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

Tran Hai Ninh - Polymer CenterHUTS

Chiu di ca mch polyme

Polyethylene
(PE)

H
C

4
1.5

109o 28

(zigzag planar)

Nu n = 10,000 th chiu di mch phn t PE khi dui thng l bao nhiu?

Tran Hai Ninh - Polymer CenterHUTS

3.1. S quay ni ti trong phn t

3.1.1. Hin tng quay ca phn t thp

etan

CH3 CH3

C
H

S ph thuc th nng phn t etan vo gc quay nhm metyl

Tran Hai Ninh - Polymer CenterHUTS

n-butan

CH3 CH2 CH2 CH3

Tran Hai Ninh - Polymer CenterHUTS

Trng thi nng lng cao

Trng thi nng lng thp

(quan st dc theo trc
C2-C3)
Tran Hai Ninh - Polymer CenterHUTS

Eo

- Thm th
nng
quay
(thm
th
nng
hot
ha)

Eo

Eoetan = 15 kJ.mol-1
Eetan = 2,1 kJ.mol-1

Thm th nng quay ni ti (Eo) l nng lng cn thit phn

t chuyn t v tr c th nng nh nht sang v tr c th nng
ln nht
Tran Hai Ninh - Polymer CenterHUTS

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

CnH2n+2

n 1 lin kt (lin kt n)

V d: phn t polyme c 10,000 nguyn t cacbon trong

C bao mch
nhiuchnh
hnhthi
sp xp ca mch phn t alkan?
s lng hnh thi sp xp ca mch
phn t l 39997 n-3
104770 !!!

Tran Hai Ninh - Polymer CenterHUTS

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.

Tran Hai Ninh - Polymer CenterHUTS

Tran Hai Ninh - Polymer CenterHUTS

10

3.1.3. mm nhit ng v mm ng hc
E
i+1

Eo

i-1

E
E1

E2

gc quay (angle of rotation)

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 .
Tran Hai Ninh - Polymer CenterHUTS

11

 Eo: (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.

Vn tc bin i
hnh thi sp
xp

Eo
E

E: Nng lng tc ng t bn ngoi (chuyn ng nhit, lc c hc hoc cc

lc khc)

mm ca mch c xc nh bng i lng E o gi l mm

ng hc (kinetic flexibility).

Tran Hai Ninh - Polymer CenterHUTS

12

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 (Eo 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.

Tran Hai Ninh - Polymer CenterHUTS

13

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.

Tran Hai Ninh - Polymer CenterHUTS

14

 phn cc ca phn t
Phn t khng phn
cc
Phn t phn cc

Tran Hai Ninh - Polymer CenterHUTS

15

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

Tran Hai Ninh - Polymer CenterHUTS

16

a. Thm th nng quay Eo

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.

Eo
(kcal/mol
)
H3C CH3

2,80

H3C C2H5

3,40

H3C
CH(CH3)2

3,90

Eo
(kcal/mol
)
H3C CF3

3,700,4
5

H3C OH

1,07

H3C SH

1,06

H3C NH2
H3C C(CH3)3
4,40
(cc gi tr c tnh khi hp
H3C SiH3
H3C
1,95
cht trng thi kh l
CH=CH2
F3C CF3
tng)
Tran Hai Ninh - Polymer CenterHUTS

1,90
1,70
4,35
17

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
CH2
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 ( - CH3) hoc
thm ch ln hn nhng sp xp tha tht trn mch chnh. (v
d polyisobutylen, poly(butadien co- styren)
Tran Hai Ninh - Polymer CenterHUTS

18

b. Khi lng phn t

Khi lng phn t ca mch tng khng lm thay i Eo ,

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
Tran Hai Ninh - Polymer CenterHUTS

19

d. Kch thc nhm th

Kch thc ln ca nhm th lm cn tr s quay ca mt xch

Polystyren

Tran Hai Ninh - Polymer CenterHUTS

20

d. Nhit

Khi nhit tng th mm do ca mch polyme tng ln nh

tng mm ng hc.

Tran Hai Ninh - Polymer CenterHUTS

21

Monte Carlo Simulation

Tran Hai Ninh - Polymer CenterHUTS

22

Tran Hai Ninh - Polymer CenterHUTS

23