Temperaturc Dependence of Polymer Viscosity.

The
Influence of Polymer Composition*

ROGER S. PORTER and .JULIAK 1:. JOHXSOX, P h a w n Research

Company, Richmond, California

Synopsis
The change of visrosity with temperat,ure has been reported in the literature for a
variety of linear, amorphous polymers. These data in terms of the flow activation
energy, E*, indicate a wide variation among polymers with each exhibiting an essentially
constant and characteristic E* at high temperature and high polymer molecular weight.
These characteristic values for E* have been evaluated in terms of rhemical composition
and structiire of individual polymer coils. The valrie of E* increases as a regdar function
of the molar vohime of pendant groups :dong the polymer chain. RIore generally, a rela-
tion is shown between E* and the steric or conformational factor u. For polyolefins,
E* also increases regiilarly with the molar volume per monomer unit and with the mean-
square displacement length per chain iuiit.

INTRODUCTION
Countless studies have bccn made on visrosity-ten~per:tture behavior
of polymers. Yet until recently, it was thought impossible to develop a
general relationship b e t w w i viscosity-temperature characteristics and
polymer composition. 1
The most common interpretation of visc.osity-tempcraturc dependence
has been in the form of eq. (1):
?1 = A ~ + * / R T
(1)
where 0 is absolute viscosity, R is the gas constant, A is a constant, T is ab-
solute temperature, and E* is flow activation energy.
This equation is of the Arrhcnim form and has been called the Guznian-
Andracle equation. Equation (1) has been derived theoretically by Ey-
Since the entropy of activation is riot expected to change signifi-
rantly with temperature, the flow activation heat, H * , has sometimes been
used interchangeably with E*. H * has been considered the temperature
coefficient of viscosity due to thermal expansion.
For individual polymer systems, the equations of Doolittle4 and of Wil-
liams, I,andel, and Ierry5 have successfully expressed H* in ternis of free
volunie. Many variations of cq. (1) have been used to provide a fit for
viscosity data on polymers. In the Eyring derivation, E*, and therefore
H*, are dcrived without a completely defined physicd model. The princi-
*Part XY of a Yeries on Flow Properties of Polymeric. Systems.
373
3i4 R. S. I'OIITER A N D J. 1'. JOIINSON

pal rec~onimendationfor the USC of E* and H* is that they represent a useful

and prccise measure of viscosity-temperature dependencc.
The simple form of eq. (1) represents reasonably well the high lempcra-
ture viscosities of concentrated systems of liricar amorphous polymers.
Plots of log viscosity versus 1/T are generally curved but approach lin-
earity a t over 100C. above the highest glass-transition temperature. For
this reason, useful comparisons between polymers in terms of E* can gen-
erally be made near 200C >loreover, B* for Newtonian flow of such
systems is ( 1 ) characteristic of the polymer systems and ( 2 ) independent
of molecular weight, M , and distribution at high molecular weight (typically
above 10,000for undiluted polymer). Plots of E* versus l/M may be used
to obtain the E* characteristic of a particular polymer a t a given teni-
perature. It will be shown later that the characteristic B* is also inde-
pendent of stress, even in the non-Newtonian region.

POLYMER COMPOSITION
A. Pendant Group Volume
Since there is a wide variation among the E* values for amorphous poly-
mers, it, is tenipting tJofind a correlation between E* and polymer composi-
tion. For several polyolefins, Schott has shown a semilog relationship
between E* and the molar volume of pendant groups per chain unit.6
Figure 1 extends this correlation with some additional data. The molar
volumes used are as given by LeRas7 and agree within 10% with values
used by Icurata and Stockmayer.8 With few exceptions, a close fit to the
curve is obtained for all polymers for which pendant volumes of X and
Y in -CH&XY- can be calculated and for which reliable E* values have
been found. This correlation permits an estimate of E* from chemical
conipositiori alone. The same general principles apply a t low molecular
weights for the effect of short pendant groups on E*.3,9The fit of poly-

i
LL 4 1
10 ,b :o 410 ;o do 710 ;o 810 d o I I O 140
PENDANT GROUP MOLAR VOLUME, CC,LE BAS UNITS

Fig. 1. Characteristic flow activation energy vs. polymer pendant group volume.
(vinyl acetate) to the curve for other polyolefiiis in Figure 1 is consistent
with the we:tkness of the ester dipole indicated by the favt that low molecu-
lar weight esters have not only a similar a* but a similar viscosity to an
eyuistructure hydrocarbon.
B. Steric Factor
It is :tlso possible to develop a gcrieral correlation of h'* with polynier
composition which is not restricted to saturated (.arbon (+hailis. This has
been accomplished by using u, the stcreoparanietcr for intraniolccwlar
hindrance to rolation, which has been indcpciidcritly shown to be gciierally
related to p e d a n t group volume.*^ lo
In general form, tlic factor, u, or conforniatioiid paranictcr, niay be
defined as:
u2 = IL"O/[L21",, ('2)
where [L2j0,,is the mean-square displacement length for fixed valcnce an-
gles and free internal rotations, and [L2]ois the unperturbed mean-square
displacement length at the theta point.
Figure 2 shows a new relationship between E'* arid u. Adjustnierits have
not been made for the difference in temperatures, -25C. and --2OO"C.,
for measurements of u and E*, respectively. The correlation in Figure 2
covers a variety of polymers (See Table I). The uncertainty in E* is
generally about 1 kcal./mole. The error in cr is about the dimensions of the
circles on the graph.* Wider variations in u have been reported for certain
polymers. The lower of two available u values for poly(viny1 acetate)
has been uscd. This lower value gives better agreement in both Figures 1

.I2 .I4 .I6 .I8 2 0 .22 .24 .26 2 8 3 0 .32 3 4 .36

LOG STERIC FACTOR. Q

Fig. 2. Characteristic flow nctivalioii ciicrgy vb. polynicr stcric f n c h r .

376 H. S . IOKIEK AND J . F. JOHNSON

and 2 . The lowest u reported for polystyrene has been used since it proba-
bly should Iiot exceed values for paramethyl, parachloro, arid 2,5-dichloro
derivatives of polystyrene, all of which have a reported u of 2.16-2.18.8f11
The E* for polyisopreric was iiiatchetl with a c for an average cis-trans
ratio.R ].or the sake of correlation the c for poly-4-methyl-1-peritene was
considered equivalent to that of poly(viny1 isobutyrate). Ether-ester
coriderisntion polymers, styrenebutadierie and ethylene-1-butene copoly-
mers were plotted assuming an additivity 011a molar basis of the respective
homopolyiner u values. Additivity calrulations for u may not always
apply.12 The inore cornsistent set of data on I$* for styrene-butadiene
rubbers was used.8

TA4BLKI
h i e a r Amorphous Pol?mers Showing a Relatioii betweeii Flow hc1iv:ttioii Ellerg).
arid Steric Factor
_ _ ~ -
~~ ~ _ _ _ _ _ _ ~ ~ _ _ _ _ _ ~

Prime ref. Symbol in

Pol) mer for E* Fig. 2
Poly(dimethy1 siloxane) 17 a
Polybii tadiene 25 0
Polytriethylene glycol ether 26 0
Linear polyethylene 27 Q
Pol?-(ethy lene-1-but eiie)
100:4 4 28 c
3
lO0:O s 28 0
Poly(decamet hyleiie sebacltte) 29 0

Pol?.(~tjreiie-biit:~dierie)GIL-S, 5 6 7 2 30 0
Polypropyleiie 81 0
Iievea rubber 32,3:5 0

Poly( c-caproarnide) 34 6
Polyibobuteiie 30,35 0
Poly(viny1 acetate) 36 -8

Polystyrene 37 c

AImy linear polyesters, which vary widely in thc molar coiiceritrutiori o f

the ester group, have an E* in the range of linear polyethylene, 8 1 *
l\cal./molc. The u values for linear esters are also similar with the excep-
tion of poly(decamethy1ene adipate). This c deviates from Figure 2 and
niny iritlic*ate an incorrect coil size nieasurenient, as has been concluded
intlrI)(~Iiclciitly.8 Poly(viny1 chloride) and its copolyniers do not fit cithcr
1Cigiirc 1 or ICigitrc 2 ; they rcj)ortc~llyh:tvc. :in uriiisu:illy high ]<*.sic If
c . i y h t allinitg w i h t s i t i s\wh 1)olyiji(~r\,:\grwiiimi w i ~ i i l ~not
l h cbupwt (vl.
1,itw:it rire valws of 20 25 ~ ~ ~ : d . / t [or i i ~poly(ii~~tlry1
k ~ iiirt Ii:tc.ryl:il t ~ )\~o111(1
iit vorrclations in Icigure 1 :~nd2.14 1tecalrul:~tiorilroni (1:tt:i vited, I i o \ \ ( v c ~ ,
indicates that thc flow activation energy is at least 30 kc:tl./mole at 200-
280C.14 The deviation is likely due to the high glass transition tempera-
<
tiire, 122C. for poly(niethy1 nicthacrylate). The deviation of thc poly-
 ~EMIERAIUIZEUEPEIZDEVCE O F 1OLYMEIZ VISCOSITY 377

aniide value in Figure 2 corresponds to a low U . Tsvetkov has given a

much higher value, 2.1, for nylon C i , C i . S
Eigure 2 can be tentatively extended to higher values as Tsvetkov has
given a u of 4 for ethyl rellulose for which an E* of 40 has been reportedj
loly(ethy1ene oxide) should appear a t the low end of the plot; but a t pres-
ent E* is riot firnily established. S o attenipt has been made to justify any
particular functional dependenre of h* on U , although there is obviously a
high correlation. The steric factor is not :Ltemperature coefficient but
strongly reflects the shape of the average potential energy function for
niotion leading to measurable variations in I$*.

C. Coil Size
The same depcriderice as shown in Figure 2 will hold for vinyl and vinyl
iIiderie polymers if the lctal factor,8 s = [L2]],/nZ2, is plotted instcad of
the corresponding U . The synibol n is the riuiiiber of chain bonds of aver-
age length, 1. Tests can be made to determine whether coil size or steric
parameter is the governing factor in defining h*. Poly(dimethy1 siloxane)
has essentially the same [L2]/nZ2 value, -6.8, a\ polyethylene; whereas,
their u values are distinctly different, -1.63 and -1.47, respectively.8
This difference is in the direction of the niarkcd difference in E* for these
polyniers, -7.1 and -4.8 kcal./mole (see 1:ig. 2).17 This coniparisort favors
the correlation of h*with u rather than [L2],,/n12.Differences also show
up in other cases such as cis and tr*anspolyisoprerie where 100% cis and
100yo trans have a u value of 1.67 and 1.38, respectively; yet their rorre-
spoiidirig chain dimensions, ( [L2]0/11/)1 X l o l l , are in the opposite direc-
tioii, 810 arid 970, respectively.* A correlation of E* with unperturbed
coil diniensioris must also be recoitciled x i t h the different sign of the teni-
perature dependences of [L2lO arid of the viscosity.
I;rom the presentations in Figures 1 and 2 , it would appear that B* is
directly related to short-range interactions along the polymer chain, viz.,
steric hindrance and torques which restrict internal rotations. Variations
in stereoregularity are expected to have little influence on E*. For poly-
styrene, polypropylene, arid poly(niethy1 methacrylate) variations in coil
size arid u with tactirity are small or negligible.5 The peiidaiit group
molar volumes for poly(niethy1 acrylate) and poly(viny1 acetate) are the
same. It is interesting that the u for the acetate, 2.02, is well within the
precision of 2.05, the u reported for poly(niethy1 arrylat(~).8This indi-
cates that inverting the pmdarit ester group do(^ not signifmmtly in-
fluence U .
I<iirat:t :uid Stoc.l,ti1:iyc.r (plot (> foiir 1):iii.sof polytiivr\ for which the. prcs-
(~tiw of :iit u-riicbiliyl groiip hwls t o :it1 itt(w:iw i t i u . ~ I-io\\c.vc~r,ilic pair
~ ) o l y t t h y l t l i ~ - ~ J ~ ~ y ~i)vrt i~i a~i t)i ~q l itn lt~L itq) i t t c . . Ilrcl u of poly1)ropylc~iie
hits ror(1tttIy i)ccli rel)orl(d t o he less tli:\li th:tt of poly(thyl(11ic, -1.44
versus - l . G 0 . 6 The E* for polypropylene IS cic+mtely higher t h:m for
polyethylene, which agrees with the pendant group correlation iii ligure 1.
If, however, u for polypropylene is less than for polyethylene, a distiiict
378 R. Y. 1'01V1'EH AND J. F. JOllNSON

discrepancy exists in Figure 2 . From heats of combustion i t has been

concluded that steric effects are not significant for polypropylene over poly-
ethylene, although the latter has a slightly higher combustion heat.'*
The heat of combustion of polyisobutene is marliedly less indicative of
steric repulsion. Heats of polymerization measurements on an extensive
series of monomers provide another test of steric effects.IY Studies of nine
polymcr pairs with and without an a-methyl group showed that the
a-methyl derivative in every case had a lower heat of polyinerization. This
is indicative of steric and/or hypercoiijugatiori effects. The decrease in
heat going from polyethylene to polypropylene is the smallest, 2-3 lical.,
between any similar pair and has been attributed largely to hypercorijuga-
tion. Thus, steric effects in polypropylene are not clearly shown. In
general, however, heats of polymerization do decrease markedly arid regu-
larly with increasing size of pendant groups in the vinyl and vinylidenc
p01ymers.l~ It would be highly desirable to compare E* to energy barriers
for chain rotation if precise values mere available for relevant model coni-
pounds. 1;ox and Allen20 have treated viscosity-temperature dependen re
with some success in terms of friction coefficient and have inferred a pos-
sible relation with the pendant group volume. This was tentatively es-
tablished earlier by Schott.6 The empirical relationships, developed in
Figures 1 and 2, probably have as their underlying basis the variation in
activation energy for viscous flow with variation in activation energy for
the average short-range motion of segnicnts along the chain.

D. Molar Volume
Just as I$* for a particular polymer can be related to volume chaiiges
with temperature, perhaps a woss correlation is possiblc which relates the
molar volume for different polymers with the corresponding arid character-
istic values of E*. For low rnolecular weight liquids, Andrade correlated
E* with the inverse first power of specific volume. Molar volume is idso
an alternate explanation to the steric factor for the rclatioiiship between E*
and pendant group volume.
Figure 3 shows a correlation between measured molar volumes a t 200C.
for vinyl polymers and the corresponding approximate molar volumes cal-
culated on the basis of additivity as in 1;igur.e 1. l\lost of the data are taken
from citations in reference 21. The correlation in 1;igure 3 is reniarkably
good with nearly a first-power dependence and zero intercept within experi-
mental error. This indicates that the molar volumes for amorphous poly-
mers are governed by the same short-range interactions as are low molecular
weight conipourids. The additive molar voliinies in Figure 3 are greater
than those measured on polymers. This is not inearit t o iniply ortlcr in the
nielt as additive molar voluiiicr huvc. not heen rxtr:tpolated to iiifiiiite
molecular weight nor corwctctl for teniper:Lture. In fact, if significant
ordering in the melt must be postulated,22it must exhibit a remarkable
rcgularity with chemical composition.
 I4OJ

V
120 c
I

POLYSTYRENE

//*
0
N
0 FOLY 4 METHYL-I-PENTENE 0

+loo-
4
0-
V

80-
3
-I FOLY I-BUTENEO

w
0

a 60-
4
2
POLYPROPYLENE / POLYISOBUTENE

/
0
I
240-
/LINEAR POLYETHYLENE
U
3
v)
4
W /
/
= 20- /
/
/
/
/
Oo I I L 1 1 1
20 40 60 80 100 120 Id

Fig. 3. Volume per monomer unit for amorphous polymers.

The question again arises as to whether inherent polymer coil size or

steric factors govern molar volume and E*. Bondi and Simkin23 have
pointed out that molecular volume can be quantitatively related to molecu-
lar flexibility through the number of degrees of freedom per molecule.
According to the Prigogine theory, the volume of pure polymeric liquid
is a function of a reduced temperature which depends on cohesive energy,
flexibility, and molecular weight. 24
The authors express appreciation to lh. &I. J. 11. Caiitow for help with this paper.

References
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480 It S. POKTER AiYD J. F. JOIINSON

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Resume
La variation de la viscosit,i: avec la tenipkratiire a irt,ir rapportbe daus la litirrature
pour pliiaieurs polymkres liriiraires amorphes. Ces rbsriltats exprim& soiis fornie dhrergie
dactivstion d6coulement E* indiquent uiie graride diffbreiice elit re les polynii.res,
chacun maiiifestaiit iiiie valeur de E* essentiellemeiitt constantmeet. caractbristiqiie B
t,empkrature klev6e et aiix poids moliiculaires 6levhs. Ces valeurs caractkrlstiques de E*
o i i t 6t6 6valiiiis stir la base de la composition chimique et. de la structure des pelotes poly-
mCriqiies individuelles. E * croit r6gulibremeiit avec le volume molaire des groupes
latkraux le long de la chairie polymkrique. De faCon plus giinkrale, il existe une rela-
hion ent.re E* et le facteur stdrique ou conformationriel u. Pour les polyoldfines, E* croit
aiissi r6giilikremeiit avec le volume molaire de lunit,6 rnonom6riqiie et avec la loiiyiieiir
quadratiyue moyenrie de d6placement, par unit6 de chaiiie.

Zusammenfassung
Angaben fiber die Temperaturabhangigkeit der T-iskositiit eiiier Tielfalt linear,
aniorpher Polymerer findeii sich in der Lit,eratiir. Diese Ilateri zeigeii, als Aktivier-
iingseneryie des Fliessens E* dargestellt, bei den verschiedenen Polymereu eiiieii breiteii
\-ariationsbereich, wobei jedes bei hoher Teniperatur wid hoheii RIolekulargewicht eiii
im wesentlichen konst,antes nnd charakteristisches E * aiifweist. Diese charakteristischen
Werte fiir E* wurden in bezug auf ihre Abhangigkeit von cheniischer Zusarnmeiiset-
zung und Struktur der individuellen Polymerknaiiel ausgewertet. E * nimmt als
Furikt,ion des Molvoliimens der Seitengruppen an der Polymerket.te in regelrniissiger
Weise zu. Allgemeiner betrachtet, besteht cine Beziehung zwischen E* und dem ster-
ischen oder Konformationsfaktor U. Bei Polyolefinen besteht auch cine regelmksige
Zunahme mit dem 3Iolvolumen des Momomerbausteins und mit der mittleren qiiadra-
t ischeri T~erschiebiuigslliigepro Kett.enbauatein.