European Polymer Journal 36 (2000) 503±508

Miscibility and phase structure of at-polypropylene/

ethylene-block-(ethylene-co-butylene)-block-ethylene
copolymer blend
Y. Kobori, I. Akiba, S. Akiyama*, K. Ishikawa
Department of Chemical Science and Technology, Faculty of Technology, Koganei, Tokyo University of Agriculture and Technology,
Koganei, Tokyo 184-8588, Japan

Received 14 December 1998; accepted 10 March 1999

Abstract

Miscibility and phase structure in blends of atactic-polypropylene (aPP) with poly[ethylene-b-(ethylene-co-

butylene)-b-ethylene] (E-b-EB-b-E) containing di€erent butylene content in the mid-block were investigated by
di€erential scanning calorimetry (DSC), transmission electron microscopy (TEM) and ®eld emission type scanning
electron microscopy (FE-SEM). In DSC measurement, blends showed single glass transition temperature in no
relation to the blend composition and the butylene contents of mid-block in the block copolymers. On the other
hand, the melting point of PE block in the block copolymers was not varied systematically with variation of the
blend composition with no relation to the butylene content. From these results, it is assumed that aPP dissolves in
the EB block in the copolymers. In morphological observation, it was revealed that all blends have the islands±sea
structures containing PE domain. In the blends using the high butylene content copolymer, it was observed that PE
domain became smaller than that of neat block copolymer. On the other hand, in the lower butylene content
copolymer, the microphase structure was not observed but ®ne dispersed phase separated structures were observed
in the blends of aPP and the copolymer. # 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction lar weight of homopolymer, MH, and that of the corre-

sponding copolymer segment, MA. On the other hand,
There are numerous reports on miscibility and phase some studies have dealt with the blends in which
structures in homopolymer/block copolymer blends in homopolymers have distinct repeating unit with those
which systems homopolymers have the repeat unit of block copolymers (i.e. X/A-b-B system) [11±19]. In
identical with those of the segment of the copolymers this case, miscibility of homopolymer and each block
(i.e. A/A-b-B system) [1±10]. It has been well known sequence of block copolymer have signi®cant e€ects on
that various phase structures appear with variation of the phase structure of the systems. In general, the mis-
the blend composition and molecular weight of the cibility in blends strongly depends on the con®gura-
component polymers. Especially, it is well known that tional chemical structures of the components. It is
macroscopic phase separation or microscopic phase expected that various phase structures should appear
separation strongly depend on the ratio of the molecu- in the X/A-b-B blends with variation of the miscibility
between X, A and B.
Then we studied on miscibility and phase structure
* Corresponding author. Fax: +81-42-381-7979. of atactic-polypropylene (aPP)/poly[ethylene-b-(ethyl-

0014-3057/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 4 - 3 0 5 7 ( 9 9 ) 0 0 1 0 9 - 3
504 Y. Kobori et al. / European Polymer Journal 36 (2000) 503±508

Table 1
Characteristics of block copolymers

Polymer  w  10ÿ4
M End-block (wt%) Mid-block (wt%) Butylene content of the mid-block (wt%)

E-b-EB-b-E(80) 30 15 70 80
E-b-EB-b-E(40) 30 15 70 40

ene-co-butylene)-b-ethylene] (E-b-EB-b-E) blends. It tage of 175 kV. Specimens used for TEM observation
has been predicted that miscibility between aPP and were prepared by casting 0.02% solution mixing using
EB or E and EB are changed by the variation of buty- toluene and 1,2,4-trichlorobenzene (1 : 1 in volume) as
lene contents in EB blocks [20]. Therefore, in aPP/E-b- a solvent. The resulting as-cast ®lms were annealed at
EB-b-E blend, it is expected that changing the butylene 1808C for 2 h and were subsequently quenched in
contents in the EB block should make the variable liquid N2. These samples were exposed to Ruthenium
structures in this system. tetraoxide (RuO4) vapor by using a 0.05% aqueous
solution of RuO4.

2. Experimental 2.5. Field emission type scanning electron microscopy

(FE-SEM)
2.1. Materials
Scanning electron micrographs were taken with an
Polymers used in this study are atactic-polypropy- ELIONIX ERA-8000FE operated at an accelerating
lene (aPP) and poly[ethylene-b-(ethylene-co-butylene)- voltage of 5 kV. The obtained as-cast ®lms were
b-ethylene] (E-b-EB-b-E). aPP is supplied by Ciba Fine annealed at 1808C for 2 h and were subsequently
Chemicals (Bistac). E-b-EB-b-E are trial products syn- quenched in liquid N2 and then fractured. The frac-
thesized by JSR. The viscosity average molecular tured surfaces of the samples were stained by RuO4
weight of aPP is 3:0  103 . Table 1 shows molecular and then observation was carried out.
characteristics of E-b-EB-b-E(X). Here X in the par-
entheses denotes butylene contents of EB sequence in
E-b-EB-b-E.

2.2. Sample preparation

Blend samples were prepared by solution mixing.

aPP and E-b-EB-b-E(X) were weighted to desired com-
position and dissolved in toluene with 5 wt% polymer
concentration at 1108C. After the polymers were dis-
solved perfectly in toluene, the solvent was removed at
room temperature for 24 h. The resulting samples were
dried under reduced pressure at 808C for 1 week and
further at 1808C for 2 h to ensure any strain or ther-
mal history.

2.3. Di€erential scanning calorimetry (DSC)

In DSC measurements, a DuPont 910 DSC was

used at a heating rate of 10 8C/min. Blend samples
were annealed for 2 h at 1808C and then quenched in
liquid N2 before measurements.

2.4. Transmission electron microscopy (TEM)

Transmission electron micrographs were taken with Fig. 1. DSC thermograms of aPP/E-b-EB-b-E(80) blends
a HITACHI H-700H operated at an accelerating vol- quenched in liquid N2 after annealing at 1808C for 2 h.
 Y. Kobori et al. / European Polymer Journal 36 (2000) 503±508 505

Fig. 4. Transmission electron micrograph of E-b-EB-b-E(80).

and 2, respectively. For each blend, one glass tran-

sition and one endothermic peak indicating melting of
Fig. 2. DSC thermograms of aPP/E-b-EB-b-E(40) blends
quenched in liquid N2 after annealing at 1808C for 2 h.
PE were detected. The single Tg between the Tg of neat
aPP and that of EB (from ÿ65 to ÿ288C) suggest mis-
cible state of aPP/E-b-EB-b-E blend in no relation to
3. Results and discussion the butylene content in the EB block and the blend
composition. The glass transition temperatures for
3.1. Miscibility of aPP/E-b-EB-b-E blends aPP/E-b-EB-b-E(X) blends are plotted as a function of
the weight fraction of aPP in the aPP/EB in Fig. 3.
DSC thermograms for aPP/E-b-EB-b-E(80) blends The solid lines in Fig. 3 were calculated by the
and aPP/E-b-EB-b-E(40) blends are shown in Figs. 1 Gordon±Taylor equation,
ÿ

Tg1 ‡ KTg2 ÿ Tg1 W2
Tg,blend ˆ 1†
1 ‡ K ÿ 1 †W 2

where Tg1 and Tg2 are the Tg values of the EB block

of E-b-EB-b-E(X) and aPP, respectively, W2 is the
weight fraction of aPP and K is the ratio of the di€er-
ence of thermal expansion coecients between the
amorphous and glassy states for aPP and EB. We
chose K as a ®tting parameter to achieve good agree-
ment between experimental data and calculated values.
The systematic compositional change in the single Tg is
observed for aPP/E-b-EB-b-E blends, suggesting the
presence of a phase composed of EB block sequence
and aPP chains. In addition, the depression of melting
points of PE block is not observed. Hence, it is
suggested that aPP or EB is immiscible with PE in no
relation to the butylene content and the blend compo-
sitions. Therefore, it can be presumed that aPP is mis-
cible with EB, and PE block is phase separated in all
blends.
Fig. 3. Composition depnedence of Tg of aPP/E-b-EB-b-E
blends anealed at 1808C. Solid lines were calculated following 3.2. Phase structure of aPP/E-b-EB-b-E blends
Gordon±Taylor equation to ®t experimental data. (w) E-b-
EB-b-E(80) k ˆ 0:95, (Q) E-b-EB-b-E(40) k ˆ 0:42. TEM micrograph for the neat E-b-EB-b-E(80) is
506 Y. Kobori et al. / European Polymer Journal 36 (2000) 503±508

Fig. 5. Transmission electron micrograph of aPP/E-b-EB-b-

E(40) =50/50 (w/w) blends.

shown in Fig. 4. Small domains of about 10 nm diam-

eter were observed. This structure is considered the
microphase structure in which domains were formed
by PE block of E-b-EB-b-E. This assumption is con-
sistent with the ratio of ethylene/EB in E-b-EB-b-E as
listed in Table 1. In E-b-EB-b-E, it is generally con-
sidered that the phase of EB block was stained by
RuO4. However it is assumed that double bonds
remained in both PE and EB block and PE phase has
higher density of electron than EB phase, because of
the crystallizing of PE. Therefore, we regarded the
domains in the Fig. 4 as the phase of PE block of E-b- Fig. 6. Field emission type scanning electron micrographs of
E-b-EB-b-E: (a) E-b-EB-b-E(80); (b) E-b-EB-b-E(40).
EB-b-E. However, such phase separated structures
could not be observed in the E-b-EB-b-E(40) by TEM.
On the contrary, in TEM observation for aPP/E-b-EB- sample preparations. Samples for TEM observations
b-E(40) blends, microscopic phase separated structure were prepared by solution casting using selectively
could be observed. The typical TEM micrographs for good solvent for EB block than for PE block. And
the aPP/E-b-EB-b-E(40) = 50/50 (w/w) blends are then the EB block and PE block are segregated
shown in Fig. 5. In these photographs, the domains of strongly. Comparing the FE-SEM micrograph of E-b-
about 10 nm diameters are observed. Unfortunately in EB-b-E(40) with that of E-b-EB-b-E(80), E-b-EB-b-
both these photographs, the structures could not be E(40) does not show microscopic phase separated
observed clearly. Therefore, we operated observation structures which are spherical domains observed in E-
by FE-SEM to obtain the more precise structures. b-EB-b-E(80). This distinction is due to the di€erence
The FE-SEM micrographs for the E-b-EB-b-E(80) of the butylene content in the EB block. The PE block
and E-b-EB-b-E(40) are shown in Fig. 6. The spherical is more attractive with the EB block in E-b-EB-b-
domains were observed in E-b-EB-b-E(80) in agree- E(40) than that of E-b-EB-b-E(80), because chemical
ment with the morphology obtained by TEM. We note structure, i.e. butylene content in EB block of E-b-EB-
that the photographs of FE-SEM images are corre- b-E(40) is more similar to that of PE block than that
sponding to negative image of TEM since FE-SEM of E-b-EB-b-E(80). The FE-SEM micrographs of aPP/
detects the second electrons as opposed to transmitted E-b-EB-b-E(80) blends are shown in Fig. 7. It is
electrons in TEM. Comparing the micrograph of TEM observed that the domains formed by PE block became
with that of FE-SEM, the domain size of FE-SEM smaller by adding the aPP. This is explained that inter-
micrographs is larger than those of TEM. This di€er- facial mean curvature which is the area per unit junc-
ence could be attributed to the di€erence of their tion of a block copolymer chain is increased due to
 Y. Kobori et al. / European Polymer Journal 36 (2000) 503±508 507

Fig. 7. Field emission type scanning electron micrographs of

aPP/E-b-EB-b-E(80) blends: (a) 20/80 blend; (b) 40/60 blend. Fig. 8. Field emission type scanning electron micrographs of
aPP/E-b-EB-b-E(40) blends: (a) 20/80 blend; (b) 60/40 blend.

blending, because the volume of the EB domains are increase with adding aPP. Then we consider that EB
increased by mixing with aPP. and PE block of the copolymer made segregation more
FE-SEM micrographs of aPP/E-b-EB-b-E(40) blends strongly by mixing aPP, and it results in the phase sep-
are shown in Fig. 8. In these photographs of the arated structure.
blends, phase separated structure was observed clearly
in spite of E-b-EB-b-E(40) in which phase separated
structure is not observed. This phase separated struc- 4. Conclusion
ture is formed due to mixing E-b-EB-b-E(40) with aPP
and by comparing Fig. 8(a) with (b) it is observed that aPP was miscible with EB block of E-b-EB-b-E(X)
the numbers of domains are decreasing with increasing in no relation to the blend composition and the buty-
aPP. The reason is that the segregation force of the PE lene content of the EB block. TEM and FE-SEM ob-
block and the EB block changed into a more strong servation reveal that E-b-EB-b-E(80) form the
segregation force by adding aPP. Therefore, it is microdomain structure in which PE block forms the
assumed that the PE phase is strongly segregated in spherical domains. By blending aPP, the domain
aPP/E-b-EB-b-E(40) blend and the domains of PE became smaller suggesting aPP was miscible with the
block were formed. However, also it can be considered EB block of the copolymer. On the other hand, in
that the domains are possible to be formed by aPP TEM and FE-SEM observation, blending E-b-EB-b-
because it can be pointed out that aPP and EB block E(40) with aPP induces formation of microphase struc-
of E-b-EB-b-E(40) are immiscible. The broad glass ture, despite of the microphase structure is not formed
transition of the blends, as shown in Fig. 2, can in the neat E-b-EB-b-E(40) on account of the segre-
suggest double Tg. But in such case, domains should gation between the EB block and the PE block being
508 Y. Kobori et al. / European Polymer Journal 36 (2000) 503±508

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