18 Hoahoc - Caophantu PDF

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HO HO HO HO H HH H C CAO PHN T C CAO PHN T C CAO PHN T C CAO PHN T

TS. on Th Thu Loan
Khoa Ho - Trng i Hc Bch Khoa Nng
http://hhud.tvu.edu.vn
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Chng 1: NHNG KHI NIM C BN
1.1. Gii thiu chung
-Ngi dn Nam M thi k tin s bit dng cao su thin nhin to
cc sn phm (1492)
-Bin tnh polyme t nhin (gia th k 19)
-Tng hp polyme (u th k 20)
-Khoa hc polyme bt u t 1920
-Khoa hc v cng ngh cc hp cht Cao phn t pht trin mnh vo nhng
nm 60-70
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1.2. Khi nimc bn
Monomer = Mono + mer
Polymer = Poly + mer
Oligomer = Oligos + mer
4
Polymer
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
Monomers
Polymer
Covalent
Bonds
5
Polymer
H
H
C
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
H
H
C
C
H
H
Monomer
Polymer
H
H
C
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
H
H
C
C
H
H
Polymer
6
Mc xch c s
)
CH
(
CH
2 n
Mc xch c s
trng hp
Ex: Polystyren
)
CH
(
CH
2 n
n: trng hp
M = n * m
M: Khi lng phn t polymer
m: Khi lng mt mc xch c s
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degree of polymerization (DP) - the number of monomer units incorporated into
a polymer chain
monodisperse - describing a polymer sample consisting of molecules, all of
which have the same chain length
(an ideal, hypothetical situation, except in natural macromolecules)
polydisperse - describing a polymer consisting of molecules with a variety of
chain lengths (and hence molecular weights) - the real life situation for synthetic
polymers
Descriptions of polymer size:
8
Polydispersity/Molecular Weight Distribution:
Types of Molecular Weight
9
M
i
: KLPT ca phn t th i
N
i
: S phn t c KLPT M
i
Khi lng phn t trung bnh (KLPTTB)
KLPTTB s
KLPTTB trng
KLPTTB nht
10
Phn b khi lng phn t
11
Example: Polydispersity of a sample
M
n
= ? g/mol
M
w
= ? g/mol
PDI = M
w
/M
n
= ?
2.5 x 10
8
1.078 x10
9
3.42924x10
9
8.6490 x 10
9
7.2828 x10
8
5,000
15,400
41,820
9,300
7,140
50,000
70,000
82,000
93,000
102,000
0.10
0.22
0.51
0.10
0.07
N
i
M
i
2
N
i
M
i
M
i
(mol wt)
N
i
(mol or # fxn)
M
i
: KLPT ca phn t th i
N
i
: S phn t c KLPT M
i
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-Various types of rheometers and viscometers is vital for processing.
-Flow under conditions of temperature, pressure or shear.
Rheological Properties
13
-Theo ngun gc:
+Polymer thin nhin
+Polymer tng hp
-Theo thnh phn ho hc ca mch chnh:
+Polymer mch cacbon
+Polymer d mch
+Polymer v c
-Polydimetylsiloxan, Polyphotphat, thu tinh,
-Grafit
1.3. Phn loi
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+Polymer mch cacbon
V d:
15
+Polymer d mch
+Polymer v c
-Kim cng
-Si Thu tinh, Aming, Bo,
16
-Theo cu trc mch:
Polymer mch thng
Branch
Crosslink
Polymer mch nhnh
Polymer mch khng gian ba
chiu
17
-Theo thnh phn monome:
Copolymers (heteropolymers)
Homopolymers
18
19
-Theo cch sp xp nhm chc trong khng gian:
Isotactic
Atactic
Syndiotactic
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21
Cht do (Plastic)
Cao su (Rubber)
Keo dn (Adhesion)
Sn, mc in (Paint, ink)
Si (Fibre)
Compozit (Composite)
-Theo phm vi s dng:
22
-Theo tnh cht c l:
Da vo hiu ng ca polymer vi nhit
-Nha nhit do
-Nha nhit rn
-Vt lu n hi
23
1.4. Nomenclature (danh php)
Poly + (monomer/repetitive unit)
Ex 1: poly(vinyl clorua) = poly + vinyl clorua
Ex 2:
Ex 3:
n CH
2
CH
Cl
CH
2
CH
Cl
( )
n
Poly(hexamethylene adipamide)
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-.. -.-poly()
n v lp li nh nht Tn ca cc nhm th
cui mch
25
Da vo tn nhmchc:
Trivial names (frequently for natural polymers)
-Source: cellulose
-Source and chemical property: nucleic acid
-Main use: starch
Trade name: nylon 6, nylon 6,6,
26
Phng php quan trng nht trong tng hp polyme: trng hp
v trng ngng
Chng 2. Polymerization (Trng hp)
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2.1. Khi nim:
Trng hp l phn ng kt hp cc monome to thnh polyme
trong thnh phn ho hc ca mc xch c s khng khc thnh
phn monome ban u
Ex:
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2.2. c im:
Phn ng trng hp lm gim chc ( khng no) ca hn hp phn
ng
Gim s phn t chung trong h v tng trng lng phn t trung bnh
Cc phn t polyme c hnh thnh rt sm vi vn tc ln
Phn ng trng hp l phn ng cng
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2.3. Phn loi
Da vo bn cht ca trung tm hot ng:
-Trng hp gc t do (TH gc chui)
-Trng hp ion: cation hay anion
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2.4. Trng hp gc chui
2.4.1. C ch: c trng ca c ch chui
Ex 2:
Ex 1
H
2
+ Cl
2
To thnh trung tm hot ng:
Cl
2
2 Cl
as h
Pht trin mch
Cl + H
2
HCl + H
H + Cl
2
HCl + Cl
t mch
H + Cl
HCl
H, Cl va vo thnh bnh v mt
kh nng hot ng
Pht trin mch
.
To thnh trung tm hot ng:
t mch
hoc
R(CH
2
CHX)
n
CH
2
CHX + R(CH
2
CHX)
m
CH
2
CHX
R(CH
2
CHX)
n
CH2CHXCHXCH
2
(CHXCH
2
)
m
R
R(CH
2
CHX)
n
CH
2
CH
2
X + R(CH
2
CHX)
m
CH=CHX
.
.
.
.
. .
.
.
.
.
.
. .
.
31
2.4.2. Cc giai on ca trng hp gc:
a. Khi mo:
-To ra cc gc t do di tc ng ca iu kin bn ngoi
a.1. Khi mo nhit :
Ex: CH
2
=CHX
CH
2
- CHX (lng gc)
.
.
*c im:
-Cc lng gc tc dng vi monome v pht trin mch to polyme
-C ch b gy ni i cha c xc nh r rng
-Di tc dng ca nhit i km vi tc dng ca oxy khng kh hoc tp cht s
thay i ton b c ch qu trnh
-Di tc dng nhit nhiu phn ng ph xy ra c khi khng khng ch c
t
o
.
.
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a.2. Khi mo nh sng (UV)
Ex:
C C
H
H H
C C
H
H
H
.
.
h
+
h
C C
H
H
.
+
H
.
or
M
h
M
*
M
*
R + R
.
.
33
*c im:
-Phng php trng hp xy ra di tc dng ca nh sng gi l trng hp quang
-Vn tc kch thch quang ho:
V
kt
= 2 I
ht
* f
I
ht
: lng t nh sng hp th
2 f: lng gc to thnh di tc dng ca mt lng t nh sng
-Nng lng hot ho ca qu trnh kch thch quang ho trng hp E=0 v khng
ph thuc nhit
-Tc phn ng xy ra nhanh khi c chiu sng v gim dn khi tt nh sng
-Ch yu dng trong nghin cu, hn ch trong sn xut do kh khn trong vic
trang b chiu sng
Khi mo nh sng (UV)
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a.3. Khi mo dng cc bc x:
-Tc nhn khi mo gm:
+Tia (e
-
)
+ Tia (He
2+
)
+ Tia X
+ Tia
*c im:
-Phng php trng hp xy ra di tc dng ca bc x c gi l trng
hp bc x
-Bn cht ging vi trng hp quang, Nng lng hot ho E=0, v khng
ph thuc nhit
-Vn tc phn ng c th ln do bc x c nng lng ln
-Sn phm c tinh khit cao
-Tr ngi duy nht l gi thnh cao (phi c thit b bo v)
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a.4. Khi mo dng cht khi mo ho hc
*Nhng cht khi mo thng dng:
-Acyl peroxides such as acetyl and benzoyl peroxides
-Alkyl peroxides such as cumyl and t-butyl peroxides
36
-Hydroperoxides such as t-butyl and cumyl hydroperoxides
-Peresters such as t-butyl perbenzoate:
Cht khi mo ho hc
37
-Azo: 2,2-Azobisisobutyronitrile (AIBN)
-H thng oxy ho kh:
Ex:
Fe
2+
+ HO-OH HO
-
+ HO + Fe
3+
.
Phng php ny ph bin nht (trong nghin cu cng nh sn xut)
Cht khi mo ho hc
38
b. Pht trin mch:
CH
2
CH
X
R
.
CH
2
CH
X
R
.
CH
2
CH
X
R
.
CH
2
CH
X
R
.
CH CH
2
X
X
CH CH
2
X
R
.
CH
2
CH
CH CH
2
X
R
.
CH CH
2
X
CH
2
CH
X
ui
u
CH CH
2
X
R
.
+
CH
2
CH
X
+
u-u
ui-u
u -ui
ui-ui
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c. Phn ng ngt mch:
~CH=CH
2
+ CH
3
-CH
2
~
disproportionation/isomerization
* Ngt mch bng cht c ch:
Ex:
Quynon
OH
OH
2 R
.
RH
.
O
O
.
O
O
+ +
Hydroquinon
40
*S dng cht lm chm
Ex:
R
.
+
RSH RH + RS
(mecaptan)
.
*iu chnh vn tc phn ng (nhanh n)
Phn ng ngt mch
41
d. Phn ng truyn mch
-Thng xy ra trong qu trnh trng hp
-Lm ngng phn ng pht trin mch phn t, nhng khng lm gim trung
tm hot ng trong h thng
- Cc loi phn ng truyn mch chnh:
+ Truyn mch sang monome
+ Truyn mch sang polyme
+ Truyn mch sang dung mi
+ Truyn mch qua cht khi mo
42
Ex 1:
R + CCl
4
RCl CCl
3
.
.
R +
RCH
2
CHX(CH
2
CHX)
m
R RH + RCHCHX(CH
2
CHX)
m
R
.
.
Ex 2:
CH
2
=CH
Br
-CH
2
-CH
Br
+
-CH
2
-CHBr
Br
CH
2
=CH
.
.
+
Ex 4:
R + (CH
3
)
3
COOH
R + (CH
3
)
3
COO
.
.
Ex 3:
Phn ng truyn mch
43
2.4.3. ng hc ca phn ng trng hp gc
a. Cc quy c n gin ho
-Trng thi dng: qu trnh trng hp gc s pht trin n mt lc t trng thi
n nh, ngha l: vn tc khi mo bng vn tc ngt mch hay nng gc t
do khng thay i theo thi gian:
d[R]
dt
.
= 0
-Kh nng phn ng ca cc gc t do khng ph thuc vo trng lng phn t
44
-Monome ch tiu hao trong qu trnh pht trin mch, cn s tiu hao
monome trong phn ng khi u v truyn mch l khng ng k
-Qu trnh truyn mch khng lm thay i hot tnh ca gc
Cc quy c n gin ho
R + CCl
4
RCl + CCl
3
.
.
Gc ban u
Gc hnh thnh
Ex: Phn ng truyn mch sang dung mi
45
b. Phng trnh vn tc
*Khi mo
+Tc phn hu cht khi mo:
= k
d
[I]
v
d
=
-d[I]
dt
(M)
.
v
i
2 v
d
= 2 f k
d
[I]
v
i = k
i
[I]
I: Cht khi mo
R: gc t do
M: monome
k
d
: hng s tc phn hu cht khi mo
k
i
: hng s tc qu trnh khi mo
k
p
: hng s tc qu trnh pht trin mch
k
t
: hng s tc qu trnh ngt mch
v
d
: tc phn hu cht khi mo
v
i
: tc khi mo
.
46
+Vn tc pht trin mch:
= k
p
[M][M]
v
p
=
-d[M]
dt
.
.
.
(M)
(M)
(M)
(M)
.
.
.
+Vn tc ngt mch:
= k
t
[M]
v
t
=
-d[M]
dt
.
.
2
Khi t trng thi dng: v
i
=v
t
.
= k
t
[M]
2
k
i
[I]
1/2
.
[M] =
k
i
[I]
k
t
= k
p
v = v
p
1/2
ki
k
t
[I]
1/2
[M]
[I]
1/2
K [M] v =
= k
p
1/2
ki
k
t
K
vi
47
Trong thc t s m c th khc:
[I]
K [M] v =
m
n
Tng qut:
CH
2
=CH
O
O - H
C
CH=CH
2
C
H - O
O
+ m >1 (thng 1,5-2) do:
-Hin tng solvat ho
-Mt s lin kt vt l bn vng tn ti
Ex:
Lin kt hydro
48
Xc nh m, n
+Tin hnh cc th nghim:
+Gi [I]=const
+Xc nh:
[M
1
] v
1
(mol/l.s)
Sau 60 s
[M
2
] v
2
[M
3
] v
3
[I]
K [M] v =
m
n
lg v = lg A + m lg M
.
.
.
.
.
lg v
lg [M]
*Xc nh tng t i vi n
49
*Chiu di mch ng hc:
v
v
t
p
=
Tng ng vi lng monome tiu hao theo thi gian
Tng ng vi s gc t do polyme tiu hao trong
mt n v thi gian, tng ng s polyme hnh
thnh trong mt n v thi gian
trng thi dng: v
i
=v
t
v
v
i
p
= = =
v
v
t
p k
p
1/2
ki k
t
[I]
1/2
[M]
(*)
50
Nhn (*) vi k
p
[M] ta c:
1/2
=
k
p
1/2
ki
k
t
[I]
[M]
2
2
[M] k
p
k
t
1/2
=
k
p
1/2
ki k
t
[I]
1/2
[M]
(*)
M:
= k
p
v = v
p
1/2
ki
k
t
[I]
1/2
[M]
=
k
t
[M]
k
p
2
2
v
51
Trng hp khng c phn ng truyn mch
*Tt mch theo c ch ti hp gc:
2 =
: trng hp trung bnh ca ca

polyme
2 RM
n
M
.
2 RM
n
MMM
n
R
[ ]
[ ]
2
1
I k
M K 2
2
i
= =
=
k
p
1/2
ki k
t
[I]
1/2
[M]
1/2
2 P =
k
p
k
i
1/2
1/2
k
i
k
t
[I]
[M]
= k
p
1/2
ki
k
t
K
*Tt mch bt t phn:
2 RM
n
M
.
2 RM
n
M + RM
n
M
=
[ ]
[ ]
2
1
I k
M K
i
= =
1/2
= P
k
p
k
i
1/2
1/2
k
i
k
t
[I]
[M]
* trng hp trung bnh
52
Trng hp c phn ng truyn mch
[ ]
[ ]
[ ]
[ ]
[ ] M k
I k
M k
S k
k
k
M k
v k
P
1
p
i
p
s
p
m
2
2
p
p t
+ + + =
i s m
k , k , k : hng s tc qu trnh truyn mch sang
monome, dung mi, cht khi mo
53
2.4.4. Cc yu t nh hng n qu trnh trng hp gc
a. Nhit :
Theo phng trnh Arrhenius:
k= A e
-E/RT
E: nng lng hot ho phn ng
Ta c:
= k
p
1/2
ki
k
t
K
RT
2
E
2
E
E
A
A
A ln
k
k
k ln
2
1
t
i
p
2
1
t
i
p
(
\
|
\
|
+
(
(
|
|
\
|
=
(
(
|
|
\
|
t i
p
E
v
[I]
1/2
K [M] v =
[ ][ ]
2
1
RT
E
2
1
t
i
p
I M e
A
A
A v
v
(
(
|
|
\
|
=
54
[ ]
[ ]
2
1
I k
M K
i
= =
[ ]
[ ]
2
1
I
M K'
= =
k
p
1/2
ki k
t
K=
1/2
= k
p
1/2
ki
k
t
K
Vi
[ ]
[ ]
RT
E
2
E
2
E
I
M
ln
A A
A
ln P ln
p
t i
2
1
2
1
i
2
1
p
p
(
\
|
+
|
\
|
+
(
(
+
(
(
=
k= A e
-E/RT
*nh hng ca nhit n KLPT polyme?
55
b.Nng cht khi mo
[I]
1/2
K [M] v =
[ ]
[ ]
2
1
I
M K'
= =
c. Nng monome
Nng monome [M] :
- Vn tc phn ng v
-Khi lng phn t polyme
d. p sut
* p sut cao (vi ngn at), khi p sut :
- Vn tc phn ng v
-Khi lng phn t polyme
56
e. Tp cht v oxy
-S nh hng ca tp cht v oxy khng kh ph thuc bn
cht monome
-Khi c mt oxy, c th lm tng hoc gim tc phn ng
-Cu to mch polyme s khng ng nht
-Tp cht thng c mt trong monome hoc dung mi,
57
2.4.5. Cc phng php tin hnh trng hp gc
C 4 phng php trng hp chnh:
- TH khi
-TH dung dch
-TH nh tng
-TH huyn ph
58
a. Trng hp khi
*Hn hp phn ng gm:
monome
Cht khi u (nu c)
*Qu trnh phn ng thng:
Gia nhit
Khuy trn
*u im:
Phng php n gin
polyme c tinh khit cao
Vn tc phn ng cao, nng sut ln
C th trng hp ngay trong khun mu, to sn phm c hnh th phc tp.
59
*Nhc im:
D b nhit cc b do nht cao
-Nn tin hnh tng hp trong thit b nh
-Khng ch qu trnh phn ng chm
-Tuy nhin s khng kinh t
Sn phm dng khi ly sn phm v gia cng kh khn
Trng hp khi
60
b. Trng hp trong dung dch
*Hn hp phn ng gm:
Monome
Cht khi u (nu c)
Dung mi
Ho tan monome v polyme
Ho tan monome, khng ho tan polyme
*Qu trnh phn ng thng:
Gia nhit
Khuy trn
*u im:
Khng c hin tng nhit cc b
Dung mi lm gim nht gip phn ng xy ra m du hn
*Nhc im:
Dung mi hu c c, t tin (khng kinh t), d chy
61
c. Trng hp nh tng (D th)
10
1
10
0
10
2
10
3
10
4
10
5
10
6
(nm)
Emulsion
polymerization
Suspension
polymerization
Nonaqueous
dispersion
Kch thc ht tiu biu t c trong trng hp d th
62
Nc
Monome
Cht nh ho Cht khi u
Cht iu ho pH
Cht iu ho sc cng b mt
*Thnh phn:
Trng hp nh tng
63
Phi c ho tan ti thiu, lin quan n s khuych tn cng
nh s tin vo ca cc gc t do.
Nu monome ho tan tt trong nc th ng thi s c trng
hp dung dch xy ra.
Nu polyme ho tan trong nc c to thnh c th lm thay
i nht ca latex.
monome
Trng hp nh tng
64
Cht khi u
Cht khi u ho tan trong nc
Dng ph bin:
+Mui kali, natri, amoni persulfate
Ti pH>6, t~50
o
C, lin kt O-O b phn ly to 2 gc ging nhau
+Cc hp cht azo tan trong nc
VD: 2,2-azo bis (2-amino propane) dihydrochloride
2
8 2
O S

4
2 SO
Trng hp nh tng
65
+H oxy ho kh vi cc peroxide
Thng dng cc h sau:
Ex1:
Fe
2+
+ HO-OH HO
-
+ HO + Fe
3+
.
2
8 2
O S
2
4
SO

4
SO
+ 3
Fe
+
+ 2
Fe + +
Ex2:

4
SO
M
+

M SO
4
2 5 6
COO) H (C
2 3 5 6
) N(CH H C

COO H C
5 6
COO H C
5 6
[ ]
+
2 3 5 6
) N(CH H C +
+
+
HO
.
M
HO - M
.
+
OOH C H C
5 6

CH
3
CH
3
+ 2
Fe

O C H C
5 6
CH
3
CH
3
+ 3
Fe

HO
+ +
+
Ex3:
Ex4:
Trng hp nh tng
66
Cht hot ng b mt (Cht nh ho, x phng, cht n nh)
Cu to phn t gm 2 u:
+ Mt u a nc
+ V mt u k nc (mch hydrocacbon di)
Vai tr: Lm gim sc cng b mt phn chia gia hai pha nc-monome
+To nn cc mixen dng phng (tm) hay dng cu
+n nh cc git monome
+n nh cc ht polyme pht trin to sn phm n nh
K nc
a nc
Trng hp nh tng
Dng bn
Dng tm
67
Phn loi cht hot ng b mt:
+ Cht hot ng b mt anionic
+ Cht hot ng b mt cationic
+ Cht hot ng b mt lng tnh
+Cht hot ng b mt khng phi ion
Trng hp nh tng
68
+Giai on I: Cc ht polyme bt u c hnh thnh
+Giai on II: s ln dn ca cc ht polyme vi s cung cp u n monome
+Giai on III: s cung cp monome dng, do vy tc gim dn
Trng hp nh tng tri qua 3 giai on:
*Qu trnh trng hp nh tng:
u tin, monome c phn tn thnh nhng git
nh, n nh bng cht nh ho to nn cc
mixen trong pha nc (Fig.1)
Fig.1
Trng hp nh tng
69
*u:
Sn phm cui cng l latex polyme vi nng cao (70-80%)
Thot nhit phn ng d dng hn
+To polyme c KLPT cao hn
Phn ng xy ra nht thp + chuyn ho monome cao trong
khong thi gian ngn
Hiu qu kinh t cao
*Nhc:
Tp cht nhiu
Trng hp nh tng
70
d. Trng hp huyn ph
-Trng hp nhng git monome nh huyn ph trong mi trng:
Nc
Parafin lng hoc dn xut clo ca hydrocacbon
Thnh phn:
monome
Cht n nh huyn ph:
+ Polyme a nc
+Cc mui v c
Cht khi u: azo, diazo, peroxide,
71
*C ch:
Ging trng hp khi, mi git xem nh l mt bnh phn ng huyn ph trong
nc, nn cn gi l trng hp khi trong git
Cc git monome phn tn trong nc th hn trong TH nh tng
H c n nh nh cht n nh huyn ph
Cht khi u tan trong monome khi mo cho phn ng trng hp xy ra trong
cc git monome to nn cc tiu phn hay cc ht hnh cu (polyme)
Cc tiu phn hay cc ht hnh cu ny d tch ra khi ngng khuy v khng cn
dng cht ng t c bit
72
*Kch thc ht ph thuc:
Tc khuy trn
Nng v loi cht n nh
*c im:
Pha nc ng vai tr l tc nhn truyn nhit hu hiu
nht trong bnh phn ng duy tr khng i
Khi lng phn t cao
a phn tn nh
73
So snh gia TH nh tng v TH huyn ph
Cht khi u tan trong monome
Kch thc ht polyme ln hn
TH xy ra trong git
Sn phm tinh khit hn
Cht khi u tan trong nc
Kch thc ht polyme b hn
TH xy ra trong cc mixen
Sn phm cha nhiu tp cht hn
TH huyn ph TH nh tng
74
2.5. Trng hp ion
-L phn ng tng hp polyme m trung tm hot ng l ion
-Da vo bn cht trung tm hot ng: TH cation v TH anion
75
2.5.1. c im:
Phn ng mang tnh chn lc, xy ra di tc dng ca xc tc TH xc tc
Ph thuc loi nhm th c mt trong monome, s dng cht xc tc thch hp:
CH
2
= CH X
+
-
CH
2
= CH X
-
+
R
+
CH
2
CH X
R
+
CH
2
CH X
+
R
(1)
(2)
R
+
tn cng vo (1) hay (2) d dng hn???
Trng hp ion
76
-Nhm th y in t (alkyl, alkoxy,) TH cation
-Nhm th ht in t (-CN, -NO
2
, -COOH,) TH anion
-i vi styren, c th tham gia TH gc, TH anion, TH cation nh h thng lin hp
vng thm
Vn tc phn ng TH ion vn tc TH gc
Phn ng thng tin hnh trong dung dch, tuy nhin ph thuc nhiu vo dung
mi, nn dng dung mi tr nhng ho tan tt monome
Ngt mch khng theo c ch ti hp gc, m do truyn mch sang monome, dung
mi hay hon nguyn xc tc
Tnh n nh thp
Thng tin hnh nhit thp
Trng hp ion
77
2.5.2. Trng hp cation:
CH
2
= CH X
+
-
+ Y
+
Y-CH
2
CHX
+
+Xc tc:
Axit Lewis (Friedels-crafts): AlCl
3
, BF
3
, SnCl
4
,TiCl
4,
, nhng cht ny khi c
mt ca ng xc tc (H
2
O, HX, ROHl nhng cht d cho proton) s to thnh
cation:
Hoc axit (HCl, H
2
SO
4
, H
3
PO
4
,) cho proton hay i in t
TiCl
4
+ H
2
O [TiCl
4
OH]
-
H
+
[TiCl
4
OH]
-
H
+
+
TiCl
4
+ HCl [TiCl
5
]
-
H
+
[TiCl
5
]
-
H
+
+
HX H
+
X
-
+
BF
3
+ H
2
O [BF
3
OH]
-
H
+
[BF
3
OH]
-
H
+
(Y
+
)
+
*C ch
78
Ex: Tng hp iso butylen vi xc tc H
2
SO
4
:
H
+
HSO
4
CH
2
= C CH
3
CH
3
-
+
CH
3
C
CH
3
CH
3
+ , (HSO
4
)
-
(ion tri du)
Trimetyl cacboni
(Trung tm hot ng)
+
hot ng ca trung tm hot ng ph thuc vo khong cch gia ion tri du v
ion cacboni (cation), khong cch cng xa ion cacboni cng d kt hp
Nhm th y in t: gia tng mt e ca ni i c i lc cao vi proton hay
cation
2
H C
+
H C
+
3
CH
) (
C
+
3
CH
3
CH
< <
79
*ng hc
Ex: Tng hp PS theo c ch TH cation
Phn ng xy ra qua 3 giai on
+Khi mo
CH CH
2
= H
2
SO
4
C
6
H
5
+

+
4 3
HSO H, C CH
C
6
H
5
k
i
+Pht trin mch:
k
p
CH CH
2
= - CH CH -
2

C
6
H
5
+
4 3
HSO H, C CH
C
6
H
5
C
6
H
5
4 2
HSO H, C CH
C
6
H
5
[ ]
1 - n 2
CH CH -
C
6
H
5
C
6
H
5
4 2
HSO H, C CH -
CH CH
2
=
C
6
H
5
+
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
4 2
HSO H, C CH -
k
p
80
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
4 2
HSO H, C CH -
+Ngt mch:
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
4 2
HSO H, C CH -
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
CH CH - = H
2
SO
4
+
CH CH
2
=
C
6
H
5
+
4 3
HSO H, C CH
C
6
H
5
k
t
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
CH CH - =
+
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
4 2
HSO H, C CH -
[ ]
n 2
CH CH -
C
6
H
5
C
6
H
5
H OSO CH CH -
3 2

' '
t
k
'
t
k
81
[ ][ ] XT M k v
i i
=
[ ][ ]
+
= M M k v
p p
[ ]
+
= M k v
t t [ ] XT
[ ]
+
M
t
v , v
p
, v
i
t
k , k
i
, k
p
Ta c:
: tc phn ng khi mo, pht
trin mch v ngt mch
: nng xc tc
: nng trung tm hot ng
trngthi n nh
: hng s tc phn ng khi mo, pht
trin mch v ngt mch
trng thi dng: v
i
=v
t
P
[M], [XT]
= P
v
v
t
p
= =
v
v
i
p k
p
k
t
[M
+
]
[M] [M
+
]
k
p
k
t
[M]
=
* trng hp trung bnh l:
*Tc trng hp
[ ] [ ][ ] XT M k M k' v P v v
i i p
= = =
t p
v P v =
P
[ ] M k' =
[ ] [ ] XT M k v
2
=
P
[ ] M k' =
v
[M]
2
, [XT]
82
Lu :
-Hin tng ng phn ho ca cc cation sinh ra to cation bn vng hn
-Hin tng ng phn ho cng mnh khi nhit cng cao
-ng phn ho lm cho s ng nht v cu to ca sn phm kh t c
Khng ch nhit phn ng thp
3
2 3
3
CH
CH CH C CH
CH
= X H +
3
3 3
3
CH
CH H C C CH
CH

+
3
3 3
3
CH
CH CH C CH
CH

+
+
Trng hp cation
83
2.5.3. Trng hp anion:
c im
-Xy ra do s tng tc ca monome vi anion ca xc tc cacbanion
-monome cha nhm ht e (-CN, NO
2
, ), lm phn cc lin kt i v lm n
nh cacbanion
Xc tc: l nhng cht cho e
+Hydrua v amidua ca kim loi kim
+Hp cht c kim v phc ca hp cht c kim
+Kim loi kim
84
[ ][ ]
-
i i
An M k v =
[ ][ ]
-
p p
M M k v =
[ ]
= M k v
t t [ ]
-
An
[ ]
M
t
v , v
p
, v
i
t
k , k
i
, k
p
Ta c:
: tc phn ng khi mo, pht
trin mch v ngt mch
: nng xc tc
: nng trung tm hot ng trng
thi n nh
: hng s tc phn ng khi mo, pht
trin mch v ngt mch
trng thi dng: v
i
=v
t
P
[M], [XT]
= P
v
v
t
p
= =
v
v
i
p k
p
k
t
[M
-
]
[M] [M
-
]
k
p
k
t
[M]
=
* trng hp trung bnh l:
*Tc trng hp
[ ] [ ][ ]
-
i i p
An M k M k' v P v v = = =
t p
v P v =
P
[ ] M k' =
[ ] [ ]
-
2
An M k v =
P
[ ] M k' =
P
[M
]2
, [XT]
ng hc
Trng hp anion thun
85
C ch: Ex: TH anion thun vi xc tc kali amit trong NH
3
lng (KNH
2
/NH
3
lg)
+ +
+
2 2
NH K NH K
HX C CH NH CHX CH NH
2 2 2 2
= +
HX C CH CHX CH NH CHX CH HX C CH NH
2 2 2 2 2 2

= +
HX C CH - CHX CH CHX CH NH CHX CH HX C CH CHX CH NH
2 2 2 2 2 2 2 2

= +
[ ] [ ] HX C CH CHX CH NH CHX CH HX C CH CHX CH NH
2 2 2 2 2 1 2 2

= +
n n
[ ] [ ]
-
2 2 2 2 2 3 2 2 2
NH X CH CH CHX CH NH NH HX C CH CHX CH NH + +
n n
+ Giai on khi mo:
2.5.3.1.Trng hp anion thun
+ Giai on pht trin mch:
+ Giai on ngt mch
86
C ch: Ex: Xc tc c kim RCH
2
Li
2.5.3.2.Trng hp anion phi tr
Li
Li
CH
2
R
CH
2
R
+
R CH Li
2

Li
Li
CH
2
R
CH
2
R
Li
CH
2
R
R CH Li 3
2

+Giai on 1:
+

Li C L
H
R
CHX CH
2
=
+
Li L L L
C
HX C H C
-
2

+
H
R
+

2
Li C CH C L L
H
R
H
X
+Giai on 2:
+
(monome vinylic)
87
+

Li C L
H
R
+
(monome divinylic)
C CH
2
=
CH
CH
3
CH
2
2 2
CH CH L L
C CH
2
Li
CH
R
CH
3
+Giai on 3:
H
HX C H C
-
2

+
+

2
Li C CH C L L L
H
R
X
HX C H C
-
2

+
+

2
Li C CH C L L
H
R
H
X
H
+

2 2
Li C CH C CH C L L
H
R
X
H
X
Trng hp anion phi tr
88
Trng hp anion phi tr
*c im:
-Phn ln to polyme c cu trc iu ho lp th
-Cu to ca phc trung gian v s phn b khng gian ca cc phn t
monome trong phc ph thuc :
+Tnh phn cc ca lin kt kim loi- cacbon trong xc tc
+Cu trc nhm alkyl ca xc tc
+ Mi trng
89
2.5.3.3.Trng hp anion vi xc tc kimloi kim
*C ch: qua giai on trng hp trung gian to thnh ion gc
CHX CH
2
=
Li
X
HLi C H C
2
+
+Na
THF
.
-
Na
+
CHX CH
2
=
X
HNa C H C
2
+
+
Cc cht c bn cht axit hoc dung mi c kh nng cho proton lm gim
phn ng TH anion :
X
HLi C H C
2
+
+ H
+
X
CH H C
2 2

+
Li
+
90
Theo c ch TH ion:
X
HLi C H C
2
+
X
HLi C H C
2
+
X X
HLi C CH H C - H C Li
2 2
+ +

+
X X X
HLi C CH CH CH H C - H C Li
2 2 2
+ +

CHX CH
2
= +
91
Tng hp copolyme khi t polyme sng
92
c im:
-L phn ng TH phi tr
-polyme thu c iu ho lp th
-Phn ng c th tin hnh trong trng thi ng th hay d th
-Vi xc tc Ziegler-Natta d th:
+monome tn cng vo v tr xc nh trn b mt mng li xc tc ca
mng li tinh th
+monome i vo mch gia b mt cht xc tc v u cui ca mch
polyme ang pht trin
2.5.3.4. Trng hp vi xc tc Ziegler-Natta
93
R
P CH H C e M
2
-

+
L
R
H C H C
2
- +
L
B
t
x
c
t
c
R R
P CH CH - CH H C e M
2 2
-

+
L
B
t
x
c
t
c
-
H e M
L
+
B
t
x
c
t
c
R R
P CH CH - CH CH
2 2
= +
Ngt mch
Pht trin
mch
3
2
-
2
3
CH
H C
Al i T
CH
CH
+
CHR CH
2
=
Trng hp vi xc tc Ziegler-Natta
94
3
2
3 2 2
3
CH
Cl CH Cl
Al Ti
CH CH CH Cl
CH
3
2
2
3
CH
CH
Al Ti
CH
CH
CHR CH
2
=
3
2
-
2
3
CH
H C
Al i T
CH
CH
+
3 2
2
2
3
CH CHRCH
CH
Al Ti
CH
CH
HR C H
CH H C i T
Al CH
CH
2
3 2
-
2
3
+
+

K C
CHR CH
CH CH Ti
Al CH
CH
2
3 2
2
3
CHR CH
2
=
Trng hp vi xc tc Ziegler-Natta
95
Chng 3: NG TRNG HP
3.1.Khi nim v phn ng ng trng hp: l qu trnh kt hp ca hai hay nhiu
monome khc nhau to thnh polyme c s tham gia ca c hai hay nhiu monome.
L L BBBAAAA AAABBBBBAA nB nA +
Copolyme
Trong mt mch c hai loi mc xch c s tr ln
Tnh cht copolyme s tt hn polyme n trng hp
S dng ci thin hoc nng cao tnh cht mt s polyme
96
3.2.ng trng hp gc
Giai on khi mo v tt mch xy ra nh khi trng hp
2R I

+
1 1
RM M R

+
2 2
RM M R
C 4 loi phn ng c bn:
3.2.1.Phng trnh thnh phn:
97
3.2.2. ng hc:
[ ][ ]
1 1 11 11
M M k v

=
[ ][ ]
2 1 12 12
M M k v

=
[ ][ ]
1 2 21 21
M M k v

=
[ ][ ]
2 2 22 22
M M k v

=
[ ]
=
dt
M d
1
[ ][ ] [ ][ ]
1 2 21 1 1 11 21 11
M M k M M k v v

+ = +
[ ][ ] [ ][ ]
2 2 22 2 1 12 22 12
M M k M M k v v

+ = +
[ ]
=
dt
M d
2
Tc tiu hao monome:
Tc phn ng
T l thay i nng monome M
1
v M
2
:
[ ]
[ ]
=
2
1
M d
M d
[ ][ ] [ ][ ]
[ ][ ] [ ][ ]
2 2 22 2 1 12
1 2 21 1 1 11
M M k M M k
M M k M M k

+
+
98
trng thi dng: bin thin vn tc khng i:
[ ]
[ ]
=
2
1
M d
M d
[ ][ ] [ ][ ]
[ ][ ] [ ][ ]
2 2 22 2 1 12
1 2 21 1 1 11
M M k M M k
M M k M M k

+
+
Chia
cho (*) ta c:
[ ][ ] [ ][ ]
1 2 21 2 1 12
M M k M M k

=
(*)
[ ]
[ ]
=
2
1
M d
M d
[ ][ ] [ ][ ]
[ ][ ] [ ][ ]
[ ][ ] [ ][ ]
[ ][ ] [ ][ ]
1 2 21 2 1 12
2 2 22 2 1 12
1 2 21 2 1 12
1 2 21 1 1 11
M M k M M k
M M k M M k
M M k M M k
M M k M M k

+
+
[ ]
[ ]
=
2
1
M d
M d
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
1 2 21
2 2 22
2 1 12
1 1 11
M M k
M M k
M M k
M M k
+ 1
+ 1
99
t:
[ ]
[ ]
=
2
1
M d
M d
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
1 2 21
2 2 22
2 1 12
1 1 11
M M k
M M k
M M k
M M k
+ 1
+ 1
[ ]
[ ]
=
2
1
M d
M d
[ ]
[ ]
[ ]
[ ]
1
2
2
1
M
M
M
M
+ 1
+ 1
r
1
r
2
(Hng s ng trng hp)
Phng trnh Mayo-Lewis
[ ]
[ ]
=
2
1
M d
M d
[ ]
[ ]
2
1
M
M [ ] [ ]
[ ] [ ]
1 2 2
2 1 1
M M r
M M r
+
+
.
100
[ ]
[ ]
=
2
1
M d
M d
[ ]
[ ]
2
1
M
M [ ] [ ]
[ ] [ ]
1 2 2
2 1 1
M M r
M M r
+
+
.
t
[ ]
[ ]
2
1
M d
M d
n =
[ ]
[ ]
2
1
M
M
x =
: t l thnh phn monome M
1
, M
2
c trong
thnh phn copolyme ti thi im t
: t l thnh phn monome M
1
, M
2
thi im ban u
[ ]
[ ]
=
2
1
M d
M d
[ ] [ ] ( )
[ ] [ ] ( ) 1 /
1 /
1 2 2
2 1 1
+
+
M M r
M M r
n=
( ) 1 /
1
2
1
+
+
=
x r
x r
n
101
5
Cc trng hp:
1-r
1
=r
2
=1: hn hp ng u (him c)
2-r
1
=r
2
=0: copolyme lun phin
3-r
1
>1, r
2
<1 copolyme giu M
1
4-r
1
<1, r
2
<1 :
M
1
d phn ng vi M
2
M
2
d phn ng vi M
1
-Copolyme trc im un giu M
2
-Copolyme sau im un giu M
1
5-r
1
<1, r
2
>1 copolyme giu M
2
6-r
1
>1, r
2
>1 kh to copolyme, thu
c hn hp 2 polyme ring l
.
.
ngha ca hng s ng trng hp
102
V d: ng trng hp 2 monome butadien (M
1
) (r
1
=1,39) v Styren (M
2
) (r
2
=0,78)
Trong qu trnh TH: tiu hao M
1
>M
2
T l x thay i nu M
1
khng c thm vo b lng tiu hao nhiu hn
Nu gi t l
[ ]
[ ]
1
M
M
x
2
1
= =
Th copolyme thu c c t l M
1
/M
2
nh sau:
( )
34 , 1
78 , 1
39 , 2
1 ) 1 / 78 , 0 (
1 1 . 39 , 1
1 /
1
2
1
= =
+
+
=
+
+
=
x r
x r
n
S phn t butadien trong copolyme
gp 1,34 ln so vi s phn t styren
103
inner tubes Butyl Rubber H
2
C=C-CH=CH
2
H
2
C=C(CH
3
)
2
adhesives
hoses
Nitrile Rubber H
2
C=C-CH=CH
2
H
2
C=CHCN
tires
SBR
styrene butadiene
rubber
H
2
C=C-CH=CH
2
H
2
C=CHC
6
H
5
films & fibers Saran H
2
C=CCl
2
H
2
C=CHCl
Uses Copolymer Monomer B Monomer A
Some Useful Copolymers
104
Chng 4: TRNG NGNG
4.1. nh ngha: l phn ng tng hp polyme xy ra nh tc dng ca cc nhm
chc (-OH, -COOH, NH
2
,-COCl ) dn n s to thnh cc lin kt mi, ng
thi sinh ra cc hp cht thp phn t (H
2
O, NH
3
, HCl,).
chc phi 2
105
Functionality is a critical importance in this reaction
Example Example Example Example
1)Condensation reaction of carboxylic acid groups with hydroxyl groups both acetic acid
and ethyl alcohol are monofunctional compounds which yield ethyl acetate with
elimination of water
CH
3
COOH +CH
3
CH
2
OH CH
3
COOCH
2
CH
3
+ H
2
O
From this polyme chain can not form.
2)If we have terephthalic acid and ethylene glycol both are difuctional
COOH COOH COOH COOH CH CH CH CH
2 22 2
- -- -OH OH OH OH COOCH COOCH COOCH COOCH
2 22 2
- -- -CH CH CH CH
2 22 2
- -- -OH OH OH OH
+ ++ + + H + H + H + H
2 22 2
O OO O
COOH COOH COOH COOH CH CH CH CH
2 22 2
- -- -OH OH OH OH COOH COOH COOH COOH
The product is an ester which have one carboxylic acid end group and one hydroxyl end-
group (i.e. it is also difunctional).
The dimers can react with molecules of acid or alcohol or dimer formation of difuctional.
106
4.2. Phn loi:
Trng ngng ng th (2 loi monome ho tan vo nhau)
Trng ngng d th (2 loi monome khng ho tan vo nhau)
Trng ngng 2 chiu: cc monome c chc 2 nhm chc (AA, BB, AB)
Trng ngng 3 chiu: monome cha >2 nhm chc
Trng ngng
Trng ngng thun nghch
Trng ngng khng thun nghch
107
*Difunctional monomers linear step polymerization
n HOOC-R
1
- COOH + nHO-R
2
- OH H [ OOC-R
1
-COOR
2
]
n
OH + (2n-1) H
2
O
Polyesters may also prepared from single monome which contain both types of functional group.
Ex: R-hydroxyl carboxylic acids (HOOC-R-OH)
the formation of linear polyesters from diacide and diol Ex:
n HOOC-R -OH HO [ OC-R-O ]
n
H + (2n-1) H
2
O
Trng ngng 2 chiu
*Trifunctional monomers branched polymer
Ex: Tetephtalic acid react with glycerol
HO CH
2
CH (OH) CH
2
OH
HOOC COOH +
Trng ngng 3 chiu
108
Non Linear Step Polymerization
The presence of a reactivity monomer with functionality > 2, causes
branching initially and crosslinking structure ultimately.
Normally the resulting polymer are rigid.
The point at which the first net work molecules is formed is known as
the gel-point (gelation) i.e. change of the Reaction mixture from a
viscous liquid to solid gel which shows no tendency to flow.
109
Example
The reaction of dicarboylic acid with a triol.
HOOC-R
1
-COOH + HO-R
2
-OH
OH
O O O O
----O-R
2
-O-C-R
1
-C-O-R
2
-O-C-R
1
-C-O-R
2
O
C = O
R
1
C = O
O O O
-----O-C-R
1
-C-O-R
2
O
C = O
R
1
-C-O-R
2
-O-----
O
110
Long reaction times are essential to
produce polymer with high average
molecular weight
Increased reaction time increases overall
product yield, but doesn't affect polymer
average molecular weight
Oligomers steadily increase in size,
polymer average molecular weight increases
as reaction proceeds
High polymer appears immediately,
average molecular weight doesn't change
much as reaction proceeds
Monomers disappear early, in favor of low
oligomers
Monomer concentration decreases steadily
as reaction time increases
The reaction mixture consists of oligomers
of many sizes, in a statistically calculable
distribution
The reaction mixture consists of high
polymer and unreacted monomers, with
very few actively growing chains
Reaction can occur independently between
any pair of molecular species
The only growth reaction is addition of
monomer to a growing chain with a reactive
terminus
Step Growth Polymerization Chain Growth Polymerization
4.3. So snh gia trng hp v trng ngng
111
112
4.4.c im
*Monomer tham gia phn ng phi c chc 2
+ chc:
Urea NH
2
-C-NH
2
O
Melamine H
2
N N NH
2
C C
N N
C
NH
2
Hydroxyl axit HO - (CH
2
)
3
- COOH
OH
Phenol
HOCH
2
CH(OH)CH
2
OH
Glyxerin
113
- chc trung bnh ( ): s lng trung bnh cc nhm chc hot ng tnh trn mt
n v monome
f
=
i
i i
n
f n
f
n
i
: s monome i c trong h phn ng
f
i
: s chc ca monome i
Ex: Hn hp phn ng gm:
10 monome 3 chc
15 monome 2 chc
( ) ( )
4 , 2
15 10
2 15 3 10
f =
+
+
=
chc trung bnh ch l khi nim ton hc
114
Cc phn ng c s:
Y A Z A X Y A 2X
Y Z A X Y - B - Y X A X + B
Qu trnh phn ng
115
Y A Z - A Z A X Y A X Y A Z A X +
Y A Z - A Z - A Z - A Z A X
Y A Z - A Z - A X Y A Z A X

+
+Qu trnh pht trin mch
116
*Nu monome c > 2 nhm chc to polyme nhnh hoc cu trc mng li
khng gian 3 chiu
X X X
Y B Z A Z B Z A X Y B Y X A X +
X X
Y B Y Y B Z A Z B Z A X +
Y B Z A Z B Z A X
Z Z
B B
Z Z
Y B Z A Z B Z A X

Y Y
B B
Z Z
Y B Z A Z B Z A X
Qu trnh pht trin mch
117
Phn ng trng ngng kt thc do:
-Ngt mch ho hc: cc nhm chc b bin i hoc ph hu trong qu trnh
phn ng hoc to gel khng gian 3 chiu
Ph hu gc COOH
To vng
-Ngt mch vt l: Khi tt c cc nhm chc ca monome cng nh hp cht
trung gian b cn tr s tham gia vo phn ng do s tng nht, gim linh ng
khi KLPT ln
+
2
CO H R COOH R
+ Kt thc qu trnh
118
*Cc phn ng xy ra ng thi vi phn ng trng ngng
OH COO HOOC
4
3
L L L
OH COO HOOC
2
1
L L L
+
OH COO HOOC
4
3
L L L
OH COO HOOC
2
1
L L L
Phn ng trao i:
OH COO HOOC OH HO COOH HOOC
2
1
2
1
+ L L L L L L
Phn ng trng ngng
Phn ng trao i
OH COO HOOC
OH COO HOOC
2
3
4
1

L L L
L L L
+
Khi lng phn t cc mch polyme tr nn ng nht a phn tn
+
119
*Phn ng trao i
Phn ng trao i ester:
2 3 4 1 4 3 2 1
R - O - CO - R R - O - CO - R R - O - CO - R R - O - CO - R + +
2 3 1 3 2 1
R - O - CO - R H - O - CO - R H - O - CO - R R - O - CO - R + +
3 1 2 3 2 1
R - O - CO - R H - O - R H - O - R R - O - CO - R + +
3 1 2 2 2 3 2 1
R - NH - CO - R NH - R NH - R R - NH - CO - R + +
Phn ng axit phn
Phn ng ancol phn
Phn ng amin phn
+Mt s phn ng trao i thng xy ra:
120
c im
O
O H O C R' CO - O R
O
O H COOH R' OC R HO
COOH R' HOOC OH R HO
2
2
+ =
+
+
Ko di mch polyme
Phn ng ng vng
Cc phn ng cnh tranh trong qu trnh trng ngng:
*Phn ng ng vng:
121
Phn ng ng vng thng khng mong mun
+
TN
n
g
v
n
g
Called the intramolecular reaction
A chain containing two mutually reactive groups can react with it self and a ring
structure forms.
O
HO-----C-OH C-O
O
122
Mc ng vng
-Vng 6 bn nht (cyclo hexan), n vng 5, 7
-Sc cng vng:
S n v cu to trong vng: 5 6 7 8
Sc cng, kcal/mol: 5,1 1,3 5,0 8,0
Mc ng vng ph thuc:
+Cu to phn t monome :
+ bn ca vng c hnh thnh
123
Example
3, 4, 8, 9, 10 and 11 rings are un stable due to bond angle strain and steric
repulsion between atoms. (Rowded into the center of the ring respectively
and usually not formed).
12 members and larger rings are more stable and can be formed.
Their probability of formation decreases as the ring size increases. This is
because the probability of the two ends of a single chain meeting decreases
as the chain length increases.
Self condensation of hydroxyl carboxylic acids
HO - (CH
2
)
3
- COOH CH
2
-CH
2
+ H
2
O
CH
2
O
C
O
124
+ Nhit : Nng lng hot ho cho phn ng ng vng > trng ngng
nhit thc y phn ng to vng v ngc li
+ Nng ca monome [M]:
[M] Tc trng ngng
[M] Tc trng ngng
125
Mt s mc xch c s ca polyme trng ngng
126
Mt s mc xch c s ca polyme trng ngng
127
Gi n
o
: s phn t ban u cha tham gia phn ng
n: S phn t ca h ti thi im t
trng ngng ( trng hp trung bnh):
n
n
P
0
=
f
i
: chc ca cht i
chuyn ho :
[ ]
f n
n n 2
x
0
0

=
S chc mt i
S chc ban u
=
|
|
\
|
=
0
n
n
1
f
2
x
x f - 2
2
P =
Phng trnh Carothers
4.5. ng hc
* Hn hp ng t lng:
Phng trnh Carothers
: chc trung bnh
=
i
i i
n
f n
f f
128
x f - 2
2
P =
Phng trnh Carothers
Xt cc trng hp:
1 x 1, f = = 1. 2 P =
5 2 3 3 5 2
H COOC CH COOH CH OH H C : Ex +
2.
2 f =
x - 1
1
P =
x
P
HO - (CH
2
)
3
- COOH HOCH
2
CH
2
OH +
Ex:
129
3. 2 f >
x f - 2
2
P =
Ex:
HO - (CH
2
)
3
- COOH HOCH
2
CH(OH)CH
2
OH +
(6 mol) (4 mol)
4 , 2
4 6
4 * 3 6 * 2
n
f n
f
i
i i
=
+
+
= =
Gi s
0,83 x P = =
130
-Khi u phn ng: t=0,
0
B
0
A
N N
H s t lng:
[ ]
[ ]
0
B
0
A
0
0
N
N
B
A
r = =
: N , N
0
B
0
A
s nhm chc ban u ca mi loi monome
[ ] [ ]: B , A
0 0
Nng mol ban u ca mi loi monome A v B
2
r
1
1 N
2
N
N N
N
2
N N
onomer m
0
A
0
A
0
B
0
A
0
A
0
B
0
A
|
\
|
+
=
|
|
\
|
+
=
+
=
( )
x N N N
x 1 N N
0 0
B
0
A
A B
A
=
=
x: chuyn ho
( ) x N N x 1 N N N
0 0 0
B A
A B A
+ = +
Vi
*Hn hp khng ng t lng
Xt phn ng trng ngng mch thng ( ): AA + BB -AB-
2 f =
131
Tng s phn t polyme hnh thnh:
2
2x
r
1
1 N
2
x 2N N N
polymer
0
A 0
A
0
B
0
A
|
\
|
+
=
+
=
trng hp trung bnh:

2
2x
r
1
1 N
2
r
1
1 N
n
n
P
0
A
0
A
0
|
\
|
+
|
\
|
+
= =
2rx r 1
r 1
P
+
+
=
n
0
: s phn t monome trc phn ng
n: s phn t thi im t
132
[ ] [ ] 1 r B A
0 0

2rx r 1
r 1
P 1 , 1
+
+
= x r
r 1
r 1
P 1 , 1
+
= = x r
x=0,98
x=1
x=0,99
1
0,99 0,98 0,97
0
1
% mol d
hoc tp cht
P
r
133
*Phng trnh quan h gia x v n
a
HOOC-R
1
- COOH + HO-R
2
- OH H [ OOC-R
1
-COOR
2
]
n
OH + H
2
O
x y z a
( )
2
0
0
a
0
0
2
a 0
y x
a z
y x
a z
N
N
N
N
N
N N
N
N N N
N N
N N
C C
C C
K
|
|
\
|
=

2
a
P
1
n
K
|
\
|
=
Khi phn ng trng ngng xy ra to
polyme c KLPT ln
0
N
N
0
n
a
: s mol n cht tch ra trn mi
mc xch c s ca polyme
n
a
a
n
K
P =
N
N
n
n
P
0 0
= =
134
a
n
K
P =
P Mun
a
n
K
*Cc phng php loi sn phm ph:
Chng ct (sp ph l nc):gp kh khn do t>100
0
C, thi gian ditin hnh p sut
thp, mi trng chn khng, dng dung mi to hn hp ng ph
Nu sp ph khng phi l nc m l axit, baztrung ho, to phc
Ex: HCl trung ho bng NaOH
135
4.6. Cc phng php trng ngng
4.6.1. Trng ngng khi (nng chy):
-Nhit phn ng ln
-Khuy mnh hn hp phn ng
- hn ch cc phn ng ph, cn tin hnh phn ng trong mi trng kh tr, cui phn
ng thng tin hnh trong mi trng chn khng v cn tch tch loi hp cht thp phn
t ra khi mi trng phn ng.
*u im:
-Thu c ngay sn phm vo cui ca phn ng
-Sn phm tinh khit
-Phn ng nhanh
- nht ca hn hp phn ng ch tng nhanh vo cui giai on phn ng
136
4.6.2. Trng ngng dung dch:
-i vi polyme c nht caokhng th dng phng php TN khi
-Tng i ging TH dung dch:
+ Phn ng tin hnh khi c dung mi
+Mononer tan trong dung mi
+ polyme c th tan hoc khng tan trong dung mi
-KLPT ca polyme tan trong dung mi> polyme khng tan trong dung mi
*u:
Thng dng i vi monome
v polyme km bn nhit
-Phn ng thng xy
ra nhit thp
Hn ch c nhiu phn ng ph
*Nhc: Thng c mt tp cht v phi tch dung mi
137
4.6.3. Trng ngng trong pha rn:
-Cha c nghin cu y
-Xy ra vi tc cao gn nhit nng chy ca monome
-Tc phn ng tng r rt khi nhit ca h tin cng gn n nhit nng chy
-C ngha ln i vi vic tng hp polyme t nhng monome d b phn hu nhit
nng chy
-Thng dng tng hp polyamit t mui ca diamin v diaxit, cc polyme c cha d
t trong mch chnh, polyme v c.
138
4.6.4. Trng ngng trn b mt phn chia pha
-Khi 2 monome khng tan vo nhau
-Thng xy ra nhit phng
-Tc phn ng cao
-Polyme c TLPT rt cao
-Polyme to thnh c th c ly trc tip ra khi mi trng phn ng, c th
trc tip to si hay to mng
-Thng dng tng hp: Polyeste, polyamit, polyuretan,
139
Chng 5: TRNG HP BC
5.1. Khi nim: Trng hp bc (TH di chuyn) l phn ng tng hp polyme xy ra bng
cch di chuyn nguyn t linh ng (thng l hydro) ca phn t monome ny ti phn t
monome khc ln mch.
Ex:
CHR CH CHR CH CHR CH CHR CH
3 2 2
= = + =
CHR CH - CHR CH CHR CH CHR CH CHR CH CHR CH
2 3 2 3
= = + =
CHR CH - CHR CH - CHR CH - CHR CH - CHR CH CHR CH
2 2 2 2 3
=
140
5.2. c im:
-Theo tin trnh phn ng, s phn t monome gim, trng lng phn t trung bnh ca polyme
tng ln ma khng xy ra s thay i thnh phn nguyn t ca cc cht phn ng. C th biu
din phng trnh tng qut ging nh phn ng TH mch:
( )
n
A nA
-Khc TH mch, phn ng xy ra bng cch kt hp dn dn tng bc cc phn t monome v
km theo vic tng tng ng trng lng phn t ca polyme
.
.
.
1
2 3
4 5 6
Thi gian TH, gi
T
r
n
g
l
n
g
p
h
n
t
nh hng ca thi gian phn ng n TLPT polyme

141
-Cc hp cht trung gian to thnh rt bn vng v c th tch ra khi mi trng phn ng
-Kh nng phn ng ca nhng hp cht trung gian v monome ban u nh nhau
-Qu trnh TH bc c th biu din nh sau:
1 n 1 n
4 1 3
3 1 2
2 1 1
A A A
.......... ..........
A A A
A A A
A A A
+
+
+
+
+
A
1
,A
2
, A
3
, : l nhng phn t monome,
dimer, trimer,
-Polyme c tng hp t olfin bng phng php TH bc c TLPT khng cao
142
Formation des polyurthanes
Ex:
143
OH OR C NH R N C O OH R HO O C N R N C O
' '
= = + = = = =
O
O C N - R - NH - C - O OR C NH R N C O
O C N R N C O OH OR C NH R N C O
'
'
= = = =
= = = = + = =
O
O
O
OH R O C NH - R - NH - C - O OR C NH R N C O
OH R HO O C N - R - NH - C - O OR C NH R N C O
' '
' '
= =
+ = = = =
O
O
O
O
diisoxyanat
diol
*Tng hp polyuretan t diisoxyanat v diol
144
- linh ng ca nguyn t hydro trong cc nhm chc tham gia phn ng nh hng n
tc phn ng
Ex:
OH OR C NH R N C O OH R HO O C N R N C O
' '
= = + = = = =
O
2
'
2
'
2
NH R - NH C NH R N C O NH R N H O C N R N C O = = + = = = =
O
diisoxyanat
diol
diisoxyanat
diamin
polyurtan
Polyur
145
-T s cc cu t ban u nh hng nhiu n TLPT polyme
1:1 1:1,01 1,01:1 1,94:1 1:1,04
T
r
n
g
l
n
g
p
h
n
t
T l cu t diol/diisoxyanat
nh hng ca t l cc cu t n TLPT ca polyurtan
- S c mt monome n chc (alcol, hydroxyl, isoxyanat,) s lm gim TLPT
-S c mt ca monome c chc >2, s to polyme c cu trc mch nhnh, khng gian
ba chiu
146
Chng 6: TRNG HP M VNG
(RING-OPENING POLYMERIZATION)
6.1. Khi nim: Trng hp m vng l phn ng tng hp polyme mch thng t nhng
monome vng khng km theo vic tch sn phm ph thp phn t v thnh phn nguyn
t ca polyme khng khc vi thnh phn nguyn t ca monome.
Ex:
147
6.2. c im:
-Ging TH mch v TH bc, sn phm polyme thu c c thnh phn nguyn t khng khc
vi thnh phn nguyn t ca polyme, qu trnh phn ng khng km theo vic tch sn
phm ph thp phn t. Phng trnh tng qut c biu din nh sau:
-Khng lm thay i cu trc in t ca cc lin kt ho hc v tng s cc lin kt
trong h, khng xut hin cc loi lin kt ho hc mi
Z R Z R n
n
148
polyethylene

diisoxyanat
diol
OH OR C N R N C O OH R HO O C N R N C O
' '
= = + = = = =
O
polyurethane

H

Polyethylene oxide

2 2
CH CH O
n
n

149
-Phn ng xy ra thun nghch
-Tc phn ng ph thuc bn vng
-Khi a nhm th vo mt trong cc nguyn t ca vng s lm gim hay mt kh
nng TH ca n
-Cc cht hot ho cho TH m vng: nc, axit, kim, xc tc loi Fridel-Crafts
(BF
3
,TiCl
4
,),
150
6.3. Cc giai on phn ng
1. Ph v thun nghch monome vng ban u
Y R X a Z R +
a: Phn t cht hot ho
X, Y : cc nhm chc c to thnh phi ph v lin kt Z bng cht hot ho
2. Tc dng tng h ca vng monome vi cc sn phm ph vng
Y - R - Z R X Z R Y R X +
Y - R - Z R - Z R X Z R Y - R - Z R X +
Y - R - Z R X Z R Y - R - Z R X +
n-1
n
151
Ex: Trng hp -caprolactam vi s c mt ca nc
-aminocaproic axit
C-(CH
2
)
5
-NH
2
O
HO
NH
(CH
2
)
5
CO
-caprolactam
H OH
NH
(CH
2
)
5
CO
C-(CH
2
)
5
-NH
2
O
HO
C-(CH
2
)
5
-NHCO- (CH
2
)
5
-NH
2
O
HO
+
NH
(CH
2
)
5
CO
C-(CH
2
)
5
-NH H
O
HO
n-1
C-(CH
2
)
5
-NH H HO
n
O
+
+
Tng qut:
NH
(CH
2
)
5
CO
H OH
C-(CH
2
)
5
-NH H HO
n
O
poly--caproamit
152
-Ngy nay, c dng trong cng nghip
tng hp poly--caproamit, polyetylenoxyt,
polysiloxan,
153
CHNG 7: TNH CHT HO HC CA POLYME
7.1. c imv phn loi phn ng ho hc ca polyme
7.1.1. c im:
-V nguyn tc polyme cng l hp cht ho hctham gia phn ng ho hc nh kh
nng phn ng ca cc nhm chc c trong mch polyme.
-Ex: polyme cha nhm chc cacboxyl vai tr mt axit
polyme cha ni i b gy lin kt i
154
Tuy nhin:
-Do TLPT polyme ln linh ng km
-Do tn ti lc tng tc ni, ngoi phn t, sp xp tng h gia cc mch phn t, kh
nng ho tan gy nh hng n kh nng phn ng ca polyme
Ex: kh nng phn ng ca OH trong xenlulo km hn OH trong glyxerin
n
Xenlulo Glyxerin
155
-Hiu sut phn ng khng bao gi t 100%: thng sau phn ng vn cn
mt s nhm chc khng tham gia
Tng kh nng phn ng:
+ Ct mch P M
p
tng linh ng
+Thay i cu trc: ho tan vo cc dung mi khc nhau tch, ko gin cc mch
i phn t ra khi nhau, nhm gim s tng tc
156
-polyme thng l nhng hp cht a chc khi tnh ton, khi nim mol cn phi thay i
R C
O
O
R' R C
O
OH
+
HO R' + H
2
O
xt
1 mol
1 mol
*khi nim mol
Polyvinyl acetate
Polyvinyl alcohol
xt
157
*Vai tr:
-Tng hp mt s polyme t cc polyme thin nhin hay cc polyme tng hp khc
Ex:
Polyvinyl acetate
Polyvinyl alcohol
Vinyl alcohol
158
-Bin tnh ho hc polymeci thin mt s tnh cht, to nn 1 s tnh cht mi
-Ghp cc polyme vi nhau polyme ng trng hp
SO
3
H SO
3
H
PS khng c kh nng trao i ion
Cationit
-iu ch cc hp cht thp phn t t cc polyme thin nhin
Ex:
Ex: iu ch cn t saccarit nh thu phn
159
7.1.2. Phn loi: 3 nhm
Khng lm thay i M
p
chuyn ho thnh polyme tng t
Tng M
p
Copolyme ghp, khi, ng rn
Gim Mp Phn hu polyme
Theo quy lut ngu nhin: lin kt
trong mch b t v tr bt k
Gii trng hp: depolyme ho
(ngc li vi trng hp, t t
lin kt cui mch)
160
Polyvinyl alcohol
7.2. Phn ng chuyn ho thnh polyme tng t - Khng lmthay i Mp
OCOCH
3
HO
-
(CH
3
CO)
2
O
Polyvinyl acetate
-Khng c s khc bit ln v M
p
trc v sau phn ng
-Khng phi ton b nhm -OCOCH
3
-OH chuyn ho khng bao gi t
c 100%
Tng chuyn ho, cn iu chnh:
+ pH
+Nhit
+ Khuy trn
*ng dng: Bin tnh ho hc cc polyme
161
Bin tnh ho hc cc polyme
C 2 phng php bin tnh:
Thay i nguyn liu: thay i cu to ca nguyn liu u
Thay i tnh cht bng cch a vo cc nhm chc mi m khng lm thay i nhiu M
p
CH
2
CH
Cl
CH
2
Cl
C
Cl
CH
2
Cl
C
Cl
Cl
2
Perclovinyl
Ex1: PVC c s dng nhiu. Tuy nhin c nhc im: kh nng bm dnh km
Bin tnh:
-ng trng hp vi vinyliden clorua
-Clo hoPerclovinyl
162
Ex 2: Xem polyme nh l cht mang
X
X
X
X
+ Y
Z
Z
Z
Z
NH
2
NH
2
NH
2
NH
2
+ RCOOH
NH
COR
NH
COR
NH
COR
NH
COR
163
7.3. Phn ng lm tng M
p
7.3.1. Phn ng khu mch
X
X
X
X
Z
Z
Z
Z
X
X
X
X
+
*Phn ng khu mch: l phn ng to thnh cc lin kt ho hc gia cc mch phn t (cn
gi l lin kt ngang hay lin kt cu) to polyme c cu trc mng li khng gian
Lin kt ngang
164
-Hin tng khu mch xy ra khi polyme c cha cc nhm chc c kh nng tham gia
phn ng vi nhau mt cch trc tip hoc gin tip qua mt cht th 3
-Cht th 3 c thm vo gi l: cht ng rn
-Khi khu mch:
+Polyme chuyn trng thi lng rn
+Polyme mt kh nng nng chy v ho tan
+Tng cc tnh cht c l ( cng, bn va p,)
165
Ex1:
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
CH
2
O CH
2
CH
2
CH
2
O
+
t
0
Qu trnh ng rn PF (trc tip)
C=C
C=C
C C
C C
(S)n + S
Ex3: Lu ho cao su
Ex4: ng rn nha epoxy
Nha epoxy + Cht ng rn sn phm ng rn
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
CH
CH
h
Ex2: Khu mch PE khi c tc dng ca bc x
166
-Tnh cht polyme khu mch ph thuc mt cu ni ngang
Mt cu ni tng Tnh cht c l tng
Tuy nhin, mt cu ni cao qu sn phm gin
Ex: Cao su lu ho c nhiu cu S cng gin, km mm do
Epoxy nhiu cht ng rn gin
iu chnh lng cu ni ngang hp l
167
7.3.2. iu ch copolyme khi v ghp
*Copolyme khi:
A A
A
B
B B
To polyme c cha nhm chc cui mch sau ghp khi bng phn ng ca cc nhm
chc ny
Ex:
H
2
N
NH
2
CH
2
CH
O
+
H
2
N
CH
2
CH NH
OH
Polyamit
Epoxy
Copolyme khi
168
*Copolyme ghp:
X
X
X
X Z
R
Z
R
Z
R
Z
R
+ R-Y
Ex1: Trong mi trng kim, khi tc dng etylen oxyt ln polyvinylacol (PVAc) thu c
sn phm mch nhnh
OH
OH
OH
OH
OCH
2
CH
2
OCH
2
CH
2
OH
OCH
2
CH
2
OCH
2
CH
2
OCH
2
CH
2
OH
+
CH
2 CH
2
O
n
PVAc
Etylen oxyt
Copolyme nhnh
169
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
CH
Tia
CH
2
CH
X
+
CH
2
CH
2
CH
2
CH
CH
CH
2
CHX
n
CH
2
CHX
m
PE
Copolyme nhnh
*Copolyme ghp:
170
7.4. Phn ng lm gimM
p
Qu trnh phn hu polyme
7.4.1. Khi nim: S t lin kt ho hc ca mch chnh di tc ng ha hc hay vt
l bn ngoi to ra polyme c M
p
nh hn nhng khng lm thay i thnh phn ho hc
ca mc xch c s gi l s phn hu polyme.
* phn hu
n
a
p =
a: s lin kt b t
n: tng s lin kt trong mch chnh
171
iu ch hp cht thp phn t t hp cht cao phn t thin nhin, tng hp
Tng kh nng phn ng ho hc cho polyme: M

p
linh ng ca polyme
Ex: Cn cao su: di tc dng ca lc c hc ct mch Mp linh ng tng
trn tt vi cc ph gia, xc tin, lu hunh,
Phn ln s phn hu khng mong mun khi gia cng sn phm v bo qun
Di tc dng ca tc nhn ho hc, mi trng, vt l: nh sng, nhit , tia t
ngoi, s phn hu polyme thc y gim tnh cht c l gim tnh nng
s dng, qu trnh xy ra theo thi gian.
S lo ho polyme
172
*Lo ho:
L hin tng kh trnh khi, xy ra ngu nhin di tc dng ca nhiu tc nhn
Chng lo ho: n nh polyme
* Khi nghin cu s phn hu polyme thit lp c cc quy lut ca qu trnh phn
hu xc nh c ch gia cng thch hp, tm cht n nh polyme thch hp
7.4.2. Phn loi
Theo quy lut ngu nhin: lin kt b t v tr bt k trong mch
Phn hu gii trng hp: lin kt b t l lin kt ca mc xch cui mch
CH
2
CH
C
6
H
5
n
CH
2
CH
C
6
H
5
n-1
CH
2
CH
C
6
H
5
CH
2
CH
C
6
H
5
CH
2
CH
C
6
H
5
n-2
Chng ct PS, PMMA
thu monome
173
7.4.3. Phn hu ho hc
Xy ra di tc dng ca cc tc nhn ho hc khc nhau nh: axit, baz, amin, ancol,..
-Thu phn
-Axit phn
- Baz phn
- Amin phn
-Ancol phn
-..
* Phn ng phn hu bng cc tc nhn ho hc:
174
*Phn hu oxy ho
-Xy ra hydro d mch cng nh mch cacbon-cacbon do tc dng ca oxy khng kh
hay cc cht oxy ho khc nhau
* bn ca polyme i vi cc cht oxy ho ph thuc vo cu trc polyme nhng ch
yu vo s nhm chc hay lin kt d b oxy ho trong mch polyme
-Qu trnh oxy ho xy ra phc tp, khng ch ct mch cho sn phm thp phn t, m
cn xut hin nhng nhm chc mi
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH CH
2 + RO
.
+ ROH
CH
2
CH
2
CH
2
CH
2
CH
+
175
7.4.4. Phn hu vt l:
* Nhit : Xy ra theo c ch gc t do, nhit cao phn hu tng ln
Thng km theo tc dng ca oxy to peroxit
*nh sng: c bit cc tia c nng lng cao (tia UV)
*C hc: xy ra khi nghin, p , trn,
Ex: Cn cao su
176
7.5. n nh polyme
7.5.1. Phng php ho hc:
-To cho polyme c cu trc bn vng vi cc tc nhn ca mi trng
Ex: -a vng thm vo
-a cc hp cht c kim (C-Si, C-B, C-Sn,)
-ng trng hp vi cc monome khc
7.5.2. Phng php vt l: (dng ch yu hin nay)
a vo polyme cc cht n nh
n nh nhit
n nh quang
n nh c hc
C th dng kt hp
177
Ex: PVC
Phn hu
HCl
-n nh PVC tng tui th sn phm:
-Dng cc mui kim loi, oxyt kim loi (Cd, Pb hay dng trc
y c trnh dng)
-Hin nay, thng dng cc hp cht c thit: octoat thit, cc
amin thm, dn xut phenol (hydroquinon)

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1

HO HO HO HO H HH H C CAO PHN T C CAO PHN T C CAO PHN T C CAO PHN T

: trng hp trung bnh ca ca

trng hp trung bnh:

nh hng ca thi gian phn ng n TLPT polyme

Tng kh nng phn ng ho hc cho polyme: M

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