Quantitative DSC Evaluation of Phase Segregation

Rate in Linear Segmented Polyurethanes and

Polyurethaneureas
YVES CAMBERLIN and JEAN PIERRE PASCAULT, Laboratoire des
MatBriaux MacromolBculaires-ERA C N R S 745, Institut National des
Sciences Appliqu&es,20, Avenue Albert Einstein, 69621 Villeurbanne,
France

Synopsis
Linearly segmented polyurethanes and polyurethaneureas are known to be phase separated; one
phase is the soft phase, the other, the hard domain. Quantitative evaluation of the degree of phase
separation was obtained by DSC. An estimation of the dispersed soft segments outside the soft phase
can be made by ACp measurements and the increase in glass transition (T,)can be attributed to
the presence of hard blocks in the soft phase. The segregation rate depends on the nature of the
soft segments which decrease from hydrogenated polybutadiene to polybutadiene to polyether. I t
also depends on the nature of the chain extender from aliphatic to aromatic diol and from aliphatic
to aromatic diamine. The presence of soft segments in hard domains can be related to the ther-
moplastic behavior of the polyurethanes and polyurethaneureas.

INTRODUCTION
Phase segregation of linear block polyurethanes or polyurethaneureas due to
thermodynamic incompatibility between the hard and soft segments is a well-
known phenomenon.' The hard segments are often composed of an aromatic
diisocyanate reacted with a diol or a diamine chain extender; the soft segments
are a low molecular weight a - w hydroxy-terminated polymer.
The phenomenon of phase separation has been proved by electron microsco-
py2y3and small-angle x-ray scattering4 and by the observation of elastomeric
proper tie^.^,^,^ Recently, a new criterion of phase separation of segmented
polyurethaneureas was reported5 by comparing the relative crystallinity of their
soft segments. In fact, this method is limited to crystalline soft segments.
Although the mechanical properties of block polyurethanes seem to be strongly
influenced by the phase segregation rate,5,8-10the quality of the phase separation
has never been studied quantitatively.
In this work we tried to determine quantitatively the segregation rate by DSC.
The heat capacity change AC, during Tgof the soft segment in polyurethanes
or polyurethaneureas was measured and compared with the AC, of the pure soft
segment by which the quantity of soft phase contained in the hard domain was
deduced. This determination was made possible by the fact that during the Tg
of hard blocks (in polyurethanes or alonel1J2)the heat capacity changes were
small and almost undetectable by DSC. Consequently, the presence of hard
blocks as impurities in the soft phase do not affect its heat-capacity determi-
nation. A similar treatment was devised by Brunette et al.7 for linear segmented

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 21,415-423 (1983)

0 1983 John Wiley & Sons, Inc. CCC 0360-6376/83/020415-09$01.90
416 CAMBERLIN AND PASCAULT

polyurethanes with butadiene soft segments and with different toluene diiso-
cyanate-butanediol hard-segment weights (18-55%).
Polyurethanes and polyurethaneureas (PUR) with hard blocks derived from
diphenyl methane diisocyanate (MDI) and alkane diol, alkane diamine, aromatic
diol, and aromatic diamine were studied. Three soft blocks with varying solubility
parameters but similar molecular weights % and functionalities were also
incorporated: polybutadiene, hydrogenated polybutadiene, and polyoxyte-
tramethylene. The mechanical and thermal properties of these linear PUR have
recently been studiedg and the results interpreted by phase segregation mea-
surements.

EXPERIMENTAL

Synthesis
For hard blocks with low dispersity in length, the polyurethanes or polyu-
rethaneureas were prepared in two steps. The characteristics of the three a--w
hydroxy terminated oligomers used in the synthesis are listed in Table I; M , was
determined by cryometry and z, by lH NMR.14
First, taking into account the oligomer’s true function, we carried out the re-
action between 1 mol of oligomer and 3 mol of MDI in toluene under argon at
80°C for 2 h before adding 2 mol of chain extender and then for 48 h. Hard- and
soft-block distribution was thus the same and independent of the different ex-
tender reactivities.13 The product was precipitated in methanol and dried under
vacuum of 60°C for 24 h, molded at a temperature according to the nature of the
chain extender, ranging from 100 to 2OO0C, and stored a t room temperature for
more tkgm two weeks before measurement. The segmental mobility of polymers
was sufficiently important to assume that the phase equilibrium was
reached.16

DSC Measurements
A Mettler TA 3000 microcalorimeterwas used for heat-capacity measurements
with heating rates of 5-7.5 K/min. When greater heating rates were used the
thermal equilibrium of cells was not obtained; consequently C, measurements
could not be made.
The amorphous soft-phase cooling rate of 10 K/min was used from room
temperature to -170°C with a sample weight of about 15 mg. In crystalline soft
segments (exclusively polytetramethylene oxide) cells are quenched a t 40°C to
liquid nitrogen to obtain fully amorphous soft segments for AC, measurements.
When pure PTMO is quenched the sample weight must be inferior to 5 mg to
eliminate crystallinity. The fully amorphous structure was verified by measuring
the recrystallization enthalpy.
Scanning from -170°C provides excellent base lines for AC, determination.
Five to ten runs were made for each product. The difference AC, between each
run was not more than f5%. Therefore, the average AC, can be estimated
within f 2 % .
 DSC EVALUATION OF PHASE SEGREGATION RATE 417

TABLE I
Characteristics of CY-wHydroxylated Oligomers Used for Polyurethanes

- - 6
M" F, T&? call/*
Oligomers (Y-whydroxylated (f5%) MJM, (.t5%) ("C) cm-3/2 mol-'
Hydrogenated polybutadiene 2280 1.3 1.8 -45.7 7.8
(initially 90% 1,2) or
copolymer ethylene-butene 1
Polybutadiene 90% (1-2) 2220 1.3 2.1 -22.5 8.2
Poly(tetramethy1ene oxide) 2400 2.1 1.8 -92.8 8.6

RESULTS AND DISCUSSION

Heat Capacities Measurements for Pure Soft Phases

First, the variations in heat capacity at Tg for the pure soft phase were mea-
sured on a--w hydroxylated oligomers (Table I). The influence of chain-end
concentration on AC, seems negligible on the contrary to the Tg. Indeed the
AC, of polybutadienes with different molecular weights of 1000-4000 did not
show significant variation. Therefore, the AC, values per gram of soft segments
in oligomers and in ideally separated block polyurethanes or polyurethaneureas
must be similarly estimated.
Consequently, the theoretical AC,, per gram of soft segments at Tgin totally
separated PUR systems can be estimated by comparing them with oligomers.
If AC,, (per gram of soft segments) is the value of a real PUR, the ratio

0 1
I
/I --

0
I L

0 I
,
,
I

I I I
- id0 - 50 0 50 T'c
Fig. 1. Temperature dependence of the heat capacity in initial prepolymers; polybutadiene (1,2)
(2), hydrogenated polybutadiene (l),and poly(tetramethy1ene oxide) (3).
418 CAMBERLIN AND PASCAULT

TABLE I1
ACp Values of Pure Soft Segments and Soft Phase in Polyurethane
Soft segments
ACpl (f2%)* AC,z ( f 2 % ) b segregation ratec
Type of soft segments (JkK) (JkK) (%)
Hydrogenated (1-2) Polybutadiene 0.430 0.356 83
(1-2) Polybutadiene 0.566 0.426 15
Poly(tetramethy1ene oxide) 0.815 0.520 64
a ACpl for initial oligomers.
ACp21gram of soft segment in MDI-butanediol polyurethanes.
ACpplACpi

ACp2/ACp1can be assimilated by the soft-phase segregation rate. (ACPl-ACp2)

will correspond to the quantity of soft segments outside the soft phase; that is,
in the hard domain or in an hypothetical interphase. These dispersed soft
segments do not relax a t the same temperature as the continuous soft phase. It
is clear that this method can be applied only to block copolymers in which phase
separation really occurs.
Figure 1 is a thermogram of oligomers. It should be noted in the case of
polytetramethylene oxide that the AHH,of crystallization is equal to AHF of fu-
sion (91J/g).
The average AC, values are listed in Table 11.

Heat Capacities of Polyurethanes from MDI, Butanediol (BD), and

Different Soft Blocks
Figure 2 shows the dependence of AC, per gram of polyurethane in polymers
that contain the same hard blocks (MDI-BD) and three different soft segments.
In the crystalline soft phase AHc 2 AHF indicates a fully amorphous structure
of the quenched product.
The average values of AC, listed in Table I1 were calculated per gram of soft
segment by taking into account the quantity of oligomer introduced into the
formulation. We can see in Table I1 that AC, in the soft phase of polyurethane
is lower than expected in the pure soft phase.
This indicates clearly that a percentage of soft segment is derived from the
soft phase mixed with hard blocks in the hard domain.
The lower the value of A6 = (&hard segments - segments), the lower is the
segregation rate (see Table I). This is the PTMO soft phase taking for
6hard segment the value 11 cm-3/2 mol-l. The highest phase segregation
(83%)was obtained for the polyolefin-urethane system which showed the greatest
incompatibility.
The influence of block miscibility on the morphology of linear polyurethanes
is revealed by the AC, measurements. The rate of separation is a function of
the difference A6 between solubility parameters. However, the well-known
uncertainty surrounding the 6 values does not allow more than a qualitative
approach.
These results also explain the mechanical properties of polyurethane?-12 We
observed the hard domain plasticity as a function of the type of soft segments.
 DSC EVALUATION OF PHASE SEGREGATION RATE 419

Fig. 2. Temperature dependence of the heat capacity in polyurethanes based on MDI, butane
diol, and hydrogenated polybutadiene (I), (1-2) polybutadiene (21, and poly(tetramethy1eneoxide)
(3).

The flow temperature of hard domains from MDI and BD was about 1'20°C in
polyolefine, 100°C in polybutadiene, and only 80°C in the polytetramethylene
oxide soft phase. It is now clear that the differences derive from the quantities
of soft segments present as impurities in hard domains which reduce the number
and the strength of interactions.

Heat Capacities of Polyurethanes and Polyurethaneureas from

Hydrogenated Polybutadiene, MDI, and Different Chain Extenders
In the second step of this work polymers were synthesized from 1 mol of hy-
drogenated polybutadiene, 3 mol of MDI, and 2 mol of the following chain ex-
tenders:
- butanediol (BD) HOfCH2NH
- hydroquinone di(0-hydroxydthyl) (HQEE)

HOfCHh-0-@OICH2hOOH

- diaminobutane (BDA) NH2fCHz%NHz

- 4,4'methylene bis( 2 chloroaniline) (Moca)

Cl k1
The weight fraction of hard blocks for these PUR is in the range of 29-35%;
420 CAMBERLIN AND PASCAULT

TABLE I11
AC,, Values of Hydrogenated Polybutadiene Soft Phase in Polyurethanes Based on MDI and
Different Chain Extenders
Soft-segment
ACp2 ( f 2 % ) segregation rate
Chain extender (Jig K) (%I
Butanediol (1-4) 0.356 83
HQEE 0.388 90.5
Butane diamine (1-4) 0.389 90.5
MOCA 0.400 93

the lower value corresponds to butanediol, the higher, to the aromatic diamine
Moca.
The ACp per gram of soft phase are listed in Table 111. It can be seen that the
segregation rate is lower for butanediol chain extender (83%). A higher value
is noted for aromatic diol HQEE and diamino butane (90,5%), whereas aromatic
diamine provides the highest segregation rate (93%).
Therefore, it appears that the segregation rate increases with the interactions
between hard segments: from aliphatic to aromatic diol and from aliphatic to
aromatic diamine. The increase in segregation rate from butane diol to butane
diamine can easily be explained by the three-dimensional structure of hydrogen
bonding in p01yurethaneureas.l~
It can also be noted that the better high-temperature behavior of linear PUR
synthesized from aromatic or diamine chain extender is not only due to higher
interactions strength, but also to a higher segregation rate.g

Thermal Transitions Behavior

If some soft segments are dispersed in hard domains, the opposite is also
possible, that is, hard blocks in soft phase. In this case the Tgof the soft phase
in PUR will be different and will logically increase with the proportion of hard
blocks.
The average glass transition temperatures of 5-10 runs are given in Table IV.
We note that the difference between the glass transition temperature of the pure
soft segments and the soft phase in polyurethanes or polyurethaneureas increases

TABLE IV
~
Glass Transition TemDeratures of the Soft Phase in Different Polvurethanes
~ ~

PUR Tg f0.5OC ATa

Hydrogenated polybutadiene
MDI-BD -35.2 10.5
MDI-HQEE -37.9 7.8
MDI-BDA -38.2 7.5
MDI-MOCA -38.8 6.9
Polybutadiene
MDI-BD -8.9 13.6
Poly(tetramethy1ene oxide)
MDI-BD -73.8 19.0
 DSC EVALUATION OF P H A S E SEGREGATION R A T E 421

OC I

L . , . .
I ,

80 9b ldo
segregaticn's rate % )

Fig. 3. Glass transition temperature of the soft phase in hydrogenated polybutadiene-based

polyurethanes as a function of the segregation rate ACpp/ACpl.

when the observed segregation rate decreases. In the PTMO soft phase, the
difference in AT is 19°C for a segregation rate previously estimated at 64%.
It is difficult to compare the AT of polyurethanes and polyurethaneureas that
contain different soft phases with different Tg(s)and different hard blocks with
different hypothetical Tg(H). In harmony with the free volume theory, AT should
depend on Tg(s,,Tg(H), Aa is the difference a ~-, CYGin which
and A q s ) ,AcY(H);
a~ and CYGare the volumetric expansion coefficients of the liquid and glass, re-
spectively.'S
We can more easily compare PUR from the same hydrogenated polybutadiene
soft phase, MDI, and chain extenders. Contrary to the affirmation of Schneider
et al.: the soft-phase glass transition temperature of all our polymers varies with
the nature of the chain extender (Table IV). The difference is more important
in polyurethanes than in polyurethaneureas. Figure 3 indicates the variations
in Tg(s)with the previously calculated phase-segregation rate. Although the
hard blocks structure is not exactly the same for all products, a linear variation
of Tg(s) was observed.
When extrapolated to loo%,the Tg of the pure soft phase was about -41.5OC;
that is, four degrees higher than the oligomer. This small difference can be at-
tributed to the chain end mobility restriction after polycondensation (this dif-
ference will be greater with a lower for the initial oligomer5J7).
An evaluation of the weight percentage of hard-block impurities present in
the soft phase was made possible by use of the Fox equation:

Unfortunately, Tghard was hardly detectable by DSC because of low heat-

capacity changes and a wide temperature range (dynamic mechanical spec-
troscopy indicates a relaxation temperature range of more than 5OoC!). However,
in MDI-BD hard blocks it is apparent that TgHcan be almost l10°C19. If Fox's
equation is applied to this type of hard block, the weight fraction in the soft
hydrogenated polybutadiene continuous phase would be about 6.7%. Taking
into account that 83%of the total soft segments make up this continuous phase,
422 CAMBERLIN AND PASCAULT

the weight percentage of hard blocks present in a secondly dispersed phase would
be 87%.
The same calculations for polyurethane, based on polybutadiene-MDI-BD,
provided a hard-block-phase segregation rate of 75%. This value is the same
as that of the soft-phase segregation rate (Table 11).
In PTMO-MDI-BD polyurethane the calculated value of hard-block segre-
gation rate was 68% the soft-phase rate was 64% (Table 11).
It can also be seen that the segregation rates of hard and soft blocks in, re-
spectively, hard domains and soft phase are similar when the calculation error
is considered.
We have studied polyurethanes with about 30%by weight of hard blocks and
note that the presence of soft segments in the hard domains (the dispersed phase)
are of much greater importance on properties than the presence of hard blocks
impurities in the continuous soft phase. In the PTMO-MDI-BD polyurethane
the segregations rates are so low (64 and 68%) that 50% in weight of the hard
domains should be formed with soft segments; this affects the mechanical be-
havior of the polymer and induces a thermoplastic flow near 80°C.8,9 A deter-
mination of the crystallinity AH, of the soft PTMO segment6 is apparently a
more complex criterion of phase separation than AC, and Tg.Recently,20we
obtained a similar relative crystallinity rate (50-30%) in a PTMO polyurethane
network with isocyanurate rings as did Schneider et a1.6 for linear segmented
polyurethaneureas. Morever, the crystallinity is due only to soft segments of
the continuous phase and gives no information about the dispersed phase.
The important mingling of soft and hard segments in this second phase is
confirmed by the amorphous structure or low crystallinity of hard segments in
polyurethanes or polyurethaneureas.12
On the other hand, in regard to the relaxation of the soft segments present in
hard domains, the wide temperature range of relaxation renders its observation
difficult on DSC, but can explain that in general the modulus of polyurethanes
or polyurethaneureas decreases regularly with temperature.
If a hydrogenated polybutadiene is used as prepolymer, the volume of soft
segments mingled with hard blocks in the hard domain reduces to 28%,thus in-
creasing their softening temperature of about 4OoC to a better rubbery pla-
teau.

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Received August 4,1982
Accepted September 13,1982