Hóa học Polyme

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1 of 72 10/16/2007 8:35 PM
B BB B i ii i g gg gi ii i n nn ng gg g
Ho hc cao phn t Ho hc cao phn t Ho hc cao phn t Ho hc cao phn t

Phn 1 Mt s khi nim c bn v Ho hc cao phn t.
1/ Khi nim: Hp cht cao phn t c hnh thnh t hng trm, hng nghn
nguyn t ni lin nhau bng nhng lin kt ho hc bn vng, v d xenluloza
(C
6
H
10
O
3
)
n
, cao su (C
5
H
8
)
n
, polivinylclorua [- CH
2
- CHCl-]
n
.
nh ngha trn tuy kh tng qut nhng khng p dng cho mi trng hp.
Khi chuyn t phn t nh sang phn t c khi lng ln (cao phn t) th tnh cht
cng thay i theo. C nhng tnh cht m polime th hin, nhng phn t nh
(monome) khng th hin v ngc li.
Phn t polime gm nhiu mt xch c bn ni lin vi nhau thnh mch. Mt
xch c bn l mt nhm cc nguyn t ti thiu c trong mch, l nhm c lp
tham gia vo cu trc ca phn t polime. Nu k hiu mt xch l A, th cng thc
phn t polime c th biu din nh sau:
-A A A A A A A A -
V d cao su isopren c cng thc:

y mt xch c bn l
nn cng thc polime c th biu din:

2. H s polime ho
Trong cng thc ca phn t polime, n c gi l h s polime ho (hay trng
hp). Vy "h s polime ho l s mt xch trong phn t polime". C th biu din
bng cng thc: n= (1)
n= h s trng hp
M: Khi lng phn t ca polime
m: Khi lng phn t ca monome (ca mt mt xch).
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T : M = n.m (2)
Vy khi lng phn t polime bng tch ca KLPT monome vi h s trng hp.
Trong nhiu trng hp mt cht cao phn t c cu to bi nhiu loi mt xch
c bn, trng hp phn t cao phn t c gi l copolime. V d 1 copolime cu
to t hai loi mt xch (hai loi monome).
- A A B A B B A B A B A A A B -
V d

Copolime polietylenpropylen; y l sn phm ng trng hp ca etylen v
propylen.
3/ Phn loi cc polime v gi tn
C nhiu cch phn loi, trong cch ph bin nht l phn loi theo cu trc
ho hc ca mch. C hai loi chnh.
+ Polime ng mch, trong mch chnh ch gm cc nguyn t cacbon.
+ Polime d mch, trong mch chnh gm c nguyn t cacbon v cc d nguyn
t (nh O, N, S, Si).
Ngoi ra ngi ta cn phn loi theo cu trc mch nhnh. Sau y xt mt s cc
polime thuc cc nhm trn.
a/ Polime ng mch
Tn gi: thm t poly vo pha trc tn ca monome.
V d: monome polyme

Tt c cc polime ng mch u to thnh t cc hydrocacbon c KLPT thp.
i vi cc dn xut ca hydrocacbon th tn gi ca polime cng da theo tn ca
monome.
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V d: monome Polime

b/ Polime d mch
- CH
2
- CH
2
- NH- CH
2
- CH
2
- NH-
Polydilenimin (polyamit)

4/ Tng hp cc polime
Qu trnh tng hp polime thng qua t nht 2 giai on:
Giai on tng hp (hoc sn xut) monome.
Giai on chuyn monome thnh polime (s polime ho).
Cc monome l hp cht c KLPT thp, rt hot ng. Do chng d tc dng
vi nhau to ra mch di c KLPT ln (cc cao phn t). Phn ng polime ho xy
ra theo c ch phn ng dy chuyn. Mun c phn ng th phn t monome phi
c nhm hot ng (c kh nng phn ng), nu monome c 1 nhm chc hot
ng gi l hp cht n chc; nu c hai nhm hot ng gi l lng chc; nu c
t 3 nhm tr ln gi l a chc.
V d:
a)

b)

4 of 72 10/16/2007 8:35 PM

Nh vy polime c th l mch thng, mch nhnh hay thm ch c mch vng
hoc xen k mch vng v cc mch thng
V phn ng to thnh polime mch thng ca hp cht lng chc c th l:
a/ Do tc dng ca cc nhm chc cng loi:

b/ Phn ng gia hai nhm chc khc loi:
Phn ng este ho gia diol v diaxt to ra polyeste.

Phn ng gia diamin v diaxt to thnh poliaminoaxit

Phn ng gia hp cht epoxy v diaxt:

vn vn
Chng 2:
Cc phng php tng hp Polime
Cng nh cc phn ng dy chuyn khc, phn ng polime ho mch theo c ch
dy chuyn t nht cng gm 3 giai on c bn: Khi u (to trung tm hot
ng); pht trin mch v ngt mch. Trung tm hot ng ca phn ng polime
ho c th l cc gc t do (cc phn t trung ho in c 1 hay 2 in t khng cp
i) hoc cc ion (cc phn t tch in (-) hoc (+)). Tu theo bn cht ca cc
trung tm hot ng m ngi ta chia phn ng polime ho thnh 2 loi: Phn ng
polime ho theo c ch gc v phn ng polime ho theo c ch ion.
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Bi 2-1: Phn ng polime ho theo c ch gc
2.1.1. Khi nim
Cc hp cht khng no (nh olefin v dn xut ca n, cc dien, axt khng
no) thng xy ra phn ng polime ho theo c ch gc t do.
Trong trng hp ny, giai on khi u to ra gc t do, gc ny phn ng vi
phn t monome to ra gc mi.
V d phn ng polime ho etylen.
Giai on khi u
I gc R

(I- initiator: cht khi u)
Giai on khi u phn ng bao gi cng tiu tn nng lng ln v tin trin chm.
Giai on pht trin mch
R

+ CH
2
= CH
2
R- CH
2
-
CH
2
Nu k hiu monome l M v gc R- CH
2
-
CH
2
l R
1
ta c:
R

+ M R

1

R

1
+ M R

2
R

2
+ M R

3

Vn vn
Vi R

2
l R- CH
2
- CH
2
- CH
2
-
CH
2
Giai on pht trin mch c nng lng hot ho nh v tc phn ng ln. Do
hiu ng nhit ca phn ng giai on ny lun >0.
Giai on tt mch:
R
i
+ R
j
P
i+j
(P
i+j
l phn t polime)
Ch : P
i+j
c th c di mch khc nhau tu thuc di ca cc gc R
i
v
R
j
.
Cc phn ng trong giai on tt mch c nng lng hot ho nh v tc phn
ng cao.
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c im ca phn ng ny l gc t do ban u (R

) nm trong thnh phn ca
polime sn phm.
2.1.2. Cc phng php khi mo phn ng polime ho theo c ch gc
2.1.2.1. KhI mo phn ng bng cht khi u
C nhiu phng php khi u phn ng polime ho theo c ch gc, trong
thng dng nht l cho cht khi u (cht khi mo) vo monome. Cht khi u
l cht c kh nng phn hu thnh gc t do trong iu kin phn ng polime ho.
S phn r phn t cht khi u thnh gc t do tiu tn mt nng lng nh hn
nng lng cn to thnh gc t dotc tip t monome. Do khi a cht khi
u vo s lm tng ng k tc phn ng khI mo dn n tc phn ng
polime ho tng.
Cc cht khi u thng dng l:
Peroxit benzoin ( C
6
H
5
COO)
2
Hydroperoxit cumen

Peroxit butyric bc ba
(Di-t-butylperoxit)
- Tert-Butyl hydropeoxit

- Nc oxi gi H
2
O
2
- Kali pesunfat K
2
S
2
O
8

- Amino pesunfat (NH
4
)
2
S
2
O
8
Azo-bis-iso butyronitril

V d: Peroxit benzoin phn hu theo phn ng vi vn tc

k
i
v v
i
l hng s vn tc v vn tc phn ng.
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K hiu nng chung ca cht khi u l [ I ] ta c:
V
i
=k
i
.[ I ] (2.1)
Gc t do C
6
H
5
COO
c th phn hu thnh gc phenyl:

C gc C
6
H
5
COO
C
6
H
5
u c kh nng khi u phn ng polime ho nn
vn tc khi u l: vn tc khi u = 2v
i
= 2k
i
.[ I ]. (2.2)
Trong qu trnh phn ng mt s gc t do b kt hp thnh phn t bn nh:
V c s tiu hao mt s gc t do to thnh phn t bn nn vn tc trn phi
c hiu chnh bng mt h s hiu chnh f, f l hiu dng ca cht khi u (
gc to thnh ban u tham gia vo phn ng).
Vy vn tc khi u s l:
V
i
= 2k
i
.f.[ I ] (2.3)
t k
i
= 2k
1
.f ta c
v
i
=k
i
.[ I ] (2.4)
Trong k
i
l hng s vn tc khi u hiu chnh, k
i
c th c gi tr khc
nhau i vi cc cht khi u khc nhau.
V d: peroxit benzoin lm cht khi u n s tham gia cc phn ng: (f = 1)

V th (gi s M l etylen) th trong sn phm polime s c c nhm
C
6
H
5
COOCH
2
CH
2
v nhm C
6
H
5
- CH
2
-
CH
2
Nu dng dinitryl ca axit azodiizo butiric, s phn hu theo s :

Trong trng hp ny h s hiu chnh f = 0,6, ngha l khong 40% gc t do hnh
thnh tham gia phn ng ph.
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Hoc

2.1.2.2. Khi mo phn ng bng nhit
Cc gc t do khi u phn ng polime ho c th hnh thnh bng cch un
nng monome.
V d: monome CH
2
= CHX (X l halogen)
Khi c nhit tc dng, phn t monome c th bin thnh gc lng chc:
Gc ny phn ng vi monome:

Gc lng chc mi ny li tc dng vi monome v c th tip tc:

Tuy nhin nu monome tinh khit th phn ng khi u bng nhit xy ra rt
chm v khI mo phn ng bng nhit cn c nng lng hot ho cao ln ti 18
20 kcal/mol (phn ng c nng lng hot ho cng ln cng kh xy ra). Nu c ln
tp cht, v d c oxi th monome d dng bin thnh hp cht peroxit,
v d

peroxit ny d phn hu thnh gc t do khi mo cho phn ng polime ho.
2.1.2.3. KhI mo phn ng bng nh sng (chiu sng)
Di tc dng ca nh sng, phn t monome b kch hot

Nng lng chiu sng cng ln, phn t monome cng d b kch hot (do tia
t ngoi kch hot phn ng d dng nht). Phn t b kch hot sau chuyn
thnh gc t do lng chc.
ri phn ng pht trin mch xy ra nh trng hp trn.
Cc nghin cu cho thy phn ng polime ho bng quang hc c nng lng
hot ho rt nh so vi polime ho bng nhit hay dng cht khi u:
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. Nu dng cht khi u hoc khi u bng nhit c E

= 20 22 Kcal/mol
. Nu khi u bng chiu sng th E

= 5 8 Kcal/mol.
Chnh v nng lng ca phn ng polime ho bng quang hc nh nn phn ng
c th tin hnh nhit rt thp, v d polime ho vinyl clorua (dng nh sng t
ngoi) tin hnh 35
o
C.
Phn ng khi mo bng nh sng cho php trng hp chn lc ni i.
2.1.2. ng hc ca phn ng polime hoc ch gc
hiu r biu thc ng hc ca phn ng polime ho, ta xt v d polime ho
etylen:
phn ng ny xy ra theo c ch gc, hay phn ng dy chuyn, c th gi gc khi
mo l X
, cc giai on ca phn ng c th biu din nh sau:

. Giai on khi u (hoc khi mo)
vi vn tc V
i
= k
i
.[ I ], vi [ I ] l nng cht khi u
. Giai on pht trin mch: K hiu phn t CH
2
= CH
2
l M (monome).

Trong k
p
l hng s tc ca tng phn ng trong dy cc phn ng pht
trin mch tng t nhau (mi ln ni thm 1 mt xch)
. Giai on tt mch: l qu trnh trit tiu cc gc t do
trong P
i+j
l phn t polime gm (i+j) phn t monome.
k
e
l hng s vn tc ca phn ng tt mch.
Ta c th xc nh tc phn ng polime ho bng tc tiu hao monome.
Theo cc phng trnh phn ng trn ta c:

n gin ta t [R
] = [R
1
] + [R
2
] + =[R
i
]
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vy (a)
Vn tc i vi cht khi mo:
(b)
Theo nguyn l n nh ca Bodeinstein ta c , tc
hay v
i
= k
p
[M][X
] (c)
Thay (c) vo (a) ta c:
(d)
p dng nguyn l Bodeinstein cho tt c cc gc t do ta c:
=k
p
[M][X
] - k
p
[M][R
1
] k
E
[R
1
][R
]
=k
p
[M][ R
1
] - k
p
[M][R
2
] k
E
[R
2
][R
] (*)
v.v
Cng cc biu thc (*) ta c:
0 = k
p
[M][X
] k
E
[R
]
2
(e)
T (e) ta c k
E
[R
]
2
= k
p
[M][X
] = v
i
Vy (f)
Thay (f) vo (d) ta c:
v = v
i
+ k
p
[M]
Nu mch polime rt ln, tc nng monome ln th tc polime ho ph
thuc ch yu vo s hng sau:
v = k
p
[M]
2-1-3. H s polime ho ( trng hp)
H s polime ho hay trng hp c xc nh bng t s gia vn tc pht
trin mch v vn tc tt mch.
m v
i
= [R
] = ; [R
]
2
=
(*)
Nhng v
i
= k
i
[ I] (**) Thay vo (*) ta c:
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t: Ta c n = K
Vy h s polime ho t l thun vi nng monome v t l nghch vi cn bc
hai ca nng cht khi mo.
2-1-4. Phn ng chuyn mch
Trong phn ng polime ho, ngoi phn ng theo c ch dy chuyn trn cn
c th xy ra phn ng chuyn mch. Phn ng ny lm mch polime ngng pht
trin nhng ng thi cng lm pht sinh ra gc t do mi, gc t do mi ny li c
th lm cht khi u cho phn ng polime ho. Gi AB l mt phn t ca mt
cht c mt trong h phn ng nh phn t dung mi, phn t cht khi u cn d
v.v

C hai kh nng pht trin mch mi:

vv
hoc

vv
a/ Chuyn mch do phn t dung mi
Mch polime ang pht trin thng b t do ko theo mt nguyn t ca dung
mi. V d: polime ho vinyl clorua trong dung mi CCl
4
:

Gc t do mi sinh ra (CCl
3
) li bt u mt phn ng mi

(mch tip tc pht trin)
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S t mch c th xy ra gia cc gc ca phn t dung mi hoc gia mch
polime v gc R
i

Hoc

Phng php ny nu chn t l gia monome v dung mi thch hp c th iu
ch c polime vi trng hp nh khong n = 10-20.
b/ Chuyn mch thng qua phn t monome.
Nu trong phn t monome c nguyn t hydro hoc halogen linh ng th
monome c th tham gia phn ng chuyn mch. V d phn ng polime ho brom
styren c th xy ra phn ng chuyn mch nh sau:

Gc mi pht sinh tip tc phn ng vi monome, v d:

vv
c/ S chuyn mch do cht khi u
Nhiu cht khi u nh peroxit benzoin, azodiizobutyronitril khng tham gia
phn ng chuyn mch, nhng cc cht khi u nh hydro peroxit li tham gia phn
ng chuyn mch vi mc ng k:

13 of 72 10/16/2007 8:35 PM

Sau gc mi to thnh ny li phn ng vi monome.

vv
Nu c cc phn ng chuyn mch k trn, h s polime ho lin h vi vn tc
cc phn ng chuyn mch theo biu thc.

trong V
S
l vn tc chuyn mch vi dung mi.
V
M
l tc chuyn mch vi monome.
V
I
l tc tt mch.
V
p
l tc polime ho.

2-1-5. iu chnh, hm phn ng polime ho
Cc phn ng chuyn mch c ng dng thc t ngn nga hin tng polime
ho cc b monome (v d khi vn chuyn hay bo qun) v cn dng iu chnh
KLPT ca polime sn phm. Trong thc t, khi bo qun monome, n c th b
polime ho tng phn (do nh hng ca nhit , nh sng, tia phng x, do oxi
khng kh tc dng vi phn t monome to ra peroxit). iu ny c th gy n
hoc to bt polime trong b cha, lm gim cht lng monome.
hn ch hoc ngn nga hin tng polime ho sm do cc yu t bn ngoi nh
hng n monome, c th cho cht c ch hm vo monome.
* Cht hm l cht c kh nng ngn chn s polime ho.
* Cht c ch (lm chm) c kh nng lm gim tc polime ho v lm cho
KLPT polime khng tng thm c.
V mt ny nhng cht c th tham gia phn ng chuyn mch khi cho vo
monome c th xy ra cc qu trnh sau:
a/ Phn ng vi gc t do to ra gc t do mi km hot ng
b/ Tc dng vi gc t do polime to ra gc khng hot ng
Cc gc t do ny ch c th kt hp vi gc t do hot ng hoc gc t do
polime to ra phn t bn( phn ng t mch).
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Nhng cht hm tt nht l cht c th phn ng ngay vi cc gc t do ban u
dp tt kh nng khi mo cho phn ng polime ho.
V d nh cc gc triphenyl metyl

hoc Diphenyl picril hydrazin (DPPH)

Nhng gc ny khng phn ng khi mo vi monome nhng hot tnh
phn ng vi cc gc ''khi mo'' to ra gc mi km hot ng v t kh nng
khi u s polime ho nh:

V cht AC ny khng ngn chn hon ton phn ng polime ho, cht ny c
gi l cht lm gim tc , hay cht c ch.
c trng cho kh nng hm (hay c ch) ca mt cht cho vo monome, ngi
ta dng khi nim thi gian cm ng (hay thi gian hm): l khong thi gian t
khi cho cht hm vo monome n khi bt u phn ng polime ho.
Vi nng
C
1
ti thi gian hm bng 0
C
2
ti thi gian hm t
2
C
3
ti thi gian hm t
3
C
3
> C
2
> C
1

d/ Nu cht cho vo monome tham gia phn ng chuyn mch v to ra gc mi c
kh nng khi mo phn ng polime ho vi tc chm hn, ngi ta c th dng
iu chnh KLPT ca polime sn phm. Cc cht ny c gi l cht iu chnh.
Cc cht iu chnh thng dng l mecaptan bc mt v bc ba vi s nguyn t
cacbon trong phn t khng nh hn 4. V d:

15 of 72 10/16/2007 8:35 PM
Hoc C
6
H
5
N = N- S- C
10
H
7
Cc cht iu chnh khng nhng lm cho KLPT ca polime khng ln m tng
ng u ca cc phn t, ngoi ra cn c th lm phn nhnh ca phn t
polime.
2-1-6. Cc yu t nh hng n phn ng polime ho theo c ch gc
2-1-6-1. Vai tr ca oxi v tp cht trong phn ng polime ho.
Khi c mt oxi trong monome c th c li hoc c hi cho phn ng polime ho
c ch gc. V d:
Trong s polime ho styren, oxi xc tin phn ng polime ho.
Ngc li oxi lm chm phn ng polime ho axetat vinyl hoc vinyl clorua.
Tc dng hai mt ca oxi c th gii thch bng kh nng to vi monome v gc t
do polime cc loi peroxit hay hydroperoxit theo s :

Nu cc peroxit hay hydroperoxit to thnh m n nh trong iu kin phn ng
th s lm chm phn ng polime ho, tri li nu cc peroxit hay hydroperoxit d b
phn hu thnh gc hotng trong iu kin phn ng th gc t do s xc tin,
lm tng tc polime ho.
Tc dng ca mt vi tp cht khc cng c c ch tng t nh oxi. Do tc dng
ca oxi nh hng phc tpn phn ng polime ho, do trc khi thc hin phn
ng polime ho cn phi loi b cc tp cht v oxi c monome tinh khit v
thng phn ng polime ho c tin hnh trong mi trng kh tr (nh N
2
, Ar, He).
2-1-6-2. nh hng ca nhit .
Nhit lm tng tc cc phn ng ho hc ni chung, v phn ng polime
ho ni ring.
V phn ng polime ho theo c ch gc xy ra theo 3 giai on, trong giai
on khi u c nng lng hot ho cao nht, giai on dt mch c nng lng
hot ho thp nht. V d khi dng peroxit benzoin kch hot phn ng polime
ho vinyl clorua, ta c:
E
i
*
= 30 Kcal/mol (khi u)
E
p
*
= 7 Kcal/mol (pht trin mch)
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E
E
*
= 3- 5 Kcal/mol (t mch)
Nh trnh by phn trn, vn tc polime ho c ch gc biu din bng cng
thc:

trong k
p
: hng s vn tc phn ng pht trin mch
k
i
: hng s vn tc phn ng khi u
k
E
: hng s vn tc phn ng t mch
[ I ]: nng cht khi u
[M]: nng monome.
T phng trnh Arrhenius hay
p dng cho cc phn ng (khiu, pht trin mch, tt mch)

vy nu t hng s tc phn ng polime ho l K ta c:

hay
t E
*
= - E
p
*
+ E
E
*
/2 E
i
*
/2 ta c:
k = A.e
-E*
/RT (a)
Vi nng lng hot ho ca phn ng khi u E
i
*
= 30 Kcal/mol
nng lng hot ho ca phn ng pht trin mch E
p
*
= 5 -7 Kcal/mol
nng lng hot ho ca phn ng tt mch E
E
*
= 3 - 5 Kcal/mol
Ly trung bnh vi E
i
*
= 30 Kcal/mol, E
p
*
= 7 Kcal/mol, E
E
*
= 4 Kcal/mol
ta c E
*
= 20 Kcal/mol.
Th tnh vi T
1
= 40
o
C (tc 313 K)
T
2
= 50
o
C (tc 323 K)
Theo (a) ta c k
T1
/k
T2
= 2,7 hay k
50
= k
40
.2,7.
17 of 72 10/16/2007 8:35 PM
Vi T
1
= 80
o
C (tc 353 K)
T
2
= 90
o
C (tc 363 K)
T kt qa th nghim vi cc khong nhit trn c th kt lun, nu nng
lng hot ng ho ca phn ng bng 20 Kcal/mol, th nhit tng thm 10
o
C,
vn tc phn ng tng ln khong t 2 n 3 ln.
Mt khc v nng lng hot ho ca phn ng khi u ln hn nng lng hot
ho ca phn ng pht trin mch, nn khi nhit thay i, vn tc phn ng khi
u thay i nhanh hn so vi phn ng pht trin mch. V d khi tng t 40
o
C
50
o
C
hay k
i, 50
= 4,4k
i, 40

i vi vn tc pht trin mch:
hay k
p, 50
= 1,4k
p, 40
Nh vy khi nhit tng t 40
o
C n 50
o
C, vn tc phn ng khi u tng ln
4,4 ln, trong khi tc phn ng pht trin mch ch tng 1,4 ln. Nh li rng,
h s polime ho c xc nh bi t s v
p
v v
i
.

Nhng khi nhit tng th vn tc khi u tng nhanh hn cn vn tc pht
trin mch chm hn, do n gim, tc l KLPT ca polime gim.
iu ny ph hp vi s liu thc nghim. V d polime ho styren tin hnh
20
o
C khi cht khi u l peroxit benzoin tuy xy ra chm nhng KLPT ca polime
sn phm t n 550 000 vC, nu phn ng tin hnh 120
o
C th phn ng kt
thc nhanh chng (khong 2 gi) nhng KLPT ca polime gim xung cn 167 000
vC. V d khc: polime ho metyl metacrylat 100
o
C cho polime c KLPT 10
500 vC, 130
o
C l 7150 v 150
o
C l 5 100 vC.
Tuy nhin khi nhit cao, phn ng c tc khng ch v tc khi u hoc
pht trin mch m c th cn do xy ra cc phn ng chuyn mch theo nhiu
phng thc
khc nhau. D sao kt qu cui cng vn l polime c KLPT gim, mch polime
sn phm ngn hn polime sn xut nhit thp.
2-1-6-3. nh hng ca nng v bn cht ca cht khi u.
T phn ng hc ca phn ng polime ho (mc 2) ta thy vn tc phn ng
18 of 72 10/16/2007 8:35 PM
polime ho t l thun vi cn bc hai nng cht khi u. Cc cht khi u khc
nhau c tc dng khc nhau i vi 1 monome, v 1 cht khi u c tc dng
khng ging nhau i vi cc monome.
V d: dng cht khi u peroxit benzoin (nng 1%) i vi phn ng
polime ho butadien 1,3. styren v acrylonitril th t l tc polime ho gia cc
phn ng l 1: 500: 100 000, trong lc nu dng cht khi u 1%
diazoaminobenzen t l tc polime ho tng ng l 1: 3: 25.
Khi nng cht khi u tng th vn tc phn ng tng nhng h s polime ho
gim, tc KLPT ca polime sn phm gim, mch polime ngn hn.
2-1-6-4. nh hng ca nng monome.
Khi phn ng polime ho xy ra trong dung mi, nh xt mc (2)
v= K[I]
1/2
[M], tc polime ho tng t l thun vi nng monome, nu pha
long bng dung mi th cc phn t monome cch xa nhau hn, phn ng polime
ho xy ra km hn, nhng phn ng chuyn mch gia monome v phn t dung
mi tng lm gim KLPT ca mch polime.
Nu dung mi tr th vn tc phn ng ph thuc nng monome theo cng
thc thc nghim sau:
V=k.[M]
x
Trong k v x l cc hng s thc nghim, thng th x=1,5. Trng hp dung
mi c tham gia phn ng (chuyn mch) th biu thc tc phn ng phc tp
hn.
2-1-6-5. nh hng ca p sut.
Trong khong p sut thp v p sut trung bnh n vi chc atm hu nh khng
nh hng n tc polime ho. Nhng khi tng p sut n hng nghn atm th tc
polime ho tng ln ng thi KLPT polime cng tng ln.
V d: polime ho styren 60
o
C vi cht khi u l peroxit benzoin t p sut
thng n 3000 atm, tc phn ng tng 7,2 ln. A. Rogovin tin hnh polime ho
metyl metacrylat 800 atm thy tc phn ng tng 3 ln v KLPT trung bnh ca
polime tng gp 2 ln.
Ngi ta gii thch s tng tc phn ng p sut cao l do tng s ln va
chm gia monome v gc t do v cc gc polime vi nhau.
Tuy nhin khi p sut tng, nht cht lng tng, s khuch tn km v kh
nng t mch cng tng ln. V cc gc polime c KLPT ln hn cc gc phn t
nh nn kh nng khuch tn km hn, kh nng t mch khng nhng khng
tng m cn c th gim. iu gii thch ti sao KLPT polime iu ch p sut
19 of 72 10/16/2007 8:35 PM
cao li ln hn KLPT polime iu ch p sut thp.
Bi 2-2. Copolime ho c ch gc
2-2-1. Khi nim copolime ho
Copolime ho l qu trnh to ra polime t phn ng kt hp mch hai hay nhiu
monome. Sn phm ca qu trnh ny c gi l copolime.
Nu k hiu cc monome l A v B th phn ng copolime ho c th vit:

a s cc copolime c cu trc khng trt t, cc mt xch khc nhau kt hp vi
nhau khng theo mt trt t nht nh. Chnh v vy bng cch thay i loi
monome v t l hm lng cc monome, ngi ta c th sn xut c cc copolime c
thnh phn v tnh cht c l thay i trong mt gii hn rt rng. Do qu trnh
copolime ho c ngha thc tin rt ln, cho php sn xut c nhiu copolime rt
khc nhau v thnh phn v tnh cht. a s cc loi cao su tng hp u l cc
copolime. Sau y l vi v d:
Polyvinyl clorua (PVC) v polyacrilonitril (PAN) ch ho tan trong cc dung
mi him c nhit si cao, nhng copolime iu ch t vinyl clorua v
poliacrynitril li ho tan tt trong axeton.

Si tng hp t poliacrylonitril c tnh cht rt ging len, nhng kh nhum
mu, nhng sn phm ca qu trnh copolime ho acrylonitril v vinyl amin li
rt d nhum mu.

y l sn phm copolime gia acrylonitril vi vinyl pyridin, t l cc cu t trong
copolime dao ng trong gii hn rng tu thuc vo kh nng phn ng ca
monome.
2-2-2. Kh nng copolime ho, hng s copolime ho
Xt phn ng copolime ho t hai monome M
1
v M
2
. K hiu gc polime c
nhm hot ng l monome M
1
l P
1
v gc polime c nhm hot ng l monome
M
2
l P
2
.
V d: gc ca cht khi mo l X
, phn ng pht trin mch to ra gc polime P

1
(tc l
Th phn ng pht trin mch c th c 4 kh nng

20 of 72 10/16/2007 8:35 PM

Trong M
1
v M
2
l phn t cc monome thnh phn.
P
1
l gc polime c nhm hot ng l M
1
P
2
l gc polime c nhm hot ng l M
2
.
k
11
, k
12
, k
21
, k
22
hng s tc phn ng.
Tc phn ng ca monome M
1
v M
2
c xc nh theo cc phng trnh ng
hc
sau:
p dng nguyn l trng thi n nh Bodeinstein i vi cc gc P
1
v P
2
ta c:
. i vi gc P
1
:

hay (c)
( phn ng (1) lng P
1
2 v phng trnh trit tiu nhau, nn khng c mt trong
phng trnh ng hc).
. i vi gc P
2
: ( phn ng (4) lng P
2
2 v trit tiu nhau).

hay (d)
Kt qu thu c trong hai trng hp l nh nhau. tm mi tng quan gia tc
tham gia phn ng ca cc monome ta bin i nh sau: chia cc v ca phng
trnh (a) cho cc v ca phng trnh (b) ta c:
(e)
chia t s v mu s ca phng trnh (e) cho v tri hoc v phi ca phng trnh
(c) hoc (d):

t v cui cng ta c:
(II.1)
r
1
v r
2
c gi l hot tnh tng i ca cc monome hay hng s copolime ho
(hay hng s ng trng hp).
21 of 72 10/16/2007 8:35 PM
C th sp xp cc s hng ca (II.1) thnh:
(II.2)
hng s r
1
v r
2
c ngha rt quan trng trong h thng copolime ho. r
1
c trng
bng t l gia hng s tc phn ng ca gc polime P
1
vi cc monome M
1
v
M
2
, cn r
2
c trng bng t l gia hng s tc phn ng ca gc polime P
2
vi
cc monome M
2
v M
1
.
. Nu r
1
ln tc tc phn ng ca gc P
1
vi monome M
1
ln hn tc phn
ng ca P
1
vi M
2
.
. Nu r
2
ln tc tc phn ng ca gc P
2
vi monome M
2
mnh hn vi
monome M
1
.
Khi t l nng [M
1
] /[M
2
] thay i th:
+ Nu r
1
> r
2
to ra copolime cha t phn M
1
nhiu hn M
2
+ Nu r
2
> r
1
to ra copolime cha t phn M
2
nhiu hn M
1
.
Nu k hiu X
2
l phn mol ca monome M
2
trong hn hp ban u v
n
2
l phn mol ca cc mt xch cha M
2
trong polime, ta c th biu din s
ph thuc ca n
2
v X
2
khi hng s copolime c gi tr khc nhau.
Trn hnh (II.1) l s biu din s ph thuc .

Hnh II.1. Biu ph thuc n
2
vo X
2
vi cc hng s copolime ho khc nhau:
ng 1) r
1
= 0,1 , r
2
= 10
r
1
= r
2
= 0,135 2.
r
1
= 10 , r
2
= 0,1 3.
r
1
= r
2
= 7,4 4.
22 of 72 10/16/2007 8:35 PM
ng cong (1) ng vi trng hp r
1
< 1 v r
2
> 1 ngha l phn ng ca gc P
2
vi M
2
cao hn so vi M
1
, do sn phm copolime cha hm lng (phn
mol) M
2
cao hn.
ng cong (3) l trng hp ngc li, r
1
> 1 v r
2
< 1, copolime c hm lng M
1
cao hn.
ng cong (2) biu din trng hp r
1
v r
2
u < 1, ngha l gc P
1
phn ng
vi M
2
mnh hn vi M
1
v gc P
2
phn ng mnh vi M
1
hn l vi M
2
.
ng cong (4) biu din trng hp P
1
phn ng vi M
1
c phn d dng hn
v P
2
phn ng vi M
2
cng d dng hn so vi trng hp (2).
T phng trnh (II-2) ta thy t l phn mol n
2
trong copolime bng phn mol trong
hn hp monome ban u khi v ch khi tho mn iu kin:
r
1
[M
1
] + [M
2
] = r
2
[M
2
] + [M
1
]
hay (r
1
[M
1
] + [M
2
])/(r
2
[M
2
] + [M
1
] =1.
Trng hp c bit, nu nng cc monome bng nhau, th iu kin ny xy
ra khi r
1
= r
2
= 1. l trng hp copolime ho ng phn (c trng bng ng cho
trn hnh II.1).
Trn thc t thng gp cc trng hp copolime ho sau:
Tng monome khng b polime ho, nhng li c s copolime ho, lc k
22
=
k
11
= 0 nhng k
21
> 0 v k
12
> 0, ngha l gc P
1
ch phn ng vi monome 2
(M
2
) v P
2
ch phn ng vi monome M
1
.
Trong trng hp ny sn phm copolime sp xp trt t
V d: t copolime ho anhidrit maleric vi 1,2 diphenyl etylen (vi r
1
= 0,03
v r
2
= 0,003) lc copolime thu c c cu trc sau:

b) Tng monome c kh nng polime ho nhng khng copolime ho ngha l k
11
>
0, k
22
> 0 nhng k
21
= k
12
= 0.
Trong trng hp cc gc t do ch phn ng vi monome cng loi, nhng khng
phn ng vi monome khc loi, kt qu thu c hn hp 2 polime.
V d h thng gm styren vinyl axetat trong nhng iu kin nht nh khng
to ra sn phm copolime, nhng trong iu kin khc li to ra copolime.

2-2-3. Cc phng php xc nh hng s copolime ho
23 of 72 10/16/2007 8:35 PM
C nhiu phng php xc nh hng s copolime ho, y s trnh by nhng
phng php thng dng.
2. 2.3. 1/ Phng php giao tuyn ca F. Maye v F.M. Lewis.
T biu thc t l tc polime ho ca cc monome M
1
v M
2
c

th sp xp
li nh sau:

hay
nu t a = v b = ta c:
r
2
= a[ b(1 + a.r
1
) 1]
hay r
2
= a
2
br
1
+ a.b b
li t A = a
2
b v B = ab b th r
2
= A.r
1
+ B (II. 4)
y l phng trnh ng thng trong h to r
2
r
1
. Nu xc nh thc nghim
c cc gi tr [M
1
], [M
2
], d[M
1
], d[M
2
] d dng tnh c A v B. Mi th nghim
cho php v mt ng thng. Lm vi th nghim c vi ng thng, t giao im
cc ng v cc trc s tm c r
1
v r
2
.

2. 2.3. 2. Phng php Faineman v Ross
Cng thc (II. 2) cn c th vit di dng
(a)
Chia v phi ca (a) cho [M
2
] ta c:
(b)
t v [M
2
]/[M
1
] = F ta c:
.F = (c)
.F.r
2
+ = 1 + r
1
/F
.F
2
.r
2
+ .F = F + r
1
.F
2
.r
2
- r
1
= F (1- )
t y = F. (1-) v .F
2
=x ta c dng phng trnh ng thng y = r
2
.x - r
1
.
24 of 72 10/16/2007 8:35 PM
Nu xc nh c [M
1
], [M
2
] v d[M
1
], d[M
2
] ta d dng xc nh c v F.
V th y = f(x), h s gc ca ng thng l r
2
v ko di ng thng ct trc
tung xc nh r
1
.

Bi 2-3. Cc phng php tin hnh polime ho
Tu theo bn cht monome v sn phm polime vi nhng mc ch s dng khc
nhau, ngi ta c th tin hnh polime ho bng cc phng php khc nhau:
Polime ho khi
Polime ho trong dung dch
Polime ho nh tng
Polime ho huyn ph.
2-3-1. Polime ho khi (mass polimerization)
Nguyn liu l monome lng tinh khit, khi u theo phng php nhit nh
sng hoc cht khi u. Trong trng hp cn thit c th thm vo mt lng cht
iu chnh hoc cht do ho. V lng cht khi u rt t, nn polime sn phm rt
tinh khit, trong sut nn thng dng trong cng ngh thu tinh hu c. Do nht
ca hn hp phn ng cao v dn nhit ca polime sn phm km nn vn ti
nhit ra khi khi phn ng tng i kh khn, dn n qu nhit cc b, lm cho
nhit khng ng u nn KLPT ca polime gim. ngoi ra trong sn phm c
th c nhng bt kh lm nh hng n tnh cht c l ca polime v cht lng
polime khng tht n nh.
Do nhng nhc im trn, nn s polime ho khi c dng rt hn ch trong
k thut, v d nh sn xut polyaxetyl metacrylat, polystyren, polyvinylaxetat vv
Mc d vy, nhng nm gn y, cng vi s pht trin v hon thin cng ngh
thc hin phn ng, phng php polime ho khi vn c ng dng v nhng u im
ca n l nng sut cao, polime sn phm rt tinh khit.
2-3-2. Polime ho trong dung dch
S polime ho trong trng hp ny c thc hin trong dung dch, ngha l ho tan
monome thch hp ri mi tin hnh polime ho. u im:
Tch nhit ca phn ng d dng hn, trnh c hin tng qu nhit cc b.
25 of 72 10/16/2007 8:35 PM
Rt thch hp cho vic nghin cu s ph thuc ca tc phn ng vi nng
monome v cc yu t khc (nh s chuyn mch thng qua dung mi, qua
cht khi u vv)
Nhc im: tinh khit ca polime sn phm khng cao (v c th cha cc tp
cht nht l dung mi).
Ngi ta thng tin hnh polime ho trong dung dch theo hai cch:
Cch 1: Khi monome v polime sn phm u ho tan trong dung mi, cch ny gi
l polime ho trong sn.
Cch 2: Khi monome tan trong dung mi, nhng polime th khng tan trong dung
mi.
Trong trng hp th nht, polime tan trong dung mi c th c dng trc tip
lm sn, keo hay tm ln cc vt liu khc lm cht chng thm. Nhc im
ca cch ny l tiu tn dung mi, cc dung mi ho tan c monome v
polime thng c, d chy v t tin. Ngoi ra, c th xy ra s chuyn mch
vi dung mi nn KLPT thng thp.
Trng hp th hai cho polime c KLPT cao hn v c nhng u im: dung mi
loi ny r, d kim v thng d tch khi polime, ng thi phn ng chuyn
mch gia gc polime vi phn t dung mi thng kh xy ra.
2-3-3. Polime ho nh tng (Emulsion polimerization)
Trong trng hp ny ngi ta dng mt cht lng lm mi trng phn ng. y
monome v polime sn phm u khng tan trong cht lng . Polime phn b
trong mi trng phn ng di dng dung dch keo hoc nh tng, khi phn ng
kt thc ngi ta lm ng t keo c polime.
d dng khuch tn monome, phi cho vo mi trng phn ng cht nh ho
(thng l mui ca axit bo nh x phng natri sterat, natri oleat hoc mui ca
sunfo axit hu c hoc cht hot tnh b mt khc.
Chc nng ca cht nh ho l lm gim sc cng b mt gia hai pha tip xc
nhau, v d monome v nc lm cho cc b mt ring ca cht phn tn tng, tc l
tng tc phn ng polime ho.
Phng php polime ho nh tng c ngha thc t rt ln, v d n pha ch chun
ho sn xut cao su butdien-styren nh sau:
Butadien75g
Styren.25g
Nc (cha laurat kim loi)...180g
Cht nh ho (laurat kali)..5g
26 of 72 10/16/2007 8:35 PM
Cht khi u (K
2
S
2
O
8
)..0,3g
Cht iu chnh KLPT (lauryl mecaptan)..0,5g
u im ca phng php polime ho nh tng:
Tc phn ng nhanh, KLPT ca polime cao.
V d sau y so snh kt qu thc hin polime ho theo hai phng php: polime
khi v polime ho nh tng:

- Cht khi u (mol/l)
- Cht nh ho (x phng)
mol/l
- Tc chuyn ho trong 1
gi (%)
- H s polime ho
Polime ho khi Polime ho nh
tng
C
6
H
5
COO
0,0428
/
3,28
800
K
2
S
2
O
8
0,010
0,027
60
37 000
Phn ng

c th hiu r bn cht s polime ho nh tng, chng ta tm hiu thm v
cu to nh tng ca monome trong mi trng phn tn khi c mt cht nh ho.
. Bn cht dung dch x phng trong nc.
X phng (v d C
17
H
35
COONa, natri sterat) rt t tan trong nc, vi dung dch rt
long, cc phn t x phng cch xa nhau nhng n mt nng gii hn no ,
cc phn t x phng t tp vi nhau to ra cc mixen (mi mixen gm hng chc,
hng trm phn t x phng). K hiu phn t x phng l
(trong biu th mch hydrocacbon ca phn t x phng, cn o biu th nhm
phn cc COO
-
ca n). Nhiu cng trnh i n kt lun rng gc hydrocacbon
(nhm k nc) th hng vo bn trong mixen, cn nhm phn cc COO
(nhm a
nc) th hng v pha nc (xem hnh 4.1).

27 of 72 10/16/2007 8:35 PM
Hnh 4.1. Hnh dng ca mixen.
Cc monome (thng l hydrocacbon) khng tan trong nc, nhng c th khuch
tn vo trong dung dch x phng trong nc v cc phn t monome khuch tn vo
bn trong mixen lm cho kch thc mixen thay i. V d styren hon ton khng
tan trong nc, nhng c th tan khong 6,8% trong dung dch x phng, cn isopren
tan trong dung dch x phng t n 9%.
Theo nhiu tc gi, phn ng polime ho xy ra bn trong mixen ( c mt cc
monome khuch tn vo ). Cht khi u ho tan vo nc ri to thnh cc gc t
do, cc gc t do khuch tn vo trong cc mixen v khi u cho phn ng polime
ho. Trong qu trnh phn ng, lng monome mi c b sung dn t nhng git
monome nh ho. Phn ng pht trin mch tip din cho n khi khng cn gc t
do v xy ra phn ng t mch. Nh vy l cc monome nh ho dn dn chuyn
thnh ht polime, cc ht polime ny cng hp ph phn khng phn cc ca phn
t x phng v to ra nh tng polime (c bo v bi cc phn t cht nh ho).
Theo W.D.Harkins, cc mixen x phng b ph v hon ton khi monome
chuyn ho c 13 14%, lc cc phn t x phng to thnh lp bo v ht
polime. T lc ny s polime ho xy ra trong ht polime nh ho (hnh 4.2).

Hnh 4.2. 1) S khuch tn cc phn t monome vo mixen
2) Dung dch monome trong mixen
3) Ht monome polime (pht trin mch)
4) Ht polime nh ho (Latex)
Khi chuyn ho t 60% cc monome nh ho cn rt t, ch yu l cc ht
polime. Kch thc ht polime cng ln khi chuyn ho cng ln. V d nu
chuyn ho 15% th ht polime c kch thc khong 65 A
o
, nhng khi chuyn ho
t 74%, kch thc ht polime l 850 A
o
. Khi ht polime t kch thc cn thit v
phn ng polime ho kt thc, ngi ta c nh tng ca polime trong nc (cht bo
v l x phng), tch polime sn phm c thc hin bng cch lm ng t
chng di tc dng ca cht in ly (nh dung dch axit, baz hoc mui v c).
Ngc li theo quan im ca Smith v Evart th trongiu kin n nh, tc
phn ng polime ho ph thuc vo nng ht polime trong dung dch nc. H
thit lp c mi quan h sau:
28 of 72 10/16/2007 8:35 PM
(4.1)
V- tc phn ng polime
N- S lng ht polime trong 1 cm
3
dung dch nc
[M]- nng monome trong ht polime.
Ngi ta nhn thy rng, lng monome trong ht polime thng dao ng trong
khong 45 65%, do c th xem l khng i, nh vy tc polime ho t l
thun vi nng ht polime trong dung dch (tc t l vi N).
Theo (4.1) ta thy, tc polime ho nh tng khng ph thuc nng ca cht
khi u, khc vi polime ho c ch gc kho st chng 2.
2-3-4. Polime ho huyn ph (suspension polymerization)
Phn ng polime ho huyn ph cng tin hnh tng t nh s polime ho nh
tng, ch khc l y cht khi u khng tan trong nc m tan trong monome,
cn cht nh ho c thay bng cht n nh dung dch huyn ph nh cc polime
ho tan trong nc, polime alcol, axit polyacrylic, tinh bt v mt s oxit nhm, t
st vv
Cht n nh c s dng vi lng ng k (n 3,5%) ngn nga s phn lp
ca cht phn tn v dung mi. Cc git monome c kch thc khc nhau t 0,1 5
mm tu theo vn tc khuy trn, bn cht v lng cht n nh. Cht khi u ho
tan trong git monome nn phn ng polime ho xy ra trong cc git monome ny.
Nu ch xt ring tng git ny th s polime ho ging nh s polime ho khi.
Nhng v cc git ny khuch tn trong nc nn s tn nhit do phn ng to ra c
d dng hn, lm cho KLPT ca polime tng ln. Polime sn phm d lm sch, do
tnh cch in n nh. Trong k thut phng php polime ho huyn ph ng
dng rng ri sau polime ho nh tng.
2-3-5. S polime ho trong pha hi.
Phng php ny cha c ng dng rng ri. V d v phn ng polime ho ny l
s polime ho ete vinylic khi c mt cht khi u Bo triflo BF
3
. c im ca s
polime ho trong pha hi l xy ra rt nhanh. KLPT ca polime sn phm tng i
nh.
4-6. S polime ho trong pha rn.
y l phng php sn xut polime mi v c nhiu trin vng v cc u im sau:
Cho php polime ho mt s monome m khng tin hnh bng phng php
khc.
Cho php polime ho c nh hng.
Tc polime ho ln vt tri cc phng php khc.
29 of 72 10/16/2007 8:35 PM
V mi ra i nn cha c nghin cu k, phng php ny i hi tip tc nghin
cu v ng dng trong k thut tng hp polime.

Bi 2-4. S polime ho c ch ion
Cc hp cht khng no khng nhng c th polime ho theo c ch gc m cn
polime theo c ch ion.
Trc y s polime ho ion t c ng dng, v d sn xut polyisobutylen, cao
su butadien vv
Nm 1953 Siegler nghin cu polime ho etylen p sut thng v 1955
Natta ln u tin tng hp c polyoxiolefin c cu trc iu ho. Cc sn phm
thu c theo cc phng php ny c c bit quan tm v cc polime thu c c
nhiu tnh cht khc vi polime iu ch theo c ch gc. Cc cht xc tc y l
cc hp cht hu c ca km.
Mt trong cc nhc im ca phng php ny l cc tp cht d (d vi lng rt
nh) cng nh hng n cht lng ca polime sn phm. Mt khc tc phn ng
rt ln nn phi tin hnh trong dung dch rt long v nhit rt thp v vn
gi nhit khng i l kh kh khn. S polime ho ion c th nu s lc nh
sau:
a/ Polime ho cation

b/ Polime ho anion

S polime ho ion xy ra di tc dng ca cht xc tc. Cc cht xc tc chia
thnh 2 loi chnh:
+ Cc cht xc tc cation nh: BF
3
, AlCl
3
, SnCl
4
, TiCl
4
, SbCl
5
, cc axit nh
H
2
SO
4
, HCl, H
3
PO
4
+ Cc cht xc tc anion nh: Li, Na, cc kim loi kim khc v cc anion alcolat
ca chng. C ch phn ng tu vo hot tnh ca monome v sn phm polime cn
iu ch.
2-4-1. S polime ho cation
30 of 72 10/16/2007 8:35 PM
Hot tnh ca cc cht xc tc trong qu trnh sp xp theo dy sau:
BF
3
>AlCl
3
> TiCl
3
> TiBr
4
> SnCl
4
> BCl
3
> BBr
3
a/ Cht ng xc tc.
Trong nhiu trng hp, nu ch dng mt cht xc tc, qu trnh xy ra chm,
nhng thm mt cht khc na vo (gi l cht ng xc tc) th phn ng tng
nhanh.
V d: BF
3
khng kch thch phn ng polime ho isocloetylen khan, nhng cho mt
lng nc nh vo th phn ng xy ra rt nhanh.
Cc cht ng xc tc chia lm 2 loi:
. Loi th nht: H
2
O, C
2
H
5
OH, axit hidric HX
. Loi th hai: alkyl halogen RX
V d i vi phn ng polime ho styren C
6
H
5
-CH=CH
2
di tc dng ca
SnCl
4
khi c mt cloro-terbutyl (CH
3
)
3
C-Cl. Trong (CH
3
)
3
C-Cl c th xem l
cht ng xc tc, SnCl
4
l cht xc tc.
Trn hnh (5-1) trnh by nh hng ca clorua butyl bc ba n phn ng polime
ho styren di tc dng ca SnCl
4
.

Hnh 5-1
ng 1: S ph thuc gia vn tc polime ho v nng (CH
3
)
3
C-Cl.
ng 2:S ph thuc ca KLPT polime vo nng (CH
3
)
3
C-Cl

Nhn xt:
Vi nhng iu kin khc khng thay i (nh nng monome, nhit , lng
SnCl
4
) ta thy khi nng (CH
3
)
3
CCl tng t 0 n 36.10
-3
mol/l th vn tc
polime ho tng lin tc t 30.10
-3
mol/l.pht n 65.10
-3
mol/l.pht.
Khi nng (CH
3
)
3
CCl tng t 0 n 12.10
-3
mol/l th khi lng phn t
31 of 72 10/16/2007 8:35 PM
polime tng t 7 000 n 9 000, sau hu nh KLPT polime khng thay i
khi nng (CH
3
)
3
CCl tip tc tng.
b/ C ch ca s polime ho cation
Mun phn ng polime ho xy ra, trc tin phi c cation khi u. Cation
khi u c th hnh thnh do s phn li ca cht xc tc, hoc do s phn li t
phc cht gia cht xc tc, cht ng xc tc hoc gia cht xc tc v cht
ng xc tc + monome.
Cho n nay ngi ta bit c 4 kh nng to thnh cation khi u , l:
1. phn ly cht xc tc.
Phn ly ca phc cht to thnh t cht xc tc v ng xc tc. 2.
Do tc dng gia cht xc tc v monome. 3.
Tc dng gia phc cht ca xc tc v cht ng xc tc vi monome. 4.
V d 1: S to thnh cc cation theo kh nng (1) l s phn ly ca mt cht xc
tc axt:

Sau cation H
+
phn ng vi monome:

V c th pht trin mch.
V d 2: S to thnh cation khi u do s phn li ca phc cht to thnh bi cht
xc tc v cht ng xc tc:
S to ra phc cht

S phn li ca phc cht

hoc nu dng cht xc tc l TiCl
4
v H
2
O l cht ng xc tc th:
S to thnh phc cht

S phn li ca phc cht
32 of 72 10/16/2007 8:35 PM

Nu dng TiCl
4
l cht xc tc, HCl l cht ng xc tc, ta c:

Sau cc cation khi u (R
+
, H
+
) s khi u phn ng polime ho v pht trin
mch theo kiu:

ion cacboni R- CH
2
- CHX- CH
2
-
+
CHX tip tc phn ng vi phn t monome
ko di mch polime cho n khi c phn ng t mch (trit tiu ht cc cation).
y ngi ta cha gii thch c vai tr ca anion sinh ra ng thi vi cation khi
u, v ng thi cng cha chng minh c cc anion lm gim hay lm tng tc
polime ho. Tuy nhin nhn thy dung mi c nh hng kh r n c ch polime
ho cation. Nu cation (nh cacbocation) b solvat ho th qu trnh polime ha b
chm li, v monome phi ph v v solvat ho tc dng vi cc cacbocation.
Tri li nu cc anion b solvat ho mnh hn cation th tc polime ho s tng,
v lc tng tc gia anion vi cation s kh hn tng tc gia monome vi cation.
Trong trng hp anion d dng tc dng vi cacbocation to nn lin kt bn th
phn ng t mch d xy ra, v d nu dng HCl lm cht khi u phn ng th
ion Cl
-
d dng tc dng vi cacbocation lm kt thc phn ng:

Do , trong phn ng polime ho phi la chn dung mi thch hp ngn
chn hin tng kt hp gia anion v cacbocation m bo phn ng polime ho
t hiu qu mong mun.
c/ Phn ng chuyn mch
Phn ng chuyn mch (chain transfer) cng thng xy ra trong s polime ho
ion. Trong phn ng ny cc cation ang pht trin chuyn proton sang phn t
monome hay phn t dung mi v tr thnh polime bn vi ni i cui mch. V
d:

Nu dng hydrocacbon lm dung mi (v d benzen) th phn ng chuyn mch c
th to ra phc cht trung tnh:

33 of 72 10/16/2007 8:35 PM
Hay hp cht trung gian tc dng vi phn t monome:

d/ Phn ng t mch
Trong phn ng polime ho cation th phn ng t mch xy ra do s chuyn
proton t gc polime sang anion cng nm trong mch, v du:

Nh vy sn phm trung tnh c th cha ni i u mch hoc ch cha cc
ni n, ng thi gii phng phn t cht xc tc ra khi mch polime gc.
e/ ng hc ca phn ng polime ho cation
S liu v ng hc phn ng polime ho cation khng nhiu lm v thng
khng khp nhau gia cc tc gi khc nhau. S d c hin tng ny v trong polime
ho cation c nhiu tp cht (d vi lng nh) cng ng vai tr nh cht ng xc
tc. iu kh khn nht l rt kh km tra v iu chnh hm lng m trong cht
xc tc ho nc, trong monome nguyn liu, trong dung mi. Tuy nhin t nhng
nghin cu c, ngi ta cng rt ra c nhng kt lun chung cho phn ng
polime ho cation, c th tm tt nh sau:
Vn tc xut hin trung tm hot ng c th xut pht t s sau:

Trong K
at
l nng cacbocation hnh thnh t cht xc tc hay do phn ng
gia cht xc tc, ng xc tc vi monome.
[M] nng monome.
k
at
Hng s vn tc khi u
i vi qu trnh pht trin mch:

th vn tc pht trin mch c th vit:
v
i
= k
p
[M] [K
at
M
+
] (b)
Trong K
at
M
+
- nng cacbocation ang pht trin.
34 of 72 10/16/2007 8:35 PM
i vi phn ng t mch n phn t:

Vi vn tc l:
v
= k

[K
at
. M
n
+
] (c)
Theo nguyn l n nh Bodeinstein ta c h s polime ho (hay polime ho
trung bnh) bng:
(c
'
)
hay
(5.1)
t K= k
p
/ k
ta c:
(5.2)
Nh vy, polime ho trung bnh t l thun vi nng monome v khng ph
thuc nng ca cht xc tc.
T (c
'
) ta c, tc polime ho V
p
biu din bng (d)
Thay (b) v (5.2) vo (d) ta c:
V
i
= K [M][M] [K
at
]
V
p
= K [M]
2
[K
at
]k
at
V
i
= K
'
[M]
2
[K
at
] vi K
'
= K. k
at
(5.3)
Vy tc polime ho t l thun vi bnh phng nng monome v nng
to cacbocation.
2-4-2. S polime ho anion
Kh nng polime ho ca nhiu hp cht khng no di tc dng ca xc tc
kim bit t lu. Lin x (c) v sau l c l cc nc u tin sn xut cao
su tng hp t butadien khi dng xc tc natri kim loi.
Nhng cht xc tc cho phn ng polime ho anion thng l cc hp cht c kim
ca kim loi kim v kim th hoc chnh cc kim loi ny nguyn cht.
a/ S s polime ho anion c trnh by tng qut l:

Cc cacbocation ny phn ng vi phn t monome:
35 of 72 10/16/2007 8:35 PM
Cc cacbocation ang pht trin kt hp vi proton lm t mch:

Proton tham gia vo qu trnh t mch c th ly t dung mi hoc tp cht
(nc, ru). Nu trong hn hp phn ng hon ton khng c cc cht c kh nng
phn ng vi cacbocation th polime vn bo tn trung tm hot ng cui mch,
v khi thm monome vo, cc mch vn c kh nng pht trin mch theo kiu
polime ho anion. Chnh v vy cc polime ny c gi l "polime sng" phn
bit vi polime t mch thng gi l "polime cht" l polime khng th pht
trin mch khi gp monome mi thm vo.
b/ ng hc phn ng polime ho anion
Cc cng trnh nghin cu v s polime ho anion cn t, cha c nhng kt lun
chung. Tuy nhin theo cng trnh ca Hifginson v s polime ho styren trong
amoniac lng di tc dng ca cht xc tc Kali amit a n kt qu:
Vn tc polime ho = k [NH
2
-
] (a)
polime ho = k
'
[Styren] (b)
Phng trnh (a) tng t nh s polime ho cation, do c ch polime ho anion c
th qua cc bc sau:
Phn li Kali amit:

Phn ng khi u:

Pht trin mch:

v c th ni mch tip din.
t mch do tc dng vi phn t dung mi.

36 of 72 10/16/2007 8:35 PM
ion NH
2
-
c th khi u mt mch mi hoc t mch do tc dng vi K
+

cng nh trong trng hp polime ho cation, y cc ion cng c th b solvat ho
v do s c nh hng (tch cc hay tiu cc) n phn ng polime ho anion.
Nu s dng cht xc tc l cc hp cht c kim, vic hnh thnh cacbocation thc
hin theo phn ng:
(Me l k hiu kim loi kim hoc kim th, R gc hydrocacbon). Sau
cacbocation RCH
2
-
-
CHX tip tc pht trin mch tng t nh trnh by trn.
Bi 2-5 S polime ho khng gian c bit
2-5-1. S phn loi polime theo cu trc khng gian
S polime ho c dn xut ca etylen vi mt nhm th theo c ch gc hay c
ch ion thng to ra polime c s sp xp hn n trong khng gian. n gin
ho, cu trc ca cc polime loi ny c trnh by nh sau: tt c cc cacbon trong
mch chnh u nm trong mt mt phng, cn cc nhm th nm pha trn hoc
pha di mt phng .

Polime c cu trc sp xp thiu trt t nh vy gi l polime atactic.
Nu tin hnh polime ho theo c ch gc hoc c ch ion trong nhng iu kin
c bit, chng hn nhit thp, s dng dung mi c bit hoc cht xc tc
c bit, ngi ta c th iu ch c polime c cu trc hi ho trong khng gian.
Nu cc nhm th c cu trc hi ho nm v cng mt pha ca mt phng th gi
l polime izotactic.

I
izotactic
Nu cc nhm th ny (v d R) ln lt nm v pha ny hoc pha kia ca mt
phng th gi l syndiotactic

37 of 72 10/16/2007 8:35 PM
Cc monome c hai nhm th v tr 1,2 kiu XCH= CHY cng c th to ra cc
polime c cu trc hi ho dng nh sau:
* Eritro- diizotactic

* Treo- diizotactic
(Hai nhm X v Y nm v hia pha ca mt phng)

* disyndiotactic

Trong thc t mch chnh ca phn t polime iu ho c cu trc khng gian
khng nm trong cng mt phng. V d trong polime izotactic, do tng tc ca cc
nhm bn, mch chnh c hnh xon c. Mch chnh ca polime syndiotactic c
dng ziczac. Thc t cho thy polime syndiotactic hnh thnh tng i t, chng ch
thu c trong mt s trng hp polime ho diolefin. i vi cc polime ny, do c
cu trc iu ho nn cc mch polime sp xp trt t cht ch v bn vng. Chnh
v vy nn t trng ca polime iu ho ln hn ng k so vi t trng ca polime
atactic. Khc vi polime atactic, cu trc ca polime iu ho thay i rt kh khn.
Ngi ta nhn thy nhng polime izotactic b phn hu di tc dng ca cht xc tc
n oligome (c KLPT t 1000 10 000) nhng cu trc izotactic vn gi nguyn.
Do cu trc cht ch nn polime izotactic bo tn tnh cht ca vt liu rn nhit
cao hn so vi polime atactic. V d polystyren atactic l mt cht lng nht
nhit thng, trong polypropylen izotactic nng chy 150
o
C, d dng to
mng, ko si v sn phm p c bn c hc cao.
Phn ng polime ho khng gian c bit quan trng i vi monome dien lin
hp. Trong phn ng polime ho c ch gc, polime c cu trc thiu trt t. Chng
hn polybutadien c th c cc cu trc mt xch c s loi 1,4- trans, 1,4- cis v
loi cu trc 1,2.

38 of 72 10/16/2007 8:35 PM

Trong cu trc 1,4- trans chim phn ch yu trong polime. Trong phn ng
polime ho khng gian c bit, polybutadien c th c 4 loi cu trc iu ho
trng thi tinh th.

a) 1,4- cis polybutadien

1,4- trans butadien b.

d) Syndiotactic polybutadien
S hnh thnh mt trong cc loi cu trc trn ph thuc vo bn cht cc cu t
trong cht xc tc v iu kin thc hin phn ng. i vi s polime ho isopren,
cu trc polime thu c khng nhng ph thuc vo bn cht cc cu t m cn ph
thuc vo t l cc cu t trong h thng xc tc.
Phn ng polime ho khng gian c bit thng tin hnh di tc dng ca h thng
xc tc gm hp cht c kim v mui kim loi. Cc hp cht c kim thng dng l
hp cht hu c ca nhm, beri, magi, km, cadimi, kim loi kim.Cu t th hai
l halogen ca cc kim loi nhm IV, V, VI, VII, l cc kim loi c lp in t
trung gian cha , ch yu l cc hp cht m kim loi c s oxi ho cha hon ton
(cha t s oxi ho cao nht). Cc cht thng dng hay gp l TiCl
4
, TiCl
3
Trn bng 5-1 cho bit nh hng ca bn cht cht xc tc n cu trc khng gian
ca polybutadien
Bng 5-1. nh hng ca cht xc tc n cu trc polybutadien
39 of 72 10/16/2007 8:35 PM
Cc cu t cht xc tc Hm lng mt xch (%)
1,4- Cis 1,4- trans 1,2
TiCl
4
+ AlR
3
, Al : Ti < 1
Al : Ti > 1
6
26 - 57
91
31 - 69
3
2 11
TiCl
3
+ Al(C
2
H
5
)
3
37 60 3
Ti + Al(C
4
H
9
)
3
88 3 9
CoCl
2
+ AlR
2
Cl 96 - 97 2,5 1 1,5
Ti(OC
4
H
9
)
4
+ Al(C
2
H
5
)
3
/ 0 - 10 90 100
TiCl
3
+ AlR
3
/ 99 1
Trn bng 5-2 trnh by nh hng ca t l cc cu t trong h thng xc tc n
cu trc ca polime.
C th ni rng iu ch c polime c cu trc iu ho theo mong mun,
vic chn h thng cht xc tc v t l thch hp ca cc thnh phn trong h thng
xc tc c vai tr cc k quan trng. Vn cn li l lm sao gii thch c ch
ca phn ng c xc tc t c nh hng ng n khi la chn cht xc tc
cho tng trng hp c th.
Bng 5-2. nh hng ca t l cc cu t xc tc n cu trc polyisopren
Cc cu t cht xc tc Hm lng mt xch (%)
1,4- Cis 1,4- trans 3,4
TiCl
3
+ AlR
3
, Al : Ti >1
Al : Ti < 1
95
/
1
95
4
5
TiCl
3
+ Al(C
2
H
5
)
3
/ 91 9
VCl
3
+ Al(C
2
H
5
)
3
/ 99 - 100 /
Axetyl axeton Vanadi + Al(C
2
H
5
)
3
/ / > 90

2-5-2. C ch s polime ho khng gian c bit.
C ch ca phn ng polime ho khng gian c bit cho n nay cha c xc
nh r rng v nhng l do sau:
+ H xc tc khng phi l mt hn hp c hc ca cc cht thnh phn c trong
h thng, m l mt phc cht hnh thnh do s tng tc ca cc cht to thnh,
cu trc ca cc phc cht ny trong nhiu trng hp cha c xc nh chnh xc.
+ Phn ng polime ho khng gian c bit c tin hnh trong h d th, do
vn tc polime ho ph thuc b mt ca cht xc tc d th v iu kin ny kh
ging nhau trong cc th nghim khc nhau (d cc iu kin khc nh nhau), ni
40 of 72 10/16/2007 8:35 PM
cch khc lp li iu kin th nghim l khng cao. C rt nhiu c ch v s
polime ho khng gian c bit c xut v nghin cu, nhiu nht l c ch
tc dng ca cc loi cht xc tc cha halogenua Titan v alkyl ca nhm.
Trong h thng xc tc ny, Titan b kh n ho tr 3 v 2 to thnh cc clorua
alkyltitan ri phn hu thnh gc t do etyl:

hoc

hoc

Nu tha tetra clorua titan th alkylhalogenua nhm cng c th tham gia phn ng
kh:

Nh nghin cu Natta chng minh rng Al(C
2
H
5
)
3
v alkylhalogenua titan
ring bit u khng c hot tnh xc tc cho s polime ho khng gian c bit.
Tri li h thng gm nhm, titan, halogen v alkyl mi c hot tnh xc tc, cho
nn qu trnh kh TiCl
4
n TiCl
3
v mt phn n TiCl
2
l mt qu trnh tt yu
trong hot ng xc tc theo c ch nu trn.
Theo Natta, c ch s polime ho khng gian c bit c xc tc c gii thch
nh sau: Qu trnh kh TiCl
4
n TiCl
3
hoc TiCl
2
lm d dng cho qu trnh hp
ph cc hp cht hu c ca cc kim loi c dng in cao v bn knh ion nh
(nh Al
3+
, Be
2+
, Mg
2+
). Trong qu trnh hp ph, to thnh phc cht vi titan c
cu ni l gc alkyl:

Phc cht ny to phc vi phn t monome:

Phc cht ny phn li:
41 of 72 10/16/2007 8:35 PM

Phc cht mi ny chuyn sang trng thi n nh hn.
Vi phn t monome mi li to thnh phc cht mi ri chu trnh lp li nh trn
to nn giai on pht trin mch. C th l:

vv
C nh vy m pht trin mch.
R rng phn t monome nh vo mch pha c cht xc tc, l im khc
bit vi s polime ho c ch gc hoc ion. S nh kt ny xy ra mt chc trt t
nn polime sn phm c cu trc trt t, hay polime iu ho.
Theo c ch ny hp cht alkyl nhm tham gia phn ng nh mt tc nhn alkyl ho
titan ti sinh tm hot tnh xc tc.
2-5-3. Copolime ho ion
Kh nng phn ng ca monome trong s copolime ho ion khc nhiu so vi
kh nng copolime ha theo c ch gc. Chng hn nu tin hnh copolime ho vi
nng ng lng ca styren v metylmetacrylat bng nhau theo c ch gc th
copolime thu c s c s mt xch c bn ca cc monome khi im gn bng
42 of 72 10/16/2007 8:35 PM
nhau.
Ngc li, nu copolime ho 2 monome ni trn theo c ch cation th ch thu c
polystyren tinh khit, cn nu polime ho theo c ch anion th ch c
polymetylmatacrylat tinh khit.
Trong trng hp copolime ho gc nu r
1
.r
2
1 th thng thng copolime ho ion
li c r
1
.r
2
1.
Rt kh tm c cp monome d dng phn ng vi nhau theo kiu copolime ho
ion. Chnh v vy trong cng nghip rt t s dng copolime ho c ch ion. Hin
nay ch c cao su Butil c sn xut bng cch copolime ho ion gm 98% iso
butylen v 2% iso prren.
2-5-4. Cu to ca monome v kh nng polime ho.
Kh nng polime ho ca cc hp cht khng no ph thuc vo cu to, vo s
lng v bn cht ca nhm th.
V mt nhit ng lc hc, s polime ho ch c th t xy ra khi nng lng t
do ca h thng cc cht phn ng gim. S thay i nng lng t do c quyt
nh bi bin thin entanpy v entropy:
G = H T. S
Phn ng polime ho thng lm gim entropy ca h S = -23 -33 cal/mol.K,
khong T. S = 7 10 Kcal/mol ( khong 300 K). Do G < 0 th phn ng
polime ho phi to nhit ngha l |H| > 10 7 Kcal/mol, hay H < -7 -10
Kcal/mol. Sau y l gi tr hiu ng nhit ca phn ng polime ho ca mt s cht
(bng 5-3)

Monome
H
R
(Kcal/mol)
Monome
H
R
(Kcal/mol)
Styren
Vinyl clorua
Vinyl axetat
Metyl metacrylat
acrylonitril
-16,5
-16,17
-21,3
-13,0
-15,7
Isopren
Butadien
Isobutylen
Etylen
Vinyliden clorua
-17,9
-17,3
-12,8
-22,35
-14,4
Theo l thuyt, khi polime ho th lin kt i ca monome bin thnh 2 lin kt
n trong monome.
43 of 72 10/16/2007 8:35 PM
H
R
=
C=C
- 2
C-C
= 145,5 2.84 = - 22,5 Kcal/mol
Theo s liu bng 5-3 ta thy cc gi tr thc nghim ca hiu ng nhit nh
hn gi tr l thuyt tnh. S d nh vy v cc l do sau:
. Tiu hao nng lng lin hp khi chuyn t monome sang polime.
. Tiu hao nng lng do xut hin sc cng khi cc monome co nhm th, sc
cng ny do sc ht - y ca cc nhm th to thnh (thng gi l hiu ng khng
gian).
Nh vy: H = 22,5 Q
1
- Q
2
Q
1
= nng lng tiu hao do lin hp.
Q
2
= nng lng tiu hao do hiu ng khng gian (sc cng do cu trc thay i).
V d trong phn t styren, lin kt i mch nhnh to nn h thng lin hp
vi cc lin kt i trong nhn benzen. Trong phn ng polime ho, lin kt C=C
mch nhnh b ph v v nng lng tiu hao lin hp l 3,2 Kcal/mol. Nng lng
tiu hao do hiu ng khng gian l 3 Kcal/mol, do -H
R
= 22,5 6,2 = 16,3
Kcal/mol (trong bng o c -H
R
= 16,5 Kcal/mol).
i vi trng hp isobutylen nng lng tiu hao do lin hp ch 1 Kcal/mol,
nhng hiu ng khng gian tn n 9 Kcal/mol.
. Ngoi ra, kh nng phn ng ca monome cn ph thuc vo tnh phn cc ca
phn t. Tnh phn cc ca phn t c c trng bng monome lng cc. i vi
etylen phn cc ca ni i bng 0. Nhng nu c nhm th c bn cht khc vi
H v sp xp bt i xng th phn cc cng ln.
V d:
Momen lng cc (bai)
CH
2
=CH
2
CH
3
- CH= CH
2
CH
3
)
2
- C= CH
2
C
6
H
5
- CH= CH
2
HO- CH = CH
2
CN- CH = CH
2
CH
2
= C- CH= CH
2
CH
3
0 D
0,36 D
0,49 D
0,37 D
1,44 D
3,88 D
0,38 D
1,42 D
44 of 72 10/16/2007 8:35 PM
CH
2
= CH- C= CH
2
Cl
Trong phn t propylen, nhm th CH
3
l nhm th y in t s y in t
v pha nhm CH
2

Trong mt s monome khc li cho nhm ht in t:

Vn tc khi u phn ng polime ho ph thuc kh nng phn ng ca
monome. Khi phn cc tng c th lm cho kh nng phn ng ca monome
tng tc l tng vn tc khi u phn ng polime ho. iu ny khng c ngha l
cc monome c momen lng cc bng khng th khng th polime ho.
Vn tc phn ng polime ho khng nhng ph thuc vo kh nng phn ng ca
monome m cn tu thuc vo kh nng phn ng ca gc t do.

Bi 2-6. Polime ho m vng
2-6-1. Khi nim
C rt nhiu hp cht mch vng c th polime ho thnh polime mch thng.
Khc vi s polime ho cc hp cht khng no, s polime ho m vng khng lm
thay i cu hnh in t ca lin kt v cng khng thay i s lin kt c sn
trong monome ban u.
Phn ng polime ho m vng biu din n gin nh sau:

Trong R gc hydrocacbon
A Nguyn t hay nhm nguyn t. Nguyn t hoc nhm A ny thng l -
O-, - S -, -S- S-, amin NH-, este COO-, axit COOH vv
Sau y l mt s cht i din v s polime ho m vng:

45 of 72 10/16/2007 8:35 PM

46 of 72 10/16/2007 8:35 PM

Cc hp cht vng c th polime ho kh nhiu, nhng cc polime c tm quan
trng thc t l polime t caprolactam, oxit etylen, oxit propylen, vng
bis-clorometyloxan. C ch phn ng polime ho caprolactam c nghin cu k
hn c.
2-6-2. Nhit ng hc phn ng polime ho m vng.
+ V phng din nhit ng lc hc, da vo biu thc nng lng t do:
G = H T S
G- Bin thin nng lng t do ca h phn ng
H- Bin thin entanpy ca h phn ng
S Bin thin entropy ca h phn ng
T nhit trong h phn ng.
S thay i thng s nhit ng lc hc xc nh bi phn ng c bn chuyn t
vng monome thnh mt xch polime.
Bin thin entanpy bng hiu gia entanpy ca mt xch v entanpy ca vng
monome. V khi chuyn t vng monome sang mt xch thng s lin kt khng
thay i, nn nu sc cng ca vng khng ng k th H 0. Nu monome vng
c sc cng ni ti ln th H < 0. Nh vy l sc cng vng lm tng kh nng phn
ng ca monome. Ngoi ra G cn ph thuc vo s bin i entropy.
2-6-3. C ch v ng hc phn ng polime ho m vng
S polime ho m vng di tc dng ca cht hot ho tri qua cc giai on sau:
Giai on hot ho 1.

X v Y l nhm chc to thnh do cht hoath ho B tc dng vi lin kt d mch.
2) Giai on pht trin mch

47 of 72 10/16/2007 8:35 PM

Phn ng tip tc cho n khi t n cn bng, v d s polime ho caprolactam
di tc dng ca nc.

Tng qut, s polime ho caprolactam c th vit gn li:

c im ca phn ng polime ho m vng l khng c phn ng t mch.
2-6-4. Cc yu t nh hng n s polime ho m vng
2-6-4-1. nh hng ca nng monome.
Khi pha long monome bng dung mi tr, kh nng phn ng ca phn t
monome khng thay i, nhng kh nng phn ng gia cc phn t gim (v khong
cch gia chng ln hn, tn s va chm gim), do cn bng chuyn dch v pha
to monome vng.

Ni cch khc, nng monome tng th d dng to ra nhiu polime hn.
2-6-4-2. nh hng ca nhit .
Phn ng polime ho ca cc hp cht d vng l phn ng to nhit. Hng ss
cn bng ca qu trnh:

Nu K gim, ngha l cn bng chuyn dch v pha to vng.
Nu K tng, ngha l cn bng chuyn dch v pha to polime.
Theo nhit ng lc hc ta c:
48 of 72 10/16/2007 8:35 PM

V H < 0, RT
2
> 0 nn dlnK/dt < 0, khi nhit tng th K gim. Nh vy gim
nhit lm thun li cho phn ng to ra polime. Trn bng 6-1 trnh by nh
hng ca nhit n hm lng polime caprolactam (sn phm polime ho
caprolactam).
Bng 6-1. Hm lng monome caprolactam trng thi cn bng
cc nhit khc nhau.

Nhit (
o
C)
Hm lng
caprolactam (%)
Hm lng polime
caprolactam (% KL)
220
260
300
1,8
6,7
8,8
98,2
93,3
91,1
Mt khc theo phng trnh arhrenius, n tng lm tng vn tc phn ng polime
ho, rt ngn thi gian phn ng v mau chng t trng thi cn bng. Khi nhit
tng, th KLPT ca polime sn phm gim. Trn hnh 6-1 biu din vn tc polime
ho caprolactam 231
o
C vi cc hm lng nc khc nhau th thi gian t vn tc
cc i khc nhau.

Nguyn nhn v giai on chm nht ca qu trnh phn ng l giai on thu
phn caprolactam, giai on ny quyt nh thi gian cm ng ca qu trnh.

Qu trnh c tnh t xc tc v hai nhm chc axit v amin to thnh sau phn
ng thu phn ny c 2 nhim v: phn ng vi phn t caprolactam bt u
mch phn ng polime ho to ra polycaproamit.
49 of 72 10/16/2007 8:35 PM

Phn ng ch tin hnh vi vn tc r rt khi nng nhm NH
2
v -COOH tng
i ln. Khong thi gian cho hot cht (H
2
O) vo n khi phn ng c vn tc r
rt gi l thi gian cm ng.
Vai tr th hai ca nhm NH
2
, COOH l xc tin phn ng gia nc v
caprolactam. Cc nhm NH
2
, -COOH (nhm hot tnh) va xc tin phn ng
thu phn (a) v phn ng polime ho pht trin mch (b). V vy tc phn ng
tng nhanh sau khi t thi gian cm ng. Khi vn tc t cc i, vn tc gim dn
v nng monome caprolactam gim, ng thi phn ng tin ti t trng thi
cn bng dng:

Ch nu cho thm mt t axit cng vi nc th c th gim hoc trit tiu hon
ton thi gian cm ng. i vi phn ng ny hot tnh xc tc ca kim km hn
hot tnh xc tc axit.
2-6-5. Polime ho hp cht d vng oxi
Cc hp cht d vng cha oxi n gin nht l oxit etylen, oxit propylen
Oxit etylen tinh khit v kh ngay nhit cao cng b polime ho rt chm.
Nhng khi c mt lng nh cht hot ho nh H
2
O, dung dch axit hay kim th phn
ng polime ho xy ra rt nhanh.
2-6-5-1. Polime ho tng bc ca oxit etylen.
Cht xc tc cho phn ng polime ho oxit etylen l nc v kim. Di tc dng
ca nc, phn t oxit etylen bin thnh etylenglycol:

Sau etylenglycol tn cng vo phn t etylen oxit

v phn ng c th tip tc nu cn oxit etylen trong h thng phn ng.
2-6-5-2. Polime ho chui ca monome d vng
Di tc dng ca axit, etylenoxit ch to thnh polime c khi lng phn t nh,
c polime ho nh hn 50, nhng cc monome d vng oxi c s cnh ln hn th
50 of 72 10/16/2007 8:35 PM
KLPT polime thu c cao hn.
Trong phn ng ny, nc ng vai tr rt quan trng.
Nu cho nc vi mt lng xc nh, vn tc polime ho t l thun bc 1 vi
nng monome (n=1).
Nu lng nc ch qu gii hn mt t th vn tc phn ng t l vi [M]
n
vi
1 < n < 2, vn tc cc i sau li gim.
C th vit phng trnh ng hc polime ho nh sau:
trong [M]- nng monome.
K v C cc hng s.
Vn tc polime ha t l thun nng monome v tin hnh theo c ch chui:
. Khi u:

. Pht trin mch

. t mch.

cc anion lm t mch (X
-
) c th l OH
-
, COO
-
hay anion khc c mt trong hn
hp phn ng nh F
-
vv
2-6-5-3. Polime ho khng gian c bit ca oxit propylen.
Oxit propylen di tc dng ca st (III) clorua trong ete 80
o
C (di p sut
nng cao) to thnh polime tinh th vi nhit nng chy 70
o
C, ng thi c c
polime v nh hnh.
Polyoxit propylen vi cu trc iu ho c to nn do tc dng ca ackoxit st, hp
cht cht ny do phn ng gia FeCl
3
v oxit propylen to ra trong giai on khi
u:

Polime oxitpropylen c cu trc iu ho c hnh thnh theo c ch sau:
1) Khi phn t monome n gn mch polime ang pht trin, nhm metyl CH
3
51 of 72 10/16/2007 8:35 PM
ca monome phi v tr trans so vi nhm metyl cui mch polime.

2)
Bi 2-7. Polime ho tng bc v tng hp Dien
2-7-1. Polime ho tng bc
L qu trnh tng hp polime bng cch tng hp dn dn cc monome vi nhau,
trong qu trnh ny mt nguyn t hydro hay mt nhm nguyn t chuyn t phn
t monome ny sang phn t monome khc, cc sn phm trung gian bn vng
nhng ng thi c kh nng phn ng nh monome ban u.
S chung ca phn ng polime ho tng bc cng ging nh polime ho chui,
nhng c ch hon ton khc.

Trong A
1
, A
2
, A
3
A
n
l phn t monome, ime, trime,polime.
Trong a s trng hp, cc sn phm cng hp xy ra i vi hp cht a chc,
trong c nguyn t hydro linh ng hay nhm nguyn t linh ng. Cht xc tc
thng l nc, mui, axit hoc kim.
V d qu trnh tng hp polyuretan t diizoxianat v glycol.

52 of 72 10/16/2007 8:35 PM

C th tip din.
. C ch ca phn ng gia diisoxianat v glycol c th trnh by nh sau:
diisoxianat tc dng vi 1 phn t glycol to thnh hp cht trung gian c 4 trung
tm hot ng, sau t n nh bng cch to thnh nhm este ca axit cacbamic.

. Cng tng t nh vy c th gii thch phn ng gia diisoxianat v diamin:

Sau hp cht trung gian ny li phn ng vi diamin v c th lp li nhiu
ln to ra mch polime.
C ch ca qu trnh ny l do diisoxianat tc dng vi diamin to thnh cht
trung gian c 4 trung tm hot ng, sau c n nh bng cch to thnh nhm
ur:

Phn ng ny xy ra nhanh so vi phn ng tng hp polyuretan trn v nguyn
t nhm amin linh ng hn H trong nhm hydroxit OH.
2-7-2. Tng hp Dien.
Tng hp Dien l phng php rt mi c th d iu ch c polime c vng
mch chnh. Ngi ta pht hin phng php ny khi nghin cu phn ng ca
xyclopentadien vi hp cht khng no loi axit maleic hoc anhidrit ca n.
V d phn ng gia butadien vi carolein to thnh xyclo-hexen-aldehit.

53 of 72 10/16/2007 8:35 PM

Cc loi dienofil thng gp l dn xut ca axit maleic vi xyclo pentadien hay
xyclo dien khc s to nn hp cht hai vng.

Trong phn ng ny c th to thnh 2 dng ng phn hnh hc.
+ nhit thp ch thu c loi en (I) v y cc nhm cha ni i sp
xp gn nhau hn dng exo (loi II), do phn ng nh dien vi dienofil d dng
hn.
+ nhit cao hnh thnh c 2 loi (I v II).

Khi tin hnh tng hp polime theo phng php Dien, c th dng bis-dien hoc
bis-dienofil hoch hp cht c ng thi c hai nhm dien v dienofil.
V d: Acrolein trong phn ng tng hp dien c th ng vai tr va l dien va l
dienofil.

Bi 2-8. a t mch thng
2-8-1. Gii thiu chung
a t cng nh cc sn phm phn ng polime ho thng thng, tin hnh trn c
54 of 72 10/16/2007 8:35 PM
s tc dng gia hai nhm nh chc (OH, COOH, NH
2
, halogen, hydro linh ng)
to nn mt nhm nh chc mi v thi ra mt hp cht ph, v d nh phn ng
t hp v phn ng este ho.
Trong trng hp ny khng to thnh polime v trong sn phm thiu cc nhm
nh chc hot ng nh COOH, -OH c th phn ng tip tc. Nhng nu trong
phn t ca hp cht ban u c t hai nhm nh chc tr ln, phn ng t hp c
th lp li nhiu ln v sn phm mi ln t hp nh vy u c cui mch cc
nhm nh chc c th phn ng tip tc.
V d phn ng a t ca axit aipic v hexametylen diamin to ra polyhexametyl
adipamit.

. Trong nhiu trng hp, mt cht c th c 2 nhm nh chc c kh nng phn
ng vi nhau, nnh aminoaxit th ch cn 1 monome cng c th thc hin a t:
K hiu mt nhm nh chc l X v nhm th 2 l Y ta c:
V d i vi aminoaxit:

Trong X v Y l cc nhm chc trong phn t monome.
Z: nhm mi to thnh trong polime (v d trn Z = CO-NH-)
A: sn phm ph to ra trong phn ng trng ngng.
V l thuyt, phn t polime bao gm rt nhiu mt xch monome v c KLPT
rt ln. Nhng thc t, polime to thnh gm rt nhiu mch polime c di khc
nhau, s d nh vy l v trong sn phm phn ng c cc cht ph nh (H
2
O) do
c th xy ra phn ng thun nghch, mt khc khi KLPT tng th tr ngi khng
gian cng tng, lm cho kh nng phn ng gim. Khi di mch ln v nu c
55 of 72 10/16/2007 8:35 PM
thun li v khng gian th c th to ra polime mch vng (do 2 u phn t
cha 2 nhm chc c th phn ng vi nhau). Ngi ta nhn thy phn ng a t ph
thuc ch yu vo bn cht cc nhm chc v rt t ph thuc vo iu kin phn
ng (nh nhit , nng monome). nh hng ln nht n chiu hng phn ng
ca hp cht X-R-Y l cu trc v bn cht ca gc R.
Trong bng 8-1 trnh by kh nng to sn phm mch vng ca cc aminoaxit.
Bng 8-1.
Aminoaxit S
cnh
ca
vng
Cng thc
vng c th
c
Sn phm ca phn ng c im
phn ng
Tn Cng thc
-Aminoaxetic
NH
2
CH
2
COOH
3
CO
CH
2
NH

NH-CO
CH
2
CH
2
CO- NH
2
Dimer
6 cnh
-Aminopropionic
NH
2
(CH
2
)
2
COOH
4
CO
(CH
2
)
2
NH
Axit acrylic
CH
2
=CH

COOH
Phn ng
tch
ammoniac
-aminopivalic
H
2
N(CH
2
)
3
COOH
5
CO
(CH
2
)
3
NH
-butyro-
lactam
CO
(CH
2
)
3
NH
ng vng
-aminovaleric
NH
2
(CH
2
)
4
COOH
6
CO
(CH
2
)
4
NH
- butyro-
lactam
CO
(CH
2
)
4
NH
ng vng
-aminocaproic
H
2
N(CH
2
)
5
COOH
7
CO
(CH
2
)
5
NH
Polime v
Caprolactam
H[NH(CH
2
)
5
CO]
n
OH
CO
(CH
2
)
5
NH
a t
ng vng
-aminoenantic
NH
2
(CH
2
)
6
COOH
8
CO
(CH
2
)
6
NH
Polime
H[NH(CH
2
)
6
CO]
n
OH
a t

56 of 72 10/16/2007 8:35 PM
Bng 8-2: Trong bng 8-2 l s bin i oxiaxit.
Oxiaxit S
cnh
ca
vng
Cng thc vng
c th c
Sn phm phn ng c
im
phn
ng
Tn gi Cng thc
-oxiaxetic
HOCH
2
COOH
3
CO
(CH
2
)
O
Glycolit
v polime
CO- O
CH
2
CH
2
O - CO
H[OCH
2
CO]
n
OH

-oxipropionic
HO(CH
2
)
2
COOH
4
CO
(CH
2
)
2
O
Axit acrylic
CH
2
=CH

COOH
Tch
nc
-oxipivalic
HO(CH
2
)C(CH
3
)
2
COOH
4
CH
2
- O
CH
3
)
2
C -
CO
Polime
CH
3
H[-OCH
2
-C-CO]
n
OH
CH
3
a t
-oxibutyric
HO(CH
2
)
3
COOH
5
CO
(CH
2
)
3
O
-bulico
lactam
CH
2
CH
2
O
CH
2
- CO
ng
vng
-oxivaliriamic
HO(CH
2
)
4
COOH
6
CO
(CH
2
)
4
O
-butyrolacton
v polime
CO
(CH
2
)
4
O
H-[O-(CH
2
)
4
-CO]
n
OH
ng
vng
v
a t
-oxicaproic
HO(CH
2
)
5
COOH
7
CO
(CH
2
)
5
O
Polime v
caprolacton
H-[O-(CH
2
)
5
-CO]
n
OH
CO
(CH
2
)
5
O
a t
v
ng
vng

T cc bng trn ta nhn thy hng to vng ch yu khi vng c 5 hoc 6 cnh.
i vi - amino axit hoc - oxi axit tng rng to vng 3 cnh th hng ch yu l
to vng 6 cnh. Cc loi -aminoaxit hoc -oxiaxit c kh nng c bit l tch
57 of 72 10/16/2007 8:35 PM
NH
3
v H
2
O v to ra axit khng no.
i vi -oxi axit c hai hng song song va to vng va a t. i vi
-amino v - oxi axit ch c kh nng a t, khng c kh nng to vng 8 cnh.
2-8-2. nh hng ca nng monome n hng phn ng.
Nu nng monome trong hn hp phn ng gim th kh nng phn ng ni
phn t khng thay i, nhng kh nng phn ng gia cc phn t gim. V phn
ng ni phn t l bc 1 v khng ph thuc nng ca monome.
i vi phn ng bc 1 ta c:
(*) hay
nng ban u ca monome a.
x- nng monome tham gia phn ng
k
1
- hng s vn tc phn ng bc 1
t
1
- thi gian phn ng.
T (*) ta c:
(**) hay
Trong k
1
l hng s tc phn ng ng vng (ni phn t)
k
2
l hng s tc phn ng gia cc phn t (y l phn ng bc 2).
Nh vy nu nng tham gia phn ng ni phn t v gia cc phn t vi lng
bng nhau, th thi gian t
1
t l vi lna cn t
2
t l nghch vi a.
Nu nng ban u ca monome gim th t
2
ln (tc phn ng gia cc phn t
chm) cn t
1
nh (tc phn ng ni phn t xy ra nhanh). Ni cch khc khi nng
ban u gim th tc phn ng ng vng tng, cn tc a t gim.
2-8-3. nh hng ca nhit n hng phn ng.
Theo phng trnh arrhenius:
k= A.e
-E*/RT
Trong k- hng s tc phn ng
E
*
- Nng lng hot ng ho
T- Nhit
58 of 72 10/16/2007 8:35 PM
Nu k hiu hng s tc a t l k
v ng vng l k
v
th nhit T
1
, t l hiu
sut a t v ng vng l:

Nu nng nhit n T
2
th t l sn phm a t v ng vng l:

Vy
Hay
(8-2)
*) Nu E
*
V
= E
*
(tc l nng lng hot ho ca phn ng ng vng v a t bng

nhau th L
1
=L
2
, hiu sut to vng v to polime bng nhau.
*) Nu nng lng hot ho ng vng ln hn nng lng hot ho polime ho th
E
*
V
- E
*
> 0, khi nhit tng (T

2
> T
1
) ta c L
1
> L
2
iu ny c ngha hiu sut
to polime gim v hiu sut ng vng tng.
*) Nu E
*
V
< E
*
, L
1
< L
2
tc hiu sut to polime tng khi nhit tng.
Phn 3
Bin i ho hc ca polime
Bi 3-1. c im phn ng ho hc ca polime
Bin i ho hc mt polime l lm thay i tnh cht v lnh vc ng dng ca
polime sn c, to ra nhng tnh nng mi ph hp vi lnh vc s dng mi.
Nhiu polime t nhin (nh xenluloza, tinh bt, protit) c nghin cu k tnh
cht ho hc, trong xenluloza c quan tm hn c. Nh phng php ch bin
ho hc ngi ta c th sn xut c axetat xenluloza t xenluloza thin nhin. T
polime mi l axetat xenluloza ngi ta sn xut ra si, mng mng, cht do, nitrat
xenluloza cho cht do mng sn, thuc sng khng khi v nhiu loi si este ng
dng trong nhiu lnh vc rt khc nhau.
*) Phn ng ho hc ca polime v nguyn tc khng khc cc phn ng ho hc
hu c i vi cc cht c KLPT thp. Nhng v phn t polime ln, c cu trc phc
tp nn c nhng c im ring m cc cht phn t b khng c.
+ Phn ng ca mt xch c bn lm bin i thnh phn polime nhng khng
lm thay i h s polime ho.
59 of 72 10/16/2007 8:35 PM
V d bin i dng

Qu trnh bin i ny xy ra trong ni phn t polime do phn ng gia nhm
nh chc vi mt cht c KLPT nh.
+ Phn ng ca polime km theo s thay i trng hp.
V d phn ng phn hu polime hay tng hp copolime, v d khi amoniac
NH
3
, tc dng ln polyisopren clo ho trong dung mi dioxan, nhm amin s thay
th nguyn t clo. Khi tng p sut, nhit v nng s lm tng kh nng va
chm ngoi phn t to nn polime mch nhnh hoc mch li.

Khi tin hnh bin i hohc polime cn ch cc c im sau:
+ Kh nng phn hu nhit ca phn t polime c th lm thay i cu trc v
KLPT ca polime.
+ nht ca hn hp phn ng to polime kh cao lm gim tnh linh ng ca
phn t polime. Khi tng nhit c th gim nht, nhng li tng kh nng phn
hu.
(.) i vi cc polime rn th c im kch thc l hng (mao qun) c tm
quan trng c bit, nu polime cng v mng li dy c th tc phn ng nh.
Bi 3-2. Bin i ho hc tng t
Rt nhiu phn ng gia hp cht thp phn t v cao phn t xy ra tng t
nhau. Sau y xt mt s v d cc loi phn ng tng t .
3-2-1. Phn ng thu phn
Phn ng thu phn i vi N-isopropyl valerolactam (hp cht thp phn t) v
polyvinyl pyrolidin (hp cht cao phn t) xy ra trong mi trng kim vi vn tc
gn nh nhau.
60 of 72 10/16/2007 8:35 PM

Ngi ta xc nh c rng nng lng hot ho ca phn ng (a) l E
*
(a)
= 27,5
Kcal/molv E
*
(b)
= 28 Kcal/mol, ngha l c gi tr rt gn nhau, iu gii thch
tc phn ng (a) v (b) gn bng nhau. Ni cch khc phn ng thu phn trong
2 trng hp ny khng ph thuc vo KLPT ca hp cht m ch ph thuc vo bn
cht ca nhm
N-CO m thi.
3-2-2. Phn ng kh nc
+ Cc glycol thp phn t nh etylenglycol, patametylen glycol vv khi b kh
nc c th to thnh ete mch vng hoc thng:

+ Tng t, ru polyvinylic c th b kh mt s phn t nc to ete mch
vng:

61 of 72 10/16/2007 8:35 PM

3-2-3. Phn ng hidro ho
+ Hp cht thp phn t, v d mononitril hidro ho thnh amin.

+ Hidro ho 1,3 dinitril cho amin mch thng hc mch vng.

+ Hp cht cao phn t nh polyacrylonitril b hidro ho cho sn phm c cu trc
phc tp, nhng hng chnh cng to thnh vng v tr 1,3 nh initril:

3-2-4. Phn ng x phng ho
Nu hp cht cao phn t l sn phm ca phn ng copolime ho th cc nhm
chc c tnh cht tng t cc nhm chc c trong monome ban u.
V d: axetat vinyl

Cn anhidrit maleic:

th copolime to ra t vinyl axetat v anhidrit maleic.

62 of 72 10/16/2007 8:35 PM

Khi b x phng ho (hay thu phn trong mi trng kim) s to ra mui ca
axit polyoxidicacboxylic.

3-2-5. Phn ng ca mt xch c bn
Trong phn ng bin i tng t, khng phi ton mch polime tham gia phn
ng m ch c mt vi mt xch hay tng on mt xch tham gia phn ng. V d
phn ng este ho axit polyacrylic, cc mt xch tham gia phn ng c lp, do
phng trnh phn ng thng vit cho mt xch c bn lp li n ln:

Trong trng hp khc, khng phi mi mt xch tham gia c lp m mt on
mt xch phn ng, v d phn ng kh nc ca ru polyvinylic th on tham gia
phn ng tng ng vi hexatriol gm 3 mt xch c bn.

3-2-6. phn ng ca polime vi hp cht a chc
Nu cho hp cht lng chc tc dng ln polime n chc s c polime mch
nhnh a chc. V d:

hoc to ra mch vng, kiu:

63 of 72 10/16/2007 8:35 PM

+ Phn ng ca aldehit vi ru polyvinylic s to ra polime mch vng:

3-2-7. Phn ng cao phn t
Cho hp cht lng chc tc dng vi 2 polime s to thnh cu ni gia cc phn
t, l hin tng "khu" cc mch chuyn polime mch thng thnh polime
khng gian.

Khi chuyn t polime mch thng sang polime mng khng gian KLPT polime
tng ln rt nhiu v tnh cht c l ca polime mng khng gian cng khc nhiu
so vi polime mch thng.
Cc polime khng gian thng khng tng hp trc tip t monome m thng i
t polime mch thng theo cch tng t nh trn. Trong mt s trng hp ngi ta c
th tng hp polime khng gian bng cch un nng vi mt lng nh nc, v d
phn ng chuyn rezol thnh rezit, hay t ru polyvinylic thnh polime khng gian
ch cn un nng tch nc:
64 of 72 10/16/2007 8:35 PM

Khc vi phn ng bin i tng t, phn ng chuyn t polime mch thng
thnh mng khng gian l phn ng cao phn t, trong ton b mch polime
tham gia phn ng, kt qu ca phn ng khng ph thuc vo mt xch no
phn ng, ch cn c mt s nhm chc tham gia lin kt lm cu ni l tnh cht
ca polime thay i nhiu.
3-2-8. Phn ng cc nhm chc ca polime.
* Polime ng mch
Cc polime ch cha cacbon v hydro thng tr vmt ho hc ging nh
Hydrocacbon no. V d polyetylen ch b clo ho hoc sunfo clo ho.

* Nu nhm th l vng thm (nh polystyren) th vng benzen c th tham gia
tt c cc phn ng ca hydrocacbon thm, nhng a s cc phn ng ny u km
theo phn ng phn hu v to thnh polime mng li.
V d: Phn ng hydrocacbon ho (c Ni lm cht xc tc) 200
o
C v p = 100
140 at

* Phn ng ca polystyren vi SO
2
trong dung mi dioxan to ra polime sunfo
ho:

Nghin cu cho thy c t 50% n 70% s mt xch b sunfo hoa polystyren
sunfohoas trn c trong nc lm cht nh ho.
65 of 72 10/16/2007 8:35 PM
. Cc copolime cng c th tham gia phn ng cc nhm th v d copolime hnh
thnh t styren v propylen c th b sunfo ho bng Ag
2
SO
4
trong axit photphoric
to ra polime mng khng gian khng ho tan nhng c nguyn t H linh ng
nhm sunfo axt d dng trao i ion nn c dng lm cht "cationit".

Cho thioamin tc dng vi polystyren clorometyl trong mi trng kim c th
thu c hydrosunfua ca polystyren:

* Hp cht polyhydrocacbon clo ho
V d polyvinyl clorua em clo ho tng hm lng clo trong

phn t, c th tng n 60 65% tng ng vi 1 nguyn t clo cho 3 mt xch:

Polime clo ho km ho tan, nhng nu em PVC tc dng vi AgOCOCH
3
th
nhm Cl c thay th bng nhm axetat v polime mi ny li d ho tan.

. Phn ng ca ru polime
V d ru polyvinylic
c th chuyn ho thnh ete thng qua hai giai on phn ng:
Giai on 1:
66 of 72 10/16/2007 8:35 PM

Giai on 2:
(Trong X l halogen)
* Polime axt: Trong loi ny axt polyacrylic c nghin cu k nht.

Cng tng t nh axt hu c thng, axt polyacrylic tc dng vi kim loi mnh
hoc vi kim cho mui v nc, tc dng vi ru cho este.

* Benzaldehit tc dng vi hydrazit ca axt polyacrylic to thnh polime
hydrazone

Rt nhiu polime c nhm th khc c cc phn ng c trng nn to ra nhiu
sn phm c tnh cht rt a dng v c nhng ng dng ring.

Phn 4. Phn hu v n nh polime
Bi 4-1. Khi nim v phn ng phn hu polime
Phn ng phn hu polime l phn ng lm t lin kt trong mch chnh v
lm gim KLPT ca polime.
Tm quan trng:
67 of 72 10/16/2007 8:35 PM
. Da vo phn ng phn hu polime c th xc nh c cu trc ca polime.
. Nh phn ng phn hu, ngi ta c th thu c nhng hp cht c gi tr nh
thu c glucoza t xenlulo hoc tinh bt.
. sn phm ca phn ng phn hu c KLPT thp hn polime ban u nn d
gia cng v s dng c tt nht.
. Nu bit c cu trc ca polime, c bit cc nhm nh chc xung yu,
c th tm c phng php hiu nghim bo v polime, trnh xy ra s phn
hu khng c li.
Cc phng php phn hu polime.
(*) Phng php ho hc: c th dng ho cht nh H
2
O, axt, ru, kim, oxi
vv
(*) Phng php vt l: nh phn hu nhit, nh sng, do tc dng c hc.
Khi nim phn hu:
Nu h s polime ho (hay trng hp) c trng cho phn ng polime ho,
th phn hu c trng cho qu trnh phn hu polime, l t s gia s
lin kt b phn hu vi tng s lin kt trong mch:
= a / n (4-1)
- phn hu
a S lin kt b phn hu (trong mch chnh)
n Tng s lin kt trong mch chnh (c lin quan n KLPT trung bnh)
Bi 4-2. Phn hu ho hc
S phn hu ho hc xy ra di tc dng ca cc cht c cc nh nc, axt, amin,
ru vv Qu trnh phn hu do tc dng ca nc c nghin cu k nht ( l
phn ng thu phn).
4-2-1. Thu phn
Qu trnh thu phn c xc tin di tc dng ca cc ion H
+
hay OH
-
(tc axt
hay kim), ngoi ra c 1 s men cng xc tin qu trnh thu phn. Nu phn ng
thu phn cc nhm chc bn lm thay i thnh phn ho hc ca polime th thu
phn lien kt mch chnh lm thay i KLPT ca polime, nu phn hu thp (
nh) th s nhm chc mi to thnh qa nh so vi s nhm nm trong mch nn
c th xem thnh phn ho hc ca polime trc khi phn hu v sau khi phn hu
thay i khng ng k.
68 of 72 10/16/2007 8:35 PM
Trong thc t vic phn hu polysaccarit (polyaxetal) to ra monosaccarit c tm
quan trng c bit.
V d thu phn xenluloza hoc tinh bt to ra glucoza v di tc dng ca
men s to ra ru etylic:

Cc polysaccarit thu phn vi tc khc nhau, trong xenluloza thu phn
kh khn nht, tinh bt v pentoza thu phn tng i d dng, nguyn nhn l v
cu trc l hc v cu to ho hc ca chng khc nhau.
. S thu phn ca polyamit c xc tin bng axt hoc kim:

nh vy sn phm thu phn ca prott l cc amino axt.
V d:

.+ Thu phn polyeste (xc tc l H
+
, OH
-
)

Trong polyeste no t glycol v iaxit thng d b thu phn nht, ngc li
polyeste t iaxit thm n nh hn di tc dng ca nc.

Phn ng ny kh thc hin v phn hu kh nh.
4-2-2. Phn hu oxi ho
Phn hu oxi ho cng l qu trnh phn hu ho hc nhng tnh chn lc km v
khng nhng polime d mch b oxi ho m polime ng mch cng c th b oxi
ho. i vi cc hp cht thp phn t nh parafin khi b oxi ho tng bc c th thu
c ru, aldehit, axt. Nhng i vi polime khi b oxi ho th km theo phn ng
69 of 72 10/16/2007 8:35 PM
phn hu.
S oxi ho ca polime xy ra theo c ch gc, v vy khi c cht khi u nh
peroxit benzoyl (C
6
H
5
COO)
2
v kim loi nh Fe, Cu, Monome th tc tng ln
ng k. iu ny thy r nh trnh by trn hnh (4-1).
ng 1- Khng c cht khi u
ng 2- 0,5% (C
6
H
5
COO)
2
ng 3- 0,75% (C
6
H
5
COO)
2
ng 4- 1% (C
6
H
5
COO)
2

Qu trnh tri qua cc giai on sau:

Cc gc to thnh trn u c kh nng pht trin mch. Trong qu trnh oxi ho
cc polime khng no, oxi c th nh vo ni i, sau phn hu thnh gc t do
hay to ra cc hydroperoxit:

Oxi c th nh c trc tip vi nguyn t cacbon bc ba, v d.

Sau hydroperoxit b phn hu thnh gc t do:

Gc t do mi ny c th b gy trc tip polime:

70 of 72 10/16/2007 8:35 PM

hay chuyn in t c thn cho mt polime khc ri tip tc phn hu:

Bi 4-3. Phn hu polime di tc dng vt l
Polime c th b phn hu di tc dng ca: nhit, nh sng, c v cc dng nng
lng khc. Trong qu trnh phn hu ny c th xy ra: s t mch hoc to ra lin
kt mi. Nu b gy mch l ch yu th s lm gim KLPT ca polime, nu to ra
cc lin kt mi th s lm bin i tnh cht c l ca polime l ch yu cn khng
lm thay i ng k KLPT ca polime.
. S b gy mch c th xy ra, v d:

Cc gc t do mi hnh thnh c th gy ra s pht trin mch theo hng khc
nhau. Gc polime t do c th tr thnh "polime cht" hoc pht trin mch mi tu
theo kh nng phn ng ca gc.

Ngoi ra, cn c th chu nh hng ca nh sng ng thi oxi ho:

Nu c mt mt gc km hot ng nh
th d dng to ra cc polime mi bn
71 of 72 10/16/2007 8:35 PM
c dng:

Cc polime ny c KLPT nh hn polime ban u.
Ngoi ra cn c cc cht hm (di tc dng ca nh sng) nh:

+ Tc dng ca nhit
Sn phm nhit phn ca mt s polime
Polime Mt xch c bn Nhit phn ng
polime ho
Kcal.mol
Sn phm nhit phn
polime
Polymetylmetacrylat
CH
3
-CH
2
- C-
CH
3
10 13 Monome > 90%
Polymetylacrylat
-CH
2
- CH-
OCOCH
3
20 Monome < 1%
Polystyren
-CH
2
- CH-
C
6
H
5
95
Monome 65% cn
li ime, trime,
tetrame.
Polymetyl
acrylonitril
CH
3
-CH
2
- C-
CN
17
Monome 85%
Polyacrylonitril
-CH
2
- CH-
CN
17,3
Monome 1%, mt
lng nh HCN
Polyvinyldinitril
CN
-CH
2
- C-
- Monome > 80%
72 of 72 10/16/2007 8:35 PM
CN
Polyetylen - CH
2
-CH
2
- 22 - 25
Monome 1%
Polyizobutylen
CH
3
-CH
2
- C-
CH
3

Monome 20 50%
PVC
CH
2
-CH-
Cl
Axt clohydric >
90%

Hóa học Polyme

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c th phn hu thnh gc phenyl:

, cc giai on ca phn ng c th biu din nh sau:

, phn ng pht trin mch to ra gc polime P

(tc l nng lng hot ho ca phn ng ng vng v a t bng

> 0, khi nhit tng (T

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