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Chng 3: Tnh mm do ca mch polyme


(Polymer Chain Flexibility)
Nguyn nhn chnh lm cho mch polyme mm do:
kch thc khng cn i ca mch polyme
kh nng quay quanh trc cc lin kt to thnh mch chnh ca
polyme
mm do ca mch polyme:
mm do ca mch polyme c thc hin bi kh nng
quay quanh trc cc lin kt to thnh mch chnh ca i
phn t
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Chiu di ca mch polyme
Polyethylene
(PE)
H
C
109
o
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Nu n = 10,000 th chiu di mch phn t PE khi dui thng l bao nhiu?
(zigzag planar)
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3.1. S quay ni ti trong phn t
3.1.1. Hin tng quay ca phn t thp
etan CH
3
CH
3
H
C
4
S ph thuc th nng phn t etan vo gc quay nhm metyl
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E
o
E
E
o
- Thm th
nng quay (thm
th nng hot
ha)
E
o
etan
= 15 kJ.mol
-1
E
etan
= 2,1 kJ.mol
-1
Thm th nng quay ni ti (E
o
) l nng lng cn thit phn
t chuyn t v tr c th nng nh nht sang v tr c th nng
ln nht
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3.1.2. Hin tng quay ni ti trong phn t polyme
Xt mt mch polyme c lp (isolated polyme chain), cc nguyn t C ch lin kt
vi nhau bng lin kt n (lin kt )
Alkan C
n
H
2n+2
n 1 lin kt (lin kt n)
C bao nhiu hnh thi sp xp ca mch phn t alkan?
3
n-3
V d: phn t polyme c 10,000 nguyn t cacbon trong
mch chnh s lng hnh thi sp xp ca mch phn
t l 3
9997
10
4770
!!!
Hnh thi sp xp ca phn t:
V tr tng i ca cc nguyn t v nhm nguyn t trong phn t c
th thay i c m khng c s ph v cc lin kt ha hc.
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mm do ca polyme
Cis
Trans
Thng b cn tr bi cc tng tc ca cc nhm th gn vi cc
nguyn t thc hin s quay
Cis- c nng lng ln nht, Trans- C nng lng nh nht
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mm do ca polyme
E
0
360
G
0
G
0
180
T
T
T
h

n
g
S thay i nng lng ca 1,2-
dicloetan khi mt phn phn t
quay so vi phn kia. Pha di l
cc hnh chiu phn t ng vi
cc gc quay
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Trong thc t, s quay ni ti ca phn t polyme b cn tr do:
Lc tc dng gia cc phn t (intramolecular interation): lc
lin kt hydro, lc Vandevan, lc phn tc, lc nh hng
Lc tc dng gia cc nguyn t (intermolecular interation)
trong cng mt mch (lc ni phn t):
Tc dng tng h khong cch gn gia cc nguyn t
ca cc mt xch ln cn cn tr quay t do.
Tc dng tng h khong cch xa l lc tc dng tng
h gia cc nguyn t hoc nhm nguyn t ca cc mt
xch cch xa nhau.
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mm do ca polyme
Phn t phi ph
v tmthi lin
kt quay ri
mi khi phc li
khi quay xong.
V tr tng i ca cc nguyn
t v nhm nguyn t trong
phn t khng th thay i
c nu khng ph v cc
lin kt ho hc, gi l hnh
thi cu to ca phn t.
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3.1.3. mm nhit ng v mm ng hc

i-1
i
i+1
E
o
E
1 E
2
E
E

E c trng cho mm nhit ng (thermodynamic flexibility) ca


polyme khi c cn bng nhit ng. mm nhit ng cho bit kh
nng bin i hnh thi sp xp ca mch v kh nng xy ra s thay i
.
gc quay (angle of rotation)
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mm ca mch c xc nh bng i lng E
o
gi l mm
ng hc (kinetic flexibility).
E
o
: (thm th nng quay potential rotation barrier or hindrance
potential) nh hng n vn tc bin i hnh thi sp xp. E
o
cng ln
th cc mt xch quay cng chm v tnh mm do ca mch cng b.
E: Nng lng tc ng t bn ngoi (chuyn ng nhit, lc c hc hoc
cc lc khc)
Vn tc bin i
hnh thi sp xp
E
o
=
E
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mm do ng hc v mm do nhit ng c th
khng trng nhau.
Khi mm nhit ng ln (E nh) nhng vn tc quay ca
cc mt xch c th b (E
o
ln) th mch vn c th cng
S quay quanh cc lin kt v thay i hnh thi sp xp
(t v tr c nng lng cc tiu ny n mt v tr c nng
lng cc tiu khc) ch c th xy ra khi c nng lng d
tr cn thit.
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Nu khng c nng lng d tr cn thit (ln hn E
o
) th
cc mt xch ch c th chuyn ng nhit c trng ring
(v d: dao ng xung quanh cc v tr c nng lng cc
tiu). Dao ng ny cng nh th mch phn t cng cng.
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phn cc ca phn t
Phn t khng phn cc
Phn t phn cc
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3.1.4. Cc yu t nh hng n tnh mm do ca mch
Thm th nng quay
Khi lng phn t
Kch thc mch nhnh
Mt mng li khng gian
Nhit
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a. Thm th nng quay E
o
Thm th nng quay ph thuc vo lc tc dng tng h bn trong
phn t v gia cc phn t v do ph thuc vo phn cc ca cc
nhm th. Hay ph thuc vo thnh phn ha hc v cu to ca mch
E
o
(kcal/mol)
H
3
C CH
3
2,80
H
3
C C
2
H
5
3,40
H
3
C CH(CH
3
)
2
3,90
H
3
C C(CH
3
)
3
4,40
H
3
C CH=CH
2
1,95
E
o
(kcal/mol)
H
3
C CF
3
3,700,45
H
3
C OH 1,07
H
3
C SH 1,06
H
3
C NH
2
1,90
H
3
C SiH
3
1,70
F
3
C CF
3
4,35
(cc gi tr c tnh khi hp
cht trng thi kh l tng)
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Mch polyme c thm th nng quay thp th c mm do cao
Polyme mch hydrocacbon: PE, PP, Polyisobutylen,
Polybutadien, Polyisopren
Polyme d mch c cha cc nhm C O C, - CO O , -
NH COO v c phn tch bi s lng lng ln nhm
CH
2

Mch polyme c cha nhm th phn cc vi hm lng thp


(v d cao su polyclopren v cao su nitril)
Mch polyme c cha nhm th kch thc nh ( - CH
3
) hoc
thm ch ln hn nhng sp xp tha tht trn mch chnh. (v
d polyisobutylen, poly(butadien co- styren)
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b. Khi lng phn t
Khi lng phn t ca mch tng khng lm thay i E
o
, nhng
kh nng bin i hnh thi sp xp tng ln.
c. Mt mng li khng gian
Khi s lng lin kt ngang tng ln th
di mch trn th hin s mm do
s gim xung.
Khi mt lin kt ngang rt ln th
mm do s bin mt hon ton.
V d cao su thin nhin lu ho vi 30% lu
hunh
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d. Kch thc nhm th
Kch thc ln ca nhm th lm cn tr s quay ca mt xch
Polystyren
S thay i hnh thi sp xp cn rt di v thc t khng xy ra
nhit thp
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d. Nhit
C tc dng tng linh ng ng hc ca cc on trong mch polyme
on hay segment l mt phn ca phn t polyme m v tr ca
n trong khng gian khng ph thuc vo v tr cc mt xch ln
cn
i lng on l thc o kh nng cun li ca i phn t,
ngha l thc o mm do ca chng. i vi mch mm l
tng th gi tr ca on bng mt mt xch phn t, phn t cng
cng th gi tr ca on cng cao