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Calorimetric investigations of glass transitions and phase systems of poly(arylate-arylenesulfone oxide) block copolymers
391
Thermochimica Acta, 85 (1985) Elsevier Science
391-394 B.V., Amsterdam
Publishers
CALORIMETRIC
INVESTIGATIONS
-Printed
in The Netherlands
OF GLASS TRANSITIONS
POLY(ARYLATE-ARYLENESULFONE
AND PHASE SYSTEMS
OF
OXIDE) BLOCK COPOLYMERS
P. J#ASKEL#INENl, I.P. STOROZHUK'and P.M. WALETSKI13 1 University of Helsinki, Department of Wood and Polymer Chemistry, Meritullinkatu 1 A, SF-00170, Helsinki 17, (Finland) 2 Moscow D.I. Mendeleyev Chemical-Technological Institute, Moscow,(USSR) 3 Institute of Organo-Element Compounds, USSR Academy of Sciences, Moscow,
(USSR)
ABSTRACT Statistical poly(arylate-arylenesulfone oxide) block copolymers derived from phenolphtalein, terephthaloyl chloride and polyarylene sulfone oxide with degree of polymerisation, DP:lO, DP:30 and DP:lOO were investigated by DSC-2. The investigations were carried out on the systems containing from 0.5% to 90% arylenesulfone oxide. The aim of this work is to study the influence of degree of polymerisation of arylenesulfone oxide on the phase behaviour of the block copolymer. The results indicate that in the case of DP:lO there was a single phase system with a single glass transition temperature, which follows the commonly used Tg-composition relations. For all compositions the block copolymers with DP:30 and DP:lOO showed a multiphase behaviour with two glass transition regions. INTRODUCTION There types
is no doubt that the connection
into block copolymers
method
of obtaining
of polymeric
segments
of different
may be at the present time the most promising
polymers
with unusual
and valuable
combinations
of
properties. One of the characteristic microphase
separation
multiphase
systems
features
of block copolymers
is the tendency
to occur in the solid state. The morphology
influences
their behaviour
for
of such
and can be controlled
by altering
the length of blocks and their ratio. Thermostable
block copolymers
with high glass transition oxide block copolymers, complex (ref.11.
preparation,
based on structurally
temperatures
(q-2)-(PASO),
0040~6031/85/$03.30
in the system
investigations
scanning
calorimetry
(q-2)-(PASO).
0 Elsevier Science
similar
homopolymers
polyarylate-arylenesulfone
have for some time been the subject of
process and property
In this work, differential
phase behaviour
including,
Publishers
B.V.
by V.V.Korshak
et al.
was used to study
392
EXPERIMENTAL Materials.
Series of statistical
phenolphthalein,
terephthaloyl
degree of polymerisation, and #-2-100-x, densation
Differential
connected
oxide
Scanning
with an Apple
Calorimetry
Measurements.
polycon-
In all series the content range of 0.5 to 90.
The glass transition using a Perkin Elmer DSC-2
with metal standards
measurements
of the enthalpy
transition
behaviour
80 K/min over the temperature
at 10 K/min
a 29.540 mg saphire disc was
scale. All measurements
rate 10 K/min over the temperature
The measurements
#-2-30-x
II microcomputer.
rate. In the heat capacity
a more repeatable
(ref.1).
from
sulfone oxide with
by a low temperature
were measured
derived
(Series 0-2-10-x,
(x) varied over the weight-%
scale was calibrated
used for the calibration heating
were prepared
Tg and heat capacities
The temperature heating
and polyarylene
in Moscow by I.P.Storozhuk
of polyarylenesulfone
temperatures
chloride
DP:lO, TIP:30 and DP:lOO
respectively)
method
((I-2)-(PASO) block copolymers
were made at a
range 323-623 K. In order to obtain
all samples were first scanned
at a rate
ranges 323-623 K and 623-323 K.
were carried
out on 10 mg (dia 4,5 mm) pellets
formed
under pressure.
RESULTS AND DISCUSSION Series
9-2-10-x
exhibit
a single, composition
DSC as has been shown by the methods depolarisation mechanical
currents,
electroconductivity
investigations
The experimental composition
dependence
relations
dependent
glass transition
of dipole polarisation,
and in the results
of thermo-
(ref.2). of Tg on composition
including
Fox (11, Gordon
follows
a number of Tg-
(2) and Fried
(3) (ref.3,4,5).
(l/Tg) = (wl/Tgl) + (w2 /Tg2)
(1)
Tg = (wlTgl + w2Tg2k) / (w, + k w,1
(21
Ln(Tg/Tgl)
by
thermostimulated
= w21n(Tg2/Tgll
/[[Wt(Tg2/Tgll
+
w2]
(3)
393 is the glass transition
T
transition
temperatures
k is an
The values calculated
temperatures,
of the system, Tgl and Tg2 glass
of homopolymers
fractions,respectively;
experimentally.
temperature
accordingly
Calculated
and WI and w2 the weight
empirical
parameter,
are compared
in table
values are satisfactorily
particularly
Tg(2), which
here k=AcpZ/ncpl=2,4095
indicates
1 with the Tg found
close to the experimental
a total phase mixing
(see Fig. la).
TABLE
1
Experimental
and calculated
glass transition
temperatures
Experimental
x (X)
Calculated T (1)
T (K) 0 (O-2)
of series f-2-10-x
T (2)
T (3)
591
5
524
580
573
579
10
512
570
557
567
20
505
550
531
545
50
478
499
478
492
70
458
469
455
465
90
445
443
438
441
100 (PASO)
431
Tg(l), Tg(2) and Tg(3) calculated
Series &2-30-x behaviour
Glass transitions complicates
of specific
in series 0-2-30-x,
then on, it remains slightly;
(series #-2-100-x) with
which
it impractical
the Tg of (d-2)
practically
this is evidence
unchanged,
of an incomplete
Tg of the (j-2) phase also decreases
10% content
to that of the initial homopolymer, at any composition as a separate
phases.
intervals
whereas phase
(see Fig.lb).
a minimum
temperatures
temperature
heat jumps and makes
of (PASO) blocks,
drastically,
the Tg of (PASO) increases
reaching
a multiphase
the degree of phase mixing.
Up to 10% content
separation
(l)(2) and (3).
Tgs.
occur within wide overlapping
the analyzing
phase decreases
With 0P:lOO
with equations
and fi-2-100-x showed for all compositions
with two distinct
to calculate
in accordance
whereas
the
PASO
(see Fig. 1~). This indicates
phase. Nevertheless of the (t-2) confirms
In all series
drastically
of (PASO) blocks and then increases
the decrease
phase remains
the isolation
again
unchanged
of (t-2) blocks
in the glass transition
the occurence
of interaction
(PASO) acts as a plasticizer
between
on the (f-2) matrix.
the
Fig. 1. Dependence of glass transition temperatures for ( -2)-(PASO) block copolymers on the PASO content. (a) DP of PASO blocks is f0; experimental values (solid line) and teoretical values calculated according to eq. (2) (broken line). (b) DP of PASO blocks is 30. (c) DP of PASO blocks is 100.
REFERENCES V.V. Korshak, P.M. Waletskii and I.P. Storozhuk, Makromol. Chem., Suppl. 6 (1984) 55-75. V.S. Voichev I.P. Storozhuk, V.A. Bologlazov, V.S. Yeryomin, P.M. Waletskii, S.V. Vinogradova and V.V. Korshak, Vysokomol.soyed. A. 26 N:o 1 (1984) 124. T.G. Fox, Bull. Am. Phys. Sot., 1 (1956) 123. J.M. Gordon. G.B. Rouse, J.H. Gibbs and M. Rise, J. Chem. Phys. 66 (1977) 4971. J.R. Fried, S.-Y. Lai, L.W. Kleiner and M.E. Wheeler, J. Appl. Polym. Sci. 27 (1982) 2869.
Thermochimica Acta, 85 (1985) Elsevier Science
391-394 B.V., Amsterdam
Publishers
CALORIMETRIC
INVESTIGATIONS
-Printed
in The Netherlands
OF GLASS TRANSITIONS
POLY(ARYLATE-ARYLENESULFONE
AND PHASE SYSTEMS
OF
OXIDE) BLOCK COPOLYMERS
P. J#ASKEL#INENl, I.P. STOROZHUK'and P.M. WALETSKI13 1 University of Helsinki, Department of Wood and Polymer Chemistry, Meritullinkatu 1 A, SF-00170, Helsinki 17, (Finland) 2 Moscow D.I. Mendeleyev Chemical-Technological Institute, Moscow,(USSR) 3 Institute of Organo-Element Compounds, USSR Academy of Sciences, Moscow,
(USSR)
ABSTRACT Statistical poly(arylate-arylenesulfone oxide) block copolymers derived from phenolphtalein, terephthaloyl chloride and polyarylene sulfone oxide with degree of polymerisation, DP:lO, DP:30 and DP:lOO were investigated by DSC-2. The investigations were carried out on the systems containing from 0.5% to 90% arylenesulfone oxide. The aim of this work is to study the influence of degree of polymerisation of arylenesulfone oxide on the phase behaviour of the block copolymer. The results indicate that in the case of DP:lO there was a single phase system with a single glass transition temperature, which follows the commonly used Tg-composition relations. For all compositions the block copolymers with DP:30 and DP:lOO showed a multiphase behaviour with two glass transition regions. INTRODUCTION There types
is no doubt that the connection
into block copolymers
method
of obtaining
of polymeric
segments
of different
may be at the present time the most promising
polymers
with unusual
and valuable
combinations
of
properties. One of the characteristic microphase
separation
multiphase
systems
features
of block copolymers
is the tendency
to occur in the solid state. The morphology
influences
their behaviour
for
of such
and can be controlled
by altering
the length of blocks and their ratio. Thermostable
block copolymers
with high glass transition oxide block copolymers, complex (ref.11.
preparation,
based on structurally
temperatures
(q-2)-(PASO),
0040~6031/85/$03.30
in the system
investigations
scanning
calorimetry
(q-2)-(PASO).
0 Elsevier Science
similar
homopolymers
polyarylate-arylenesulfone
have for some time been the subject of
process and property
In this work, differential
phase behaviour
including,
Publishers
B.V.
by V.V.Korshak
et al.
was used to study
392
EXPERIMENTAL Materials.
Series of statistical
phenolphthalein,
terephthaloyl
degree of polymerisation, and #-2-100-x, densation
Differential
connected
oxide
Scanning
with an Apple
Calorimetry
Measurements.
polycon-
In all series the content range of 0.5 to 90.
The glass transition using a Perkin Elmer DSC-2
with metal standards
measurements
of the enthalpy
transition
behaviour
80 K/min over the temperature
at 10 K/min
a 29.540 mg saphire disc was
scale. All measurements
rate 10 K/min over the temperature
The measurements
#-2-30-x
II microcomputer.
rate. In the heat capacity
a more repeatable
(ref.1).
from
sulfone oxide with
by a low temperature
were measured
derived
(Series 0-2-10-x,
(x) varied over the weight-%
scale was calibrated
used for the calibration heating
were prepared
Tg and heat capacities
The temperature heating
and polyarylene
in Moscow by I.P.Storozhuk
of polyarylenesulfone
temperatures
chloride
DP:lO, TIP:30 and DP:lOO
respectively)
method
((I-2)-(PASO) block copolymers
were made at a
range 323-623 K. In order to obtain
all samples were first scanned
at a rate
ranges 323-623 K and 623-323 K.
were carried
out on 10 mg (dia 4,5 mm) pellets
formed
under pressure.
RESULTS AND DISCUSSION Series
9-2-10-x
exhibit
a single, composition
DSC as has been shown by the methods depolarisation mechanical
currents,
electroconductivity
investigations
The experimental composition
dependence
relations
dependent
glass transition
of dipole polarisation,
and in the results
of thermo-
(ref.2). of Tg on composition
including
Fox (11, Gordon
follows
a number of Tg-
(2) and Fried
(3) (ref.3,4,5).
(l/Tg) = (wl/Tgl) + (w2 /Tg2)
(1)
Tg = (wlTgl + w2Tg2k) / (w, + k w,1
(21
Ln(Tg/Tgl)
by
thermostimulated
= w21n(Tg2/Tgll
/[[Wt(Tg2/Tgll
+
w2]
(3)
393 is the glass transition
T
transition
temperatures
k is an
The values calculated
temperatures,
of the system, Tgl and Tg2 glass
of homopolymers
fractions,respectively;
experimentally.
temperature
accordingly
Calculated
and WI and w2 the weight
empirical
parameter,
are compared
in table
values are satisfactorily
particularly
Tg(2), which
here k=AcpZ/ncpl=2,4095
indicates
1 with the Tg found
close to the experimental
a total phase mixing
(see Fig. la).
TABLE
1
Experimental
and calculated
glass transition
temperatures
Experimental
x (X)
Calculated T (1)
T (K) 0 (O-2)
of series f-2-10-x
T (2)
T (3)
591
5
524
580
573
579
10
512
570
557
567
20
505
550
531
545
50
478
499
478
492
70
458
469
455
465
90
445
443
438
441
100 (PASO)
431
Tg(l), Tg(2) and Tg(3) calculated
Series &2-30-x behaviour
Glass transitions complicates
of specific
in series 0-2-30-x,
then on, it remains slightly;
(series #-2-100-x) with
which
it impractical
the Tg of (d-2)
practically
this is evidence
unchanged,
of an incomplete
Tg of the (j-2) phase also decreases
10% content
to that of the initial homopolymer, at any composition as a separate
phases.
intervals
whereas phase
(see Fig.lb).
a minimum
temperatures
temperature
heat jumps and makes
of (PASO) blocks,
drastically,
the Tg of (PASO) increases
reaching
a multiphase
the degree of phase mixing.
Up to 10% content
separation
(l)(2) and (3).
Tgs.
occur within wide overlapping
the analyzing
phase decreases
With 0P:lOO
with equations
and fi-2-100-x showed for all compositions
with two distinct
to calculate
in accordance
whereas
the
PASO
(see Fig. 1~). This indicates
phase. Nevertheless of the (t-2) confirms
In all series
drastically
of (PASO) blocks and then increases
the decrease
phase remains
the isolation
again
unchanged
of (t-2) blocks
in the glass transition
the occurence
of interaction
(PASO) acts as a plasticizer
between
on the (f-2) matrix.
the
Fig. 1. Dependence of glass transition temperatures for ( -2)-(PASO) block copolymers on the PASO content. (a) DP of PASO blocks is f0; experimental values (solid line) and teoretical values calculated according to eq. (2) (broken line). (b) DP of PASO blocks is 30. (c) DP of PASO blocks is 100.
REFERENCES V.V. Korshak, P.M. Waletskii and I.P. Storozhuk, Makromol. Chem., Suppl. 6 (1984) 55-75. V.S. Voichev I.P. Storozhuk, V.A. Bologlazov, V.S. Yeryomin, P.M. Waletskii, S.V. Vinogradova and V.V. Korshak, Vysokomol.soyed. A. 26 N:o 1 (1984) 124. T.G. Fox, Bull. Am. Phys. Sot., 1 (1956) 123. J.M. Gordon. G.B. Rouse, J.H. Gibbs and M. Rise, J. Chem. Phys. 66 (1977) 4971. J.R. Fried, S.-Y. Lai, L.W. Kleiner and M.E. Wheeler, J. Appl. Polym. Sci. 27 (1982) 2869.