Die Angewandte Makromolekulare Chemie 113 (1989) 163 - 181 (Nr.

2876)

* Department of Polymer Chemistry, Jilin University, China

** Department of Industrial Chemistry, Chiba Institute of Technology,
2-17-1, Tsudanuma, Narashino, Chiba, 275 Japan

Molecular Aggregation of PEEK with PES Blends

and the Block Copolymers Composed of PEEK and
PES Components

Zhongwen Wu*, Yubin Zheng*, Hongmao Yan*, Tomoki Nakamura**, Takafumi

Nozawa**, and Ryutoku Yosomiya**

(Received 8 November 1988; revised 7 February 1989)

SUMMARY:
Polymer blends of PEEK with PES were prepared by the solution blending
method. Copolymers composed of PEEK and PES components were synthesized
from these oligomers. The formation conditions exerted an influence over the mole-
cular aggregation and the crystallization behaviors of the blend films and block co-
polymers which were examined by X-ray diffractometry and DSC analysis. As a
result, phase-separation in the blend films was found when the formation tempera-
ture was high. The blend films formed at 340"C, quenched and annealed at 18O"C,
exhibited the same crystallization behavior as those of PEEK. In the case of the blend
films formed at 300"C, the annealing of the films at 250°C was required to crystallize
the blend films. The Tg of a copolymer with a PEEK component content of more than
50% tends to shift toward a higher temperature than the Tg of PEEK itself, and the
T, of the copolymer toward a lower temperature than that of PEEK.

ZUSAMMENFASSUNG:
Rdntgendiffraktometrische Untersuchungen und DSC-Messungen an Blend-
Filmen, die aus Ldsungen von PEEK und PES hergestellt wurden, zeigen eine Pha-
senseparation bei den Filmen, die bei 340 "C hergestellt wurden. Das Kristallisations-
verhalten von Filmen, die bei 340 "C hergestellt, anschlienend abgeschreckt und bei
180 "C getempert wurden, ist identisch mit dem von PEEK. Filme, die bei 300°C her-
gestellt wurden, kristallisierten erst durch Tempern bei 250 "C. Blockcopolymere, die
aus Oligomeren von PEEK und PES erhalten wurden, unterscheiden sich in dieser
Hinsicht von Blends der gleichen Zusammensetzung. Die Glastemperatur von Copo-
lymeren mit einem PEEK-Gehalt von mehr als 50% liegt hoher als die von PEEK
selbst, wiihrend der Schmelzpunkt dieser Copolymeren niedriger als der von PEEK
ist .

0 1989Hiithig & Wepf Verlag, Basel 0o03-3146/89/$03.00 163

 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

I . Introduction

In recent years, a number of patents or patent applications which claim

polymer blends or blending of polyetheretherketone (PEEK) with other
superengineering plastics to improve the physical properties of PEEK have
been reported'-5. However, very few fundamental studies on the polymer
blends or blending have been found. In our previous reports6, PEEK and
polyethersulfone (PES) solutions synthesized by condensation polymeriza-
tion, independently, were homogeneously mixed together and were precipi-
tated and refined to form a polymer blend of PEEK with PES. Such polymer
blends produced in such a manner had significantly different dynamic visco-
elasticities depending on the film forming conditions. It has been revealed
that these different dynamic viscoelasticities were attributed to the differen-
ces in phase separation behavior between polymers. As to the crystal struc-
ture of PEEK, many literatures have been found7-I2. Furthermore, the syn-
thesis of a block copolymer with other superengineering plastics is another
way for We succeeded in the synthesis of block copoly-
mers composed of PEEK with PES components, and investigated the effect
of the composition and other factors on their molecular aggregation.

2. Experimental

2.1 Materials

Blends of PEEK with PES having different compositions were prepared as

described in a previous report6. The blend samples were formed into films of 0.5 mm
in thickness with a compression molding press at 340 "C or 300 "C, 100 kg/cm2, for 10
min. For preparation of amorphous film samples, the above films were placed on an
aluminium plate and annealed at 360 "C for 5 min and immediately put into a mixture
of water and ice for quenching. Crystalline film samples were prepared by annealing
the amorphous films at various conditions, and after a predetermined time, cooling
the samples spontaneously to room temperature.

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 Molecular Aggregation of PEEK with PES Blends

2.2 Synthesis of PES Oligomers with a Hydroxy End Group

PES oligomer was synthesized according to Eq. (1).

(n/2 + I ) H O a S 0 2 0 0 H + ni2 C l o S 0 2 - @ l + (n+2) NaOH -Sulfolane

220-c

+ (n+2) H 2 0 + n NaCl (1)

For the present study, PES oligomers with a definite average degree of
polymerization (x
= 25) were prepared.

2.3 Synthesis of PEEK Oligomer

PEEK oligomer with a fluorine containing end group was synthesized according to
Eq. (2).

Lhphenylsulfone
(n+l) F G r i G F + n H*OH + n (0.1K,C03.0.9Na2C03) c
320°C
0

[Ill
+ 2n ( 0 . l K F - 0 . 9 N a F ) + n CO, + n H,O (2)

For the PEEK oligomers with varying average degree of polymerization, the mole
ratios of 4,4'-difluorobenzophenoneand hydroquinone and the average degrees of
polymerization are shown in Tab. 1.

2.4 Synthesis of a Block Copolymer Composed of PEEK with PES

Component

The synthesis of a block copolymer composed of PEEK with PES component was
carried out according to Eq. (3).

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 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R.Yosomiya

+ N a O - @ S 0 2 ~ O ~
m
2 ~ O N -
a

The amounts of PES oligomers and PEEK oligomers with different average degrees
of polymerization in the copolymers are shown in Tab. 2.

Tab. 1. Relation between and mole ratio (r) of hydroquinone (HQ) and 4,4'-di-
fluorobenzophenone in PEEK oligomers.

4,4'-difluorobenzo- 0.2004 0.2008 0.2040 0.2081 0.2168

phenone (mol)
Hydroquinone (mol) 0.2000 0.2000 0.2000 0.2000 0.2000
mole ratio (HQ)/ 0.998 0.996 0.980 0.961 0.923
( D W (r)
-
x, 1000 500 100 50 25

Tab. 2. Ratios of PEEK oligomers with PES oligomers in copolymers.

PEEK oligomer 1000 500 loo 50 25

PEEK weight (g) 57.7 57.8 58.5 59.4 61.3
PES weight (g) 2.32 4.66 23.61 47.9 98.8
mole ratio (PEEK : PES) 20 : 1 10 : 1 2:1 1 : l 1:2
ratio of weight 96: 4 92.5 : 7.5 71 : 29 55 : 45 38 : 62
(PEEK : PES) (Vo)

2.5 Measurements

Samples were identified by X-ray diffractometry on a X-ray diffractometer (Model

VG-1O8R, Shimazu Co.) with Cu-Ka radiation, 0.15 mm receiving slit, scanning

166
 Molecular Aggregation of PEEK with PES Blends

speed 2"/min at 40 KV, 30 mA. For the X-ray diffraction measurements of heated
samples (from room temperature to high temperature), the heating rate was
10"C/min. Differential Scanning Calorimetry (DSC Model 11, Perkin-Elmer) was
carried out in nitrogen atmosphere at a heating rate of 10"C/min.

3. Results and Discussion

3.1 Effects of Formation Temperature on Molecular Aggregation

Fig. 1 shows the X-ray diffraction results of the films of the various
blends formed at 340°C. Diffraction peaks in the same pattern as those of
PEEK appeared at 28 of 18.5", 20.4" and 28.3'. This suggests that the
crystalline structure of each sample can be attributed to the component in
the film. Moreover, as seen in the diffraction patterns (a), (b), (c) and (d),

10 20 30 40 50
28 (degs)
Fig. 1. X-ray diffraction patterns of polymer blends formed at 340°C. PEEK/PES:
(a) 80/20, (b) 70/30, (c) 60/40, (d) 50/50.

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 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

the intensity of the diffraction peaks increased with increasing the content of
PEEK. Then the crystallinity was determined according to the method of
Blundell et al. '3.
Fig. 2 shows the crystallinity of the blend films having different composi-
tions. There was found a tendency that the apparent crystallinity of the
blend films decreased in proportion as the content of PES was increased.
However, the crystallinity of the PEEK component in the films was almost
constant, irrespective of the blend compositions.

\
"\
"\
o\ 0

10
0 50 100
PES (96)
Fig. 2. Relation between crystallinity and blend composition; ( 0 )apparent crystal-
linity of the blend films, (A)crystallinity of the PEEK component in the
films.

Fig. 3 shows the X-ray diffraction results of the blend films formed at
300°C having different compositions. In a similar manner as described
above, Fig. 4 shows the correlation between the crystallinities and the
compositions. The comparison of the results in Fig. 2 and Fig. 4 reveals that
the absolute values of the apparent crystallinities of the films and also the
crystallinities of the PEEK components in the films were significantly
different from each other, though the tendencies of the changes in the
crystallinities were the same. More particularly, the films formed at 340"C
had a crystallinity of the PEEK component of about 30%. On the other

168
 Molecular Aggregation of PEEK with PES Blends

I I I I I
10 20 30 40 50
26 (degs)

Fig. 3. X-ray diffraction patterns of polymer blends formed at 300°C. PEEK/PES:

(a) 80/20, (b) 70/30, (c) 60/40,(d) 50150, (e) 40160.

hand, the crystallinity of the PEEK component in the films formed at 300 "C
was about 46%. This value is equal to the maximum crystallinity of PEEK.
In brief, the crystallinities of the PEEK components were considerably
different, depending on the different film-formation temperatures. It is
possible that the differences in crystallinity were caused by the differences in
dispersion state of the PEEK and PES components in the films. More
particularly, the blends used in this report were prepared by dispersing the
two components homogeneously at a molecular level. Accordingly, it seems
that the PEEK component was in molten state while the blend was formed
into a film at 340°C (higher than the melting point of PEEK), and was
crystallized in PEEK phase during the spontaneous cooling without
influences by the PES component. This assumption is compatible with the

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 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

50 t
h
I A- - A -
,.'A
A
-

?5
x
40
L

20 L I I
0 50 100
PES ( % I

Fig. 4. Relation between crystallinity and blend composition; (0) apparent crystal-
linity of the blend films, ( A ) crystallinity of the PEEK component in the
films.

dynamic viscoelastic behaviors described in the previous reports that the a

transition regions of PEEK and PES were separately exhibited. On the other
hand, it seems that the behavior of the PEEK components in the films
formed at 300 "C can be attributed to the low temperature crystallization
behaviors caused by the annealing.
Fig. 5 shows scanning electron microphotographs of the films formed at
300°C and 340°C. As shown in Fig. 5 , the film formed at 340°C suffered a
definite phase separation. On the contrary, the film formed at 300°C was
kept in homogeneous dispersion state without phase separation. For further
identification of the above phenomena, these films were subjected to DSC
measurement. The DSC curve revealed only one glass transition point as
shown in Fig. 6. These experimental evidences suggest that the film formed
at 300 "C was a film in which the two components were homogeneously dis-
persed without phase separation.

170
 MolecuIar Aggregation of PEEK with PES Blends

Fig. 5. Scanning electron microphotographs of blend films, (a) formed at 340°C,

(b) formed at 300°C.

z1
Y

B
0
iZ0 .*oO I
t
0
W
I

f I I I I I
100 150 200 250 300 350
Temperature ('C)

Fig. 6. DSC curves of various blend compositions formed at 300°C. PEEK/PES:

(a) 30/70, (b) 4O/60,(c) 50/50, (d) 70/30, (e) 80/20.

171
 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

3.2 Effects of Annealing on Molecular Aggregation of the Blends

The quenched blend samples were subjected to X-ray diffraction

measurement as shown in Fig. 7. For both samples, the diffraction peaks
near 28 of 20" disappeared, and broad halos were presented instead. This
suggests that the quenched samples were amorphous. Fig. 8 shows the DSC
curve of those samples. For both samples, obvious exothermic peaks, which
are accompanied with low temperature crystallization, appeared near
200°C. This means that the quenched blend samples took an amorphous
molecular aggregation.

I I I I 1
10 20 30 40 50
28 (degs)
Fig. 7. X-ray diffraction patterns of the quenched blend films; (a, b) blend films
formed at 300°C; PEEK/PES: (a) 80/20,(b) 70/30), (c) blend film formed
at 340°C (PEEK/PES: 70/30).

Fig. 9 shows the relation between the glass transition temperature (Tg),the
low temperature crystallization peak temperature (T,) and the melting peak
temperature (T,) obtained by the above results. As seen in Fig. 9, the Tg and
T, of the samples were higher than those of PEEK. Also, as the content of
PES was increased, the Tg and T, were elevated. Referring to a probable
reason for the phenomena, the Tg of PES is 225 "C, and the molecular chains
of PES are in glassy state below 200°C and take a motion with much
difficulty. This imposes a significant restriction on the movement of the

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 Molecular Aggregation of PEEK with PES Blends

4
z 1.0
4
t

I
0.0

W I I I L
I

160 150 200 250 300 350 400

Temperature (“C)

Fig. 8. DSC curves of the quenched blend films. (a, b, c) blend films formed at
300°C;PEEK/PES: (a) 50/50, (b) 70/30,(c) 80/20), (d) blend film formed
at 340°C (PEEK/PES: 70/30).

Tm
(“C)

- 300

:“)J/f
140
0 50 100

Fig. 9. Relation between Tg,T,, and T, on the blend compositions.

173
 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, andR. Yosomiya

molecular chains of PEEK in the blend film. Therefore, the kinetic energy
necessary to cause the transition of the molecular chains of PEEK is higher
than that for homopolymers of PEEK, which made the transition tempera-
ture of the blend films shift to a higher temperature side.

3.3 Peculiar Behavior of Blends Containing more than 90% of PEEK

The molecular aggregation of the blend films containing down to 80% of

PEEK is crystalline. Based on the X-ray diffraction patterns, the crystals in
the films are analogous to that of PEEK. However, this is not true for the
molecular aggregation of the blend films containing more than 90% of
PEEK. A blend with a PEEK content of 90% was formed into film at 300 "C
and was analyzed by X-ray diffraction as shown in Fig. 10. The comparison

28 (degs)
Fig. 10. X-ray diffraction patterns of the blend films containing 90% of PEEK.

with the results in Fig. 3 clearly shows that new diffraction peaks of high
intensity appear at 20 of 38.5" and 55.6", in addition to the diffraction
peaks at 20 of 18.5", 20.4", 22.4" and 28.3" which correspond to those of
PEEK. This suggests that a new order structure was formed in the molecular
aggregation of the blend film, in addition to the crystalline structure of
PEEK.

174
 Molecular Aggregation of PEEK with PES Blends

For examination of a new order structure which might be produced, the

blend films were annealed at 360°C and immediately put into a mixture of
water and ice for quenching. The quenched film and the quenched films
further annealed at 180°C and 250°C for 2 h were subjected to X-ray
diffraction. For the quenched film, all the diffraction peaks attributed to
crystals of PEEK disappeared to present broad halos instead, but the sharp
peaks at 28 of 38.5" and 55.6" remained unchanged as shown in Fig. 11.
For the film annealed at 180 "C, the diffraction peaks were hardly changed.
However, for the film annealed at 250"C, the diffraction peaks which
seemed to be caused by the crystals of PEEK were presented. In this case, the
diffraction peaks at 28 of 38.5" and 55.6" remained unchanged.

I I I I I I
10 20 30 40 50 60
26 (degs)

Fig. 1 1 . X-ray diffraction patterns of the quenched film and the quenched films
further annealed at 180"C, 250°C for 2 h, (a) annealed at 25OoC, (b) an-
nealed at 180°C, (c) quenched film.

Further, the X-ray diffraction measurements were carried out with the
blend films heated from room temperature to various temperatures as shown
in Fig. 12. The diffraction peaks caused by the crystals of PEEK were

175
 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

I I I I I 1
10 20 30 40 50 60
28 (degs)
Fig. 12. X-ray diffraction patterns of the blend films heated from room temperature
to (a) 34OoC, (b) 330°C, (c) 310"C, (d) 270"C, (e) 25°C.

presented in the temperature range of room temperature to about 310°C.

However, above 330 "Cthese diffraction peaks were changed to broad halos
because of the melting of the PEEK. On the contrary, no changes in the
diffraction peaks at 28 of 38.5" and 55.6" were found. Though the new
diffraction peaks have not completely been understood, it is suggested that
they are due to the formation of so-called mixture liquid crystal s t r ~ c t u r e ' ~
or the partial order structure by the intermolecular interactions of the blend
polymer Is, "j.

3.4 Molecular Aggregation of the Block Copolymers

The results of DSC curves for copolymers with different compositions are
shown in Fig. 13. A difference between the copolymers and blends with a

176
 Molecular Aggregation of PEEK with PES Blends

3
0
LL
t 2.0
U
Q,

I1 .o]
0.oJ

50 100 150 200 250 300 350

Temp ( " C )

Fig. 13. DSC curves of various block copolymers. PEEK/PES component ratio:
(a) 20 : 1, (b) 10 : 1, (c) 2 : 1, (d) 1 : 1 , (e) 1 : 2.

similar composition is clearly observed. The behavior of copolymers with a

greater PEEK component resembles that of PEEK itself, suggesting that the
copolymers are crystalline polymers similar to PEEK. However, all Tg's of
the copolymers shift forward to higher temperatures as compared with those
of PEEK, while the melting points of the copolymers shift to temperatures
lower than that of PEEK. When the PES component is further increased to
the component ratio PEEK/PES = 2: 1 , the Tg shifts to higher temperature
accompanied by a great change in melting behavior. As the figure shows, a
considerably broad melting zone appears at a temperature of about 200 "C
forming two peaks at 255.6"C and 288.2"C. When the component ratio
further changes to 1 : 1 and 1 :2 , the Tg shifts toward lower temperatures than
that for the ratio of 2 : 1 and the endothermic peak for the melting point
disappears, suggesting that the copolymer with this component ratio is
amorphous in its molecular aggregation. Especially, the copolymer with the
component ratio PEEK/PES 1 :2 has the Tg's of both PES and PEEK.
The plotting of these Tg and T,,, values against the compositions is shown
in Fig. 14. As can be seen from this figure, the copolymers are entirely

177
 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

350

Tm
\O \
\
0 '7
150-6 \ -300
/ \
\
A- - - A- - -
-40

100
0
PES component (%)

Fig. 14. Relation of Tg(0)

and T, ( A ) to the composition of block copolymers.

different in behavior from the PEEK-PES polyblends molded under the

same molding conditions. For copolymers, a single Tg is exhibited irrespec-
tive of their compositions, and its value rises with an increase of the PES
component and takes the maximum value at the component ratio 2: 1, but,
beyond this ratio, comes to show little change, becoming almost constant
and is accompanied by disappearance of the endothermic peak for the
melting point. Thus the difference in thermal properties between copolymers
and blends is considered to be caused by the difference in the molecular ag-
gregation due to that in the molecular structure.
In order to clarify this point, X-ray diffraction analysis was carried out;
the result is shown in Fig. 15. The copolymers with the component ratios
20: 1 and 10: 1, having PEEK as the principal component, show their major
diffraction peaks at 28 = 18.5", 20.4", 22.4" and 28.3", the same with the
values exhibited by the crystalline structure of PEEK itself; hence, the
crystallinity of these copolymers can be deduced. The values of 28 for above
diffraction peaks are approximately the same as those of PEEK itself, and
this suggests that crystalline character originates in the PEEK blocks of the
copolymer. The relative intensity of each peak, however, shows a little varia-

178
 Molecular Aggregation of PEEK with PES Blends

I I I I I I
10 20 30 40 50 60
28 (degs)
Fig. 15. X-ray diffraction patterns of the various block copolymers. PEEKIPES
component ratio: (a) 20 : I , (b) 10 : 1 , (c) 2 : I , (d) 1 : I , (e) 1 : 2.

tion; for PEEK itself, 28 = 18.5" is found to be of the highest intensity,

while for the copolymer it is at 28 = 22.4". This suggests that the crystalline
structure of the copolymer is affected by the existence of PES blocks in the
molecular chain. Further decrease in the PEEK component causes dis-
appearance of the peak near 20 = 20" and formation of a broad halo,
making possible the deduction for the existence of the PEEK blocks in the
copolymer as an amorphous state. In the diffraction patterns above,
considerably intense peaks are found at 20 = 38.5" and 55.8" beside the
principal diffraction peak for PEEK, suggesting the existence of some new
ordered structures in the molecular aggregation of these copolymers.

3.5 Effect of Annealing on the Molecular Aggregation of CopoQmers

As described above, the copolymers with lower PEEK component con-

tents did not exhibit the principal diffraction peak for PEEK but showed a

179
 Z. Wu, Y. Zheng, H. Yan, T. Nakamura, T. Nozawa, and R. Yosomiya

broad halo. Samples were subjected to annealing for 2 h each at 200"C,

250 "C and 300 "C, and to X-ray diffraction analysis; the results are shown in
Fig. 16. As can be seen from the figure, for a sample annealed at a tempera-
ture exceeding 250 "C, diffraction peaks supposedly due to crystallization of
the PEEK blocks are observed.

1 I I I I I
10 20 30 40 50 60
28 (degs)

Fig. 16. X-ray diffraction patterns of the annealed block copolymers; (a) annealed at
300°C for 2 h, (b) at 250°C for 2 h, (c) at 200°C for 2 h, (d) unannealed.

In the case of copolymers in contrast, considerably great effect of the

molecular movement of the PES blocks in the molecular chain can be
estimated. A similar tendency was found with the copolymer having a
component ratio 1 :1 . In the case of the copolymer with the component ratio
1 :2, having the least PEEK component, the diffraction peak due to crystall-
ization did not appear at all even after annealing as above. It is found, there-
fore, that the copolymer with a lesser PEEK content as above is amorphous,
not being effected by annealing.
Summarizing the experimental results of X-ray diffraction and DSC
analysis, it is clearly found that the copolymers composed of PEEK and PES
components are essentially different from the blends of the same component
ratio. Detailed discussion of the block copolymer structure and mechanical
properties will be reported elsewhere.

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180
 Molecular Aggregation of PEEK with PES Blends

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181