Korean Chem. Eng. Res., Vol. 42, No. 3, June, 2004, pp.

326-331

Poly(ethylene-co-1,4-cyclohexylenedimethylene)
Terephthalate Oligomer

447-1
, 2004 4 28 )

139-701
(2003 12 26

Kinetics of the Formation of Poly(ethylene-co-1,4-cyclohexylenedimethylene)

Terephthalate Oligomer by Various Catalysts
Sang Soon Park and Joong So Choi
Department of Chemical Engineering, Kwangwoon University, 447-1, Wolgye-dong, Nowon-gu, Seoul 139-701, Korea
(Received 26 December 2003; accepted 28 April 2004)

230 C

Dimethyl terephthalate (DMT), ethylene glycol (EG), 1,4-cyclohexane dimethanol (CHDM)

.
.
,
.
Ti > Pb > Zn > Mn > MBTO > Co > Cd > Mg > Li
.

Abstract A kinetic analysis of the esterification of dimethyl terephthalate (DMT) with ethylene glycol (EG) and 1,4-cyclohexane dimethanol (CHDM) was investigated in the presence of various catalysts at 230 oC. The conversion was followed by
the measurement of output of methanol which was distilled from the reactor. The catalytic activity was increased with the
increase of molar ratio, agitator speed, and catalyst concentration. Also, the decreasing order in catalytic activity on the esterification was Ti > Pb > Zn > Mn > MBTO > Co > Cd > Mg > Li.
Key words: Poly(Ethylene-co-1,4-Cyclohexylenedimethylene) Terephthalate, Heat Shrinkable Tube, Esterification, Catalytic Activity

1.

PET
.
Poly(ethylene terephthalate) (PET)[2-4] PVC
,
,
. PET
.
3 PET .
PET
[5, 6] 2 . Tomita Ida[7]
PET
,
. Fontana [8-10]

.
PET 1,4-cyclohexanedimethanol(CHDM)
3 PET
.

, ,

.


, , code
, // ,
, [1].
PVC

.
PVC
PVC
To

whom correspondence should be addressed.

E-mail: jschoi@kw.ac.kr
326

 Poly(ethylene-co-1,4-cyclohexylenedimethylene) Terephthalate Oligomer

2.

(C) 1 DMT(A) 2 (B)

(P) .
(W)

.

(1) .
DMT+Glycols+Catalyst Product+Side-product
A
B
C
P
W

.
(C ) C =N /V={C /(1+ X )} C
(5) .
C

XA

(1)

, C , C : A B
, C : C
, k , k : , t:
--------- = k C C C a=1
(1) dC
dt DMT
a=0
(2) .
1

dC
r A = ---------A = k1 C A CB
dt

(2)

A B (N , N ) N =N (1X ) N =N (1-X ) (V)
V=V (1+ X ) . X X A B
(=(V -V )/V , V :
, V : ) .
C =N /V N V C ={N (1-X )/V (1+ X )}
N /V =C C ={C (1-X )/(1+ X )} .
C =N /V C ={N (1-X )/V (1+ X )}={C (1-X )/(1+ X )}
. (M) M=C /C C =MC .
A B 2 2C X =C X
. X =2X /M C ={C (M-2X )/
(1+ X )} .
r =dC /dt r ={C dX /(1+ X )dt}
.
(2) (3) .
A

A0

100

100

A0

A0

B0

A0

B0

A0

B0

A0

A A

A0

B0

A0

XA

B0

A0

(5)

1 - ----------------------------- ( + 1 ) 2 ln ( 1 X )
Y 2 = ---------------A
A
2
( M 2)
(6)

A X A ( M 2)
1
2
- ( A + 1 ) ln ( 1 XA )
Y 12 = Y1 + Y2 = ----------------- ---------------------------(M 2)
2
( MA + 2 ) ( M 2XA ) A M ( M 2X A )
ln ------------------------ + ---------- ln -----------------------+ ------------------------M
4
M
2
= ( k1 + k2 CC0)CA0t = Kapp.12t
2

1 + A XA

A0

- = k C dt
0 (-----------------------------------------1 XA ) ( M 2X A ) 0 1 A0

A M ( M 2XA )
1
ln ------------------------ = k 1C A0t
Y1 = ----------------- ( 1 + A ) ln ( 1 XA ) + ---------(M 2)
M
2
(4)
= Kapp.1t
dCA
a
--------- = k2 CA CB CC
(1)
1
dt
dC
A
b=1
.
--------- = k2 CA CB CC
dt

(7)

3-1.
PET
dimethyl terephthalate(DMT:
),
ethylene glycol(EG:
), 1,4-cyclohexane dimethanol(CHDM:
Aldrich)
.
zinc acetate(Zn), tetrabutyl
titanate(Ti), magnesium acetate(Mg), lead acetate(Pb), lithium acetate(Li),
monobutyl tinoxide(MBTO), manganese acetate(Mn), cobalt acetate(Co)
Aldrichl
.

3-2.
poly(ethylene-co-1,4-cyclohexylene
dimethylene) terephthalate(P(ECHDMT)) Scheme 1
1 2
.
1 L
(Scheme 2)
.
DMT, EG, CHDM
230 C .
dimethyl terephthalate(DMT), ethylene glycol(EG),
1,4-cyclohexane dimethanol(CHDM) 1 PET
poly(ethylene-co-1,4-cyclohexylenedimethylene) terephthalate (P(ECHDMT))
.
.
o

(3)

(Y ) (4).

3.

a
A

0 k2 CA0 CC0dt

2
A XA ( M 2 )

(5) (Y ) (6).

B0

dC
a
a
r A = ---------A = k1 C A CB CA + k2 CA CB CC
dt

C0

(4) (6) (1) a=0, b=1

(7) .

k2

A+B+C P' + W'

( 1 + A X A )
------------------------------------------ dX =
( 1 X A ) ( M 2XA ) A

A+B P+W

( MA + 2 ) ( M 2X A )
ln ------------------------ = k2CA0CC0t = Kapp.2t
+ ------------------------M
4

k1

327

4.

4-1. Zinc acetate

. Fig. 1 DMT
2.1, 230 C, zinc acetate(Zn) zinc
acetate 1.010 - 5.010 mol/mol DMT
.
o

Korean Chem. Eng. Res., Vol. 42, No. 3, June, 2004

328

Scheme 1. Synthesis scheme of P(ECHDMT) copolymer.

Scheme 2. Reaction apparatus of esterification reactor.

DMT (EG CHDM)

.
50 Zn
1.010 mol/mol DMT 21, 2.010 mol/mol DMT 18,
3.010 - 5.010 mol/mol DMT 14.
Zn
, Zn
3.010 mol/mol DMT
.
Fig. 1
180 30% .
(7) DMT

4
4

42 3 2004 6

Fig. 1. Effect of zinc concentration ( 104 mol/mol DMT) on the

esterification of DMT and glycols (EG and CHDM) at 230 oC
(molar ratio 2.1); 0,
1, 2
3 4 5.

.
Fig. 1 (7) Y -t
Fig. 2.

.
Fig. 3.
Fig. 3 (7) Fig. 2 Y -t
(K ) .
Fig. 1 60
0 Y .
60
. (C )
12

12

app.12

12

A0

 Poly(ethylene-co-1,4-cyclohexylenedimethylene) Terephthalate Oligomer

Fig. 2. Plot of kinetic value (Y) calculated from data of Fig. 1;

2 3 4 5.

1,

Fig. 3. Dependence of rate constant, LnKapp.12, on the concentration

of zinc acetate (104 mol/mol DMT).

(C ) (K )
. Zn
,
Zn 3.010 mol/mol DMT
. Zn
3.010 mol/mol DMT
.
4-2.

.
C0

app.23

329

Fig. 4. Effect of molar ratios on the esterification of DMT and glycol

with zinc acetate (3.0 104 mol/mol DMT) at 230 oC;
M=2.1,
M=2.5,
M=3.0,
M=3.5.

Fig. 5. Plot of rate constant, LnK app.12, against molar ratio in data of
Fig. 4.

DMT, (EG CHDM)

(3.010 mol/mol DMT) DMT (EG+
Fig. 4.
2.1 14, 2.5 10, 3.0
3.5 5
. 120
2.1 89.6%, 2.5 95.7%, 3.0 98.9% 3.5 99.7%
.
Fig. 5 (7) Fig. 4 , Y -t
, (K )
.
230 oC
Zn
CHDM)
50%
7

12

app.12

Korean Chem. Eng. Res., Vol. 42, No. 3, June, 2004

330

Fig. 6. Effect of agatator speed on the esterification of DMT and glycol with zinc acetate (3.0 104 mol/mol DMT) at 230 oC;
40 rpm,
80 rpm,
120 rpm.

Fig. 7. Plot of rate constant, LnKapp.12, against agitator speed in data

of Fig. 6.

(EG CHDM)

2.1)
.
50% 40 rpm 17, 80 rpm 14,
120 rpm 12
. 120 40 rpm 92.0%,
80 rpm 93.2%, 120 rpm 94.1%
.
Fig. 7 (7) Fig. 6 , Y -t
, (K )
.
.
4-4.


. ligand atom
Shah [9] Class A Class B . , Class A
donor atom 1 (i.e. N, O, F )
ligand , Class B
donor atom 2 (i.e. P, S, Cl ) ligand
, ligand
Class B . (Zn),
(Ti), (Pb) Class
A . Class A ligand
Fig. 8.
Fig. 8 230 C DMT (EG CHDM) 2.1
(3.010 mol/mol DMT) zinc
4-3.
DMT
Fig. 6 230 oC
(Zn
: 3.0 104 mol/mol DMT,

12

app.12

acetate(Zn), magnesium acetate(Mg), lead acetate(Pb), lithium acetate(Li),

42 3 2004 6

Fig. 8. Effect of catalyst type (conc. 3.0 104 mol/mol DMT) on the
esterification of DMT with glycol at 230 oC; Co, Ti,
Cd, Li,
MBTO,
Mg, Mn, Pb, Zn.

monobutyl tinoxide(MBTO), manganese acetate(Mn), cobalt acetate(Co),

tetrabutyl titanate(Ti) cadmium acetate(Cd)
.
50%
Mg 30 , Pb 14 , Li 35
, Zn 13 , MBTO 17 , Mn 16 , Co 18 , Ti 12 , Cd 18
.
180
Mg 85.6%, Pb 93.3%, Li 83.7%, Zn

93.2%, MBTO 91.9%, Mn 92.6%, Co 91.3%, Ti 94.3%, Cd 91.3%
Ti .

(-COO-) () (>C=O)
, -
()

 Poly(ethylene-co-1,4-cyclohexylenedimethylene) Terephthalate Oligomer

331

2002
. .

Fig. 9. Plot of rate constant, LnKapp.12, against catalyst type in data of

Fig. 8.

[7].
Fig. 9 Fig. 8 (7)
(K ) .
Ti > Pb > Zn > Mn > MBTO > Co > Cd >
Mg > Li Ti .
app.12

5.

DMT, EG, CHDM P(ECHDMT)

, .
Zn ,

, P(ECHDMT)
. Zn
.
. Ti > Pb > Zn >
Mn > MBTO > Co > Cd > Mg > Li Ti
.

1. Yoo, T. J., Insulating Materials of Electric Power Cable, Polym.

Sci. Tech., 9, 381-388(1998).
2. Park, H. S., Weight Loss Effects of PET Fibers by Quaternary
Ammonium Salts Containing Palmityl Aliphatic Group, HWAHAK
KONGHAK, 33(1), 113-120(1995).
3. Chung, S. H., Lee, J. H., Shim, J. J., Kim, J. S. and Kim, S. W.,
Decomposition of PET in High Pressure Subcritical Water, HWAHAK KONGHAK, 40(6), 709-714(2002).
4. Yuk, H. M., Park, J. H., Park, S. D. and Lee, C. H., Hydrolysis of
Polyethylene Terephthalate(PET) under Subcritical and Supercritical
Water using Batch System, HWAHAK KONGHAK, 41(2), 249-255(2003).
5. Hovenkamp, S. G., Kinetic Aspects of Catalyzed Reactions in the
Formation of Poly(ethylene terephthalate), J. Polym. Sci., 9, 3617-3625
(1971).
6. Walker, C. C., The Inhibitory Effect of Carboxylic Acids on the
Catalyzed Reaction between Dimethyl Terephthalate and Ethylene
Glycol, J. Polym. Sci., 21, 623-626(1983).
7. Tomita, K. and Ida, H., Studies on the Formation of Poly(ethylene
terephthalate): 3. Catalytic Activity of Metal Compounds in Transesterification of Dimethyl Terephthalate with Ethylene Glycol,
Polymer, 16, 185-190(1975).
8. Fontana, C. M., Polycondensation Equilibrium and the Kinetics of
the Catalyzed Transesterification in the Formation of Poly(ethylene
terephthalate), J. Polym. Sci.; Part A-1, 6, 2343-2358(1968).
9. Shah, T. H., Bhatty, J. I. and Gamlen, G. A., Aspects of the Chemistry of Poly(ethyleneterephthalate). III. Transesterification of Dimethyl Terephthalate with Ethylene Glycol in the Presence of Various
Catalytic Systems, J. Macromol. Sci.-Chem., 21(4), 431-443(1984).
10. Park, S. S., Jun, H. W. and Im, S. S., Kinetics of Forming Poly
(butylene succinate) (PBS) Oligomer in the Presence of MBTO Catalyst, Polym. Eng. Sci., 38, 905-914(1998).

Korean Chem. Eng. Res., Vol. 42, No. 3, June, 2004