnh vi phn t khc trong iu kin c th ca phn ng trng
hp polyme.
H C
O
H
OH
Xt phn ng gia phenol v formandehyt
*
*
*
OH
v tr hot ng
H C
O
H
OH
H
OH
H
+ +
OH OH
CH
2
- H
2
O
S chc ca phenol = 4
H
2
C CH CH
2
OH OH OH
- Tu thuc vo iu kin phn ng, s chc c th khc nhau.
t
0
< 180
0
C : s chc l 2
t
0
> 180
0
C : s chc l 3
Glyxerin
Polyesters: Synthesis
Example
formation of polyester
nHO-R-OH + nHOOC-R-COOH H-(O-R-OOC-R-CO-)
n
OH+(2n-1)H
2
O
Kinetics of condensation (step Growth ) polymerization
Consider the synthesis of polyester from a diol and a diacid. The first step is the
reaction of the diol and the diacid monomers to form dimer,
HO-R-OH + HOOC-R"-COOH--> HO-R-OCO-R'-COOH + H
2
O
The dimer then forms trimer by the reaction with diol monomer,
HO-R-OCO-R'-COOH + HO-R-OH--> HO-R-OCO-R'-COO-R-OH +H
2
O
and also with diacid monomer,
HO-R-OCO-R'-COOH + HOOC-R'-COOH-->
HOOC-R'-COO-R-OCO-R'-COOH + H
2
O
Polyesters: Structure-property relationships
Polyesters: Structure-property relationships
Other commercially important polyesters:
Polyamides
Nylon 66
Polyamides