Polymer Constitution and Fiber Properties*

K. HILL and E. E. WALKER, Imperial Chemical Industries Ltd., Research Labora-

tories, Hexagon House, Blackley, Manchester 9,England

INTRODUCTION
THE MECHANICAL and physical properties of a fiber depend
partly on the chemical structure of the polymer from which it is made and partly
on the manner in which the fiber is built up from the polymer.
It is now generally accepted that a fiber contains ordered regions called
" crystallites" which are separated from one another by disordered (amorphous)

regions. The crystallites are oriented in such a manner that the molecules from
which they are built are parallel with the fiber axis. The crystallites themselves
are so small that a single polymer molecule can take part in the structure of several,
passing through the disordered regions in between. In the case of a synthetic fiber
(which possesses no cellular structure), it is the crystal structure, relative size, quan-
tity, and arrangement of these crystallites which largely determine the mechanical
and physical properties of the fiber.
In synthesizing a fiber-forming polymer the problem is to devise a chemical
structure which can be spun into filaments and given this oriented crystallite struc-
ture by stretching. As a result of work carried out very largely by Carothers, but
also by other workers such as Staudinger, Mark, Astbury, and Fuller, the main out-
line of the chemical structure required for a polymer to possess fiber-forming proper-
ties has been determined. It is unnecessary to discuss this work in detail but, in
1931, when Grst announcing the fiber-forming properties of super-polyesters, Caro-
them and Hill' stated that: (a) the polymer must consist of very large molecules,
the molecular weight not less than 12,000 and the molecular length not less than
1000 8.;(b) the polymer must be capable of crystallizing, this property being
possessed generally by linear polymers, provided there are no bulky side groups to
destroy the linear symmetry of the chains; and (c) the three-dimensional polymers
such as the glyptals are unsuitable.
Broadly speaking this specification holds today and is a tribute to the great
insight of its author; but, in the light of our present knowledge, it is now possible
to fill in the picture and to obtain a clearer idea of the chemical structures that are
desirable.
In this paper the chemical structure of a large number of linear polymers is
correlated with their spinnability and their ability to assume a polycrystalline form
possessing adequate thermal stability. These are the primary fiber-forming proper-
* Some of the unpublished work mentioned in this article is the subject of patent applica-
tions due for publication shortly.
1 W. H. Carothers and J. W. Hill, J. Am. Chem. Soc., 54,1579 (1932).

Volume 3, No. 5 (1948 609

 R. H I L L A N D E. E. W A L K E R

ties which are least affected by the previous history of the polymer. At the present
stage of knowledge of this subject it is not possible to correlate the detailed mechani-
cal properties of fibers with the chemical structure of the polymers from which they
are made. These properties depend very much upon the Gne structure of the poly-
mer as it exists in the fiber. This, in turn, is determined to a large extent by the
conditions of spinning and drawing and by the nature of any subsequent heat treat-
ments to which the fibers may be subjected; therefore, a close correlation cannot
be made now and may not be possible. However, it is possible to correlate gross
differences in the mechanical properties of fibers with chemical structure; and it
will be shown how certain structures lead to the absence of definite fher-forming
properties or to a low degree of crystallinity and rubberlike elasticity.
I n addition to this, some properties of fibers, such as solubility, moisture sen-
sitivity, and certain dyeing characteristics, can be correlated, to some extent, with
chemical structure, though in this case also, the crystallite structure-as deter-
mined by the manner of spinning, the draw ratio, and other treatments given to the
fibers-exerts a very powerful influence. Thus, for example, undrawn polyethylene
terephthalate (Terylene) fibers are dyed comparatively readily by most acetate
dyestuffs, while the drawn oriented fiber dyes with greater difficulty.
Effect of Molecular Weight on Fiber-Forming Properties
The effect of molecular weight on fiber-forming properties and on the proper-
ties of fibers, when formed, is very critical, but the average molecular weight that
must be reached before fiber-forming properties become apparent varies with the
chemical nature of the polymer. Carothers and van Natta2showed that in the case
of the polymer from w-hydroxydecanoic acid weak filaments can be spun at a molecu-
lar weight (number average) of 7300 but that these cannot be cold drawn. Cold-
drawing begins at 9300, but the fibers are weak. Strong fibers are obtained at 16,-
900. Carothers and Hill1 conclude that the lower limit of molecular weight for
polyester fibers is 12,000 and perhaps a little lower for polyamides. A molecular
weight of 20,000 has been recorninended for polythene fibers; and probably the
lower the interchain cohesive forces, the higher is the molecular weight at which
useful fiber properties appear (compare Mark3). The molecular weight distribu-
tion undoubtedly affects fiber properties but, according to Flory,' polymers formed
by polycondensation reactions should possess similar molecular weight distributions.
This theoretical molecular weight distribution has been confirmed to a very large ex-
tent in the case6 of 66-nylon polymer; therefore, differences from this cause may
be expected to be slight among this group of polymers.
The chemical structure of the intermediates and the nature of the condensation
process have important effects on the ease with which high molecular linear poly-
mers can be attained. Side reactions that result in the loss of reactive end groups
and so prevent the growth of the polymer chain must be avoided. Side reactions
that result in branched-chain formation may cause cross linking and the formation
2 W. H. Carothers and F. J. van Natta, J . Am. Chem. Soc., 55,4714 (1933).
a H. Mark, J . Am. Chem. Soc., 34, 1343 (1942).
4 P. J. Flory, Chem. Reus., 26, 137 (1940).
6 G. B. Taylor, J . Am. Chem. Soc., 69, 638 (1947).

610 Journal of Polymer Science

 POLYMER CONSTITUTION AND FIBER PROPERTIES

of a gelled polymer which cannot be spun. The necessity for avoiding intermediates
which readily form ring structures is well known. This aspect of polycondensation
reactions was studied in very great detail by Carothers and his associates,6and need
not be discussed here. Similarly, the use of intermediates which give rise to an
unfavorable monomer-polymer equilibrium (e.g., caprolactam’) leads to complica-
tions it is well to avoid.
In technological work the molecular weight of a polymer is generally charac-
terized by intrinsic viscosity [ q ] . For most condensation polymers this should be
at least 0.5 if fiber-forming properties are to be fully developed, and a higher value
is needed to obtain the best physical properties. Fiber-forming properties appear
in urea polymers at a lower intrinsic viscosity than in the case of other polymers,

Structural Factors Affecting Crystallinity and Crystallite

Melting Points of Linear Polymers
The attempt to correlate crystallinity with chemical structure meets with dif-
ficulties at the outset, owing to the fact that no exact measure of the degree of
crystallinity exists. The so-called crystalline-amorphous ratio of polythene has
been measured by x-ray diffraction* and by density relationship^,^ and this ratio
has been measured for stretched rubber by various authors.l0Sl1 Various other
attempts have been made but the value of the ratio depends, within limits, on the
method of measurement. In this paper no attempt is made t o estimate the degree
of crystallinity in various polymers, but considerable importance is attached to the
crystallite melting point and, where available, to direct observations on Gber-
forming properties (i.e., ability to spin and cold draw). The crystallite melting
point may be regarded as a measure of the tendency of the polymer to crystallize.
It may certainly be taken as a measure of the stability of the crystallite structure.
It also possesses great practical significance, since the melting point of a textile
Gber must be well above ironing temperature and, if melt spun, must be below de-
composition temperature.
The melting point of a crystalline substance depends very much on the ar-
rangement of the molecules in the crystal lattice; this applies also to crystalline
polymers. Therefore, a full understanding of the effects of chemical structure on
melting point can be reached only after the crystal structures of a large number of
polymers have been determined. X-ray work on the crystal structure of selected
polymers is being carried on in these laboratories; but this work takes time, and
meanwhile certain general conclusions can be drawn by direct comparison of melting
points and fiber-forming properties with chemical structure.
In this paper the hydrocarbon, polythene, is taken as the parent Gber-forming
polymer, and the effects studied of the insertion of various polar links and ring
6 W. H. Carothers, Chem. Revs., 8, 353 (1931).
7 Synthetic Fiber Developments in Germany, B.I.O.S. File No. XXXIII-50, H. M. Stationery
Office, London.
8 H. C. Raine, R. B. Richards, and H. Ryder, Trans. Fwuday Soc., 41,56 (1946).
9 E. Hunter and W. G. Oakes, Trans. Fwuduy SOL,41,49 (1946).

10 J. E. Field, J . AppZiedPhys., 12, 23 (1941).

11 A. J. Wildschut, Rubber Chem. and Tech., 19,1124 (1946).

Volume 3, NO. 5 (1948) 611

 R. H I L L A N D E. E. W A L K E R

structures in the hydrocarbon chain according to a regular pattern-and of the at-

tachment of various side groups to it-on the crystallite melting point and fiber-
forming properties. However, before attempting to make this comparison, it is
necessary to study the effect of the spacing of the polar links because this has a
profound effect on the crystallite melting point. In any one series the melting

1
I 3Ol 2 3. 4

-n-
5 6 7 8 9 10

NUMBER OF CARBON ATOMS

IN ACID
Fig. 1. Melting points Figure 2
of polyesters containing
decamethylene glycol.

points of polymers containing only even numbers of --CHZ- groups between the
polar links lie on a different curve than do those of polymers which contain an odd
number of -CH2-- groups. The result is that the melting point curves of homol-
ogous series of polymers have a zig-zag form (see Figs. 1-4). This has been in-

, 5 0 1 170; I '
3 4 5 6 7 8 9 1 0
' I ' ' ' I '
3 4 5 6 7 8
NUMBER OF CARBON ATOMS IN ACID
Figure 3 Fig. 4. Melting points of polyamides
containing pentamethylene diamine.

vestigated by Fuller and his a s s o c i a t e ~ l ~in- ~the

~ case of polyesters by means of
x-ray diffraction measurements. It is concluded that this phenomenon is related
to the planar zig-zag structure of these polymers, and an explanation is offered based
on the crystal forms observed and on the direction of the bonding forces. This
I* C. S. Fuller and C. L. Erickson, J . Am. Chem. Soc., 59, 344 (1937).
1s C.S. Fuller and C. J. Frosch, J. Am. Chem. Soc.,61,2575 (1939).
1 4 C. S. Fuller and C. J. Frosch, J . Phys. Chem., 43, 323 (1939).

612 Journal of Polymer Science

 POLYMER CONSTITUTION AND FIBER PROPERTIES

planar zig-zag structure has been proved for polyamides by BUM and Garner,15
and it has been shown that in the case of hexamethylene adipamide (66) and hexa-
methylene sebacamide (610) polymers the molecules are arranged in sheets in such
a manner that the -NH- of one molecule is hydrogen bonded to the -CO- of
the neighboring molecule. Assuming this planar zig-zag structure for all poly-
amides, the cases shown in Figure 5 are possible. Each case has its own particular
arrangement of -CO.NH- groups which must and does affect the manner in

No.OF AMINO- EVEN AMINO-ODo ACID NW ACID EVEN ACID ODD AClO 000
C-ATOMS. ACID AMINE EVEN AMINE 000 AMlNE EVEN AMlNE ODD

AMIDE
GRWPSWEU. HALF ALL ALL HALF HALF HALF
PUCE0 FOR
H-BONDING

MELTING
POM
l LOW HIGH HIGH LOW LOW LOW
Fig. 5. Effects of zig-zag planar configuration on hydrogen bonding.

which the chains pack together. Cases a, b, c, and d were investigated for poly-
esters by Fuller and co-workers; Fuller gives his own explanation based on the dif-
ferent crystal packings observed. It is sufficient to point out here that in cases
b and c (high-melting forms*) the arrangement of the -CO - NH- groups along
the chain is such that every -CO- group can be brought exactly opposite an
-NH- group in a neighboring chain. In cases a,t d , c, andf (low-melting forms*),
l6 C . W. Bunn and E. V. Garner, Proc. Roy. Soc. London, A189, No. 1016.39 (1947).
* “High” and “low” melting forms in this context mean that they occupy the peak and
the trough, respectively, of the melting-point curve.
t For a, it is possible to envisage an alternative arrangement in which the molecules lie side
by side, head to tail. In this case all -CO- groups can come opposite -NH- groups.

613
 R. H I L L A N D E. E. W A L K E R

only half the -CO- groups can be brought exactly opposite -NH- groups in
any one arrangement.
Fuller also showed that for polyesters, the fiber repeat period of the high-
melting forms is equal to the chemical repeat period, while in the low-melting forms
it is equal to twice this quantity. The necessity for this is illustrated by Figure 5 if
-0- atoms are substituted for -NH-.
Reference to Figures 1-4 shows that these zig-zag melting-point curves are
found in the cases of aliphatic polyesters, polyamides, and polyurethans. It is
even shown in the case of aromatic polyesters containing an aliphatic chain, and,
as Fuller says, it is a necessary consequence of the planar zig-zag structure of the
aliphatic-chain. It is evident that the melting points of the polyamides change
much more from member to member of an homologous series than do the aliphatic
polyesters. This is probably due to the fact that the molar cohesion of the amide
link (16,200) is much greater than that of the ester link (3460), and that the diluent
effect of the -CH%- group (990) is, therefore, more marked in the former case.16
In Table I it is shown that isomeric linear polyamides formed from components
possessing even numbers of carbon atoms in the chain possess roughly similar melt-
TABLEI
INFLUENCE OF “ODD” AND L ‘ E ~COMPONENTS
~~’’
ON THE MELTING POINTS OF POLYAMIDES
Total
number
Numberof of chain Meleg Melting
Numberpf Catoms atomain poult point
Catomsin indibaeic repeating foreven for odd
diamine acid unit components compouents Footnote

4 6 12 295 17
5 5 12 198 17
2 10 14 254 17
4 8 14 250 17
5 7 14 183 17
6 6 14 265
4 10 16 239 18
5 9 16 179 18
8 6 16 235 18
5 11 18 176 18
6 10 18 215 19
8 8 18 216”
10 6 18 230 19
8 10 20 197 18
9 9 20 177 19
10 8 20 208”
0 Interpolated values.
18 These values are given by Dunkel and Wolff and quoted by H. Mark in Physical Chemis-
try of High Polymeric Systems, Interscience, New York, 1940, p. 11. The value for -CO.O-
is obtained by difference from -CO.OGHS (6230) and --CzHs (2770).
17 Brit. Pat. 506,125.
18 Brit. Pat. 474,999.
19 W. 0. Baker and C. S. Fuller, J. Am. Chem. Soc., 64,2401 (1942).

614 Journal of Polymer Science

 POLYMER CONSTITUTION AND FIBER PROPERTIES

ing points. Polyaniides isomeric with these, but made from components possessing
an odd number of carbon atoms in the chain, melt much lower. The similarity be-
tween the melting points of even-numbered isomers, and the fact that the melting
points of homologous series of polyamides and polyesters made from even-num-
bered components lie on a smooth curve, make it possible to estimate the melting
points of missing members of some series with a fair degree of accuracy. These
facts have been utilized in this paper. It is interesting to compare the melting
point (198°C.) of pentamethylene glutaramide (55 polymer), in which only half the
amide groups seem l,o be capable of a normal degree of hydrogen bonding, with that
of decamethylenesebacamide (1010 polymer, m.p. 194OC.), which contains about
half the number of amide links but all of them hydrogen bonded. Biggs, Frosch,
and EricksonZ0have investigated the effect of varying degrees of N-alkylation on
the melting points of polyamides, and this work gives strong support to the view
that the high melting points of the polyamides are due mainly to hydrogen bonding.
Influence of Polar Links on Melting Points
of Polycondensation Polymers
By selecting siutable di-reactive components and causing them to interact, a
very wide variety of linear polymers containing various polar links spaced at various
TABLE I1
MELTINGPOINTS
OF POLYESTERS,
POLYURETHANS,
AND POLYUREAS
POLYAMIDES,
class of polym3f Repeating unit
Ester.. .................................. .
.- 0 (CH2),,. 0 .CO.CHI-(CHI),'-CHt. C O -
Urethan.. ................................
.-NH.(CH,),.NH.CO. O .(CHr),'. O .CO-
.
Amid0 ................................... .-NH .(CHI)II .NH CO *CHz.(CHt),,'-
CH2.C-
,. . .
Urea. .................................... .-NH. (CH2) NH CO NH .(CHa),'.NH .CO-
n............................
...........................
n'
4
4
6
4
6
6
10
6
8
8
10
10

Ester.. .............. a56"C. 58°C. 67OC. 73°C. 73°C. -

Urethan. ............. 193" 180 O 140-150" b1540 - 138-145 "
Amide.. ............. 250" a235 215 O 194 a1940 -
Urea. ................ - - >300° - 260 " 210"
dec.
Urethan.. .......................................... .-NH.(CH&-O-CO- (m.p. 150°C.)
Amide. ......................................... .-NH.(CH&-CHI-CO- (m.p. 223°C.)
For comparison
Polythene.. ..................................................... .-CH- (m.p. 1lOOC.)
Polyethylene oxide.. ..................................... .-CHS*CH~-O- (m.D. 55-70°C.)
Value for nearest even-numbered isomer employed.
a
Value by interpolation from next higher and next lower even-numbered homolog.
References: polyesters, 14,21; polyurethans, 7,22,23; polyamides, 17,18,19; polyureas
7,23,24.
zO B. S. Biggs, C. J. Frosch, and R. H. Erickson. Znd. Eng. Chern., 38,1016 (1946).

I1 W. H. Carothers and G. A. Arvin, J . Am. Chem. Soc.. 51, 2560 (1929).

2z U. S. Pat. 2,284,637.
2s Brit. Pat. Appl. 32,979/38:
24 Lieser and Gehlen, Ann., 556, 127 (1944).

Volume 3, No. 5 (1948) 615

 TABLEIT1
EFFECT
OF METHYL.
GROUPSON FIBER-FORMING
PROPERTIES
OF POLYAMIDES
AND PQLYESTERS
-
For-
mula Fiber forming M.p.. Foot-
Repeating unit Cryatallinit y oc. note
num-
ber
4
1 -CO .CHZ .CHz .CHz * CHz .CO .NH .CHz .CHZ. CHz .CHz CHz .CHz NH- Yes Yes 265
2 -CO .CH2. CHZ. CHZ * CHz .CO .NH .CHz * CHz. CH * CHI. CHz * CHz*NH- - Yes 180 17

LH3
3 -CO .CHZ * CH * CHZ-CHz * CO .NH .CHz. CHz * CHz CHz .CHn * CHz *NH- - Yes 216 17

AH,
4 -CO CH,. CH2 * CHz. CHz .CO .N .CH2 * CHZ. CHz .CHz * CH,. CHz * N- No (forms crys- Yo (inter oly -75 (sets tc 29
talline inter- mers Ler: brittle resin:
AH3 AH3 polymers) forming)
5 -0.CHZ .CIIz. CHZ. CHz .CO .NH .CH,. CHZ .CHz .CHz .CHa. CHz N- Yes About +145 20

AH:
6 -CO *
.CHz. CHz.CHz*CHz.CO 0 .CHz. CHz .0- Yes Yes 52-54 13
7 -CO .CHz .CHz .CHz .CHz .CO .O. CH CHz .O- Syrup thickeni to rubber on 30
increasing the , lecular weight

8 Yes Yes 256 31

9 -CO. .
CH .C H ~O-
C)CO.O- No (glassy) No 122 30

AH:
10 Yes Yes 221 32

11 No (glassy) No About 80 30

12 Yes Yes 140 30

 POLYMER CONSTITUTION AND FIBER PROPERTIES

intervals along the chain can be synthesized. Table I1 gives melting points for
series of comparable polyesters, polyurethans, polyamides, and polyureas. In Fig-
ure 6 melting points are plotted graphically against the number of chain atoms in
the total repeat period. It is interesting to note that the melting points of the
polyesters are all below that of the parent hydrocarbon, polythene. The others all
lie above that of polythene in the order : urethan, amide, urea. The melting-point
curves plotted against the repeat period all seem to be approaching the value for
the hydrocarbon as the repeat period increases (Fig. 6). This would be expected if
the crystalline structure is similar. Since the polar link --CO*O- has a molar
cohesive power greater than that of the
-CH2. CH2- group it replaces, it seems
that there must be some other influence
tending to lower the melting point. Ether
links, which also lower the melting point,
are believed to activate the rotation of the
neighboring carbon links, and so increase
the flexibility of the molecule.25 There
is some evidence that ester links produce
the same effect. This increased flexibility

5op+--- Polyesters
would render the molecule more mobile
at a given temperature, and so lower the
melting point. It is interesting to note
that high molecular polyethylene oxide
NUMBER OF CHAIN ATOMS IN REPEATING UNIT melts in the same temperature range as
Fig. 6. Melting point trends of polymer the majority of the polyesters. Low
series. molecular decamethylene oxide polymer
(M.W. 1200) melts at 58-6O0Cz6
Very little information is available on thioamide polymers, but it seems clear
that they are lower melting than the corresponding amide polymers. The following
information has been published:27
Polymer ma., C.

Hexamethylene thioterephthalamide................................... 190

(decomposes)
Thiocaproamide (softens 65 "C.)....................................... 120
(spins and cold draws)
Decamethylene thiosebacamide. ....................................... softens at 85-90
(rubbery)
~~~

E. Guth, H. M. James, and H. Mark,Advances in CoZZoid Science, Voi. 11. Interscience,

New York, 1946, p. 262.
26 J. W. Hill, J . Am. Chem. Soc., 57, 1131 (1935).

27 Brit. Pat. 535,934.

28 Brit. Pat. 534,699.

2% Brit. Pat. 568,977.
30 Miscellaneous unpublished work carried out in the Research Laboratories of Imperial
Chemical Industries Ltd.
a1 J. H. Whi&eltf, ,'ature, 158, 930 (1946).
32 Brit. Pat. 578,079.

Volume 3, No. 5 (1948) 617

 R. H I L L A N D E. E. W A L K E R

The melting points of the corresponding amide polymers are above 350", 212O, and
194"C., respectively. The aliphatic polymers are soluble in pyridine, and some
are soluble in dioxane. They are apparently noncrystalline, but the thiocapro-
amide polymer can be spun into fibers and shows signs of cold drawing. Thiourea
polymers also melt lower than the corresponding urea polymers.2s Polymers with
intrinsic viscosities in the neighborhood of 0.3 spin and cold draw (20-60%).
Broadly speaking, comparable high molecular monomeric hydrocarbons,
ethers, alkylcarbamic acid esters, amides, and ureas form melting-point series in
the same order as those of the polymers. Thus, for example, hexadecyl palmitate
melts a t 53-54°C. and dicetyl ether at 57-58"C., the corresponding C33hydrocarbon
melting a t 71°C. Complete series of comparable esters, hydrocarbons, urethans,
amides, and ureas are difficult to find, but a search of the literature shows that the
higher homologs follow broadly the same trends as the polymeric substances.
Effect of Inert Substituents in the Polymer Chain
Hydrocarbon side chains reduce crystallinity. Table I11 shows the effect of
introducing methyl groups into polyamides and polyesters. In every case the
melting point is lowered, and, in some cases, crystallinity (observed a t room tem-
perature) is eliminated completely. Solubility in organic solvents is generally in-
creased. Thus formula 1is insoluble in alcohols, 3 is soluble, and probably 2 also.
Probably, the methyl groups act by increasing the separation of the chains and
(particularly when unsymmetrically placed) by introducing linear and lateral dis-
order. The terephthalic ester series is particularly interesting. The single un-
symmetrical methyl groups in 9 and 11 give noncrystalline polymers with melting
points reduced by 135-140°C. On the other hand, the two symmetrically arranged
methyl groups in 12 give a crystalline, fiber-forming polymer with a melting-point
reduction of only 80°C. The slight crystallinity of polyvinyl chloride and the very
pronounced crystallinity of polyvinylidene probably arise from the same cause,
Substitution of the hydrogen in the -NH-CO- group by methyl or other
alkyl groups has an even more profound effect (Nos. 4 and 5).
TABLEIV
ADIPAMIDE
OF POLYHEXAM.ETHYLE;NE
METHOXYMETHYLATION
Amide
Meltins Elastio
Polymer Meaowk%
&Y%* point,
OC.
-tch.
%
Polyhexamethylene adipamide (unoriented) 0 0 264 45
N-Methoxymethylated polymex 5.77 22 185 285
N-Methoxymdylated polymer 7.81 32 130 370

The effect of methoxymethylation is due mainly to the elimination of hydro-

gen bonding, but the side-chain effect is probably there as well. The general effect
of progressive N-akylation of polyamides is, first, to reduce crystallinity and melt-
ing point, and then, to give the polymer increasing rubberlike properties.20~33
Brit. Pat. 534,699.
88 W. 0. Baker and C. S. Fuller, J . Am. C k m . Soc.,65, 1120 (1943).

618 Journal of Polymer Scienue

 POLYMER CONSTITUTION AND FIBER PROPERTIES

By dissolving a polyamide in formic acid and warming with paraformaldehyde

and an alcohol, alkoxymethyl groups are introduced into the polymer :
-CH2CHZ.CONCHZ-CHZ-
I
CH2.0R
Progressive alkox) methylation reduces the melting point of the polyamide, in-
creases its elasticity (i.e., increases reversible extension and decreases modulus), and
increases its solubility in ethanol.34 These effects are illustrated in Table IV.
Crystallinity of the polymers is progressively reduced, but the polymers are spinn-
able provided the molecular weight is high enough. The fibers possess rubberlike
elasticity. Linear polymers possess rubberlike elasticity when (1) the molecular
weight is high, (2) crystallinity is suppressed (or much reduced), and (3) the second
order transition temperature is low. The structural factors affecting second-order
transition temperatures are discussed by Boyer and Spencer3sand by Harper et al.36
These factors will .lot be treated here. Nevertheless, it is of interest to note that
high molecular aliphatic polyesters, with their low second-order transition tempera-
tures, give rubber) polymers when crystallinity is suppressed, whereas most poly-
amides and aroma tic polyesters, with their high second-order transition tempera-
tures, give glassy polymers under similar circumstances. N-Alkylation or N-
alkoxymethylation of polyamides appears to reduce both crystallinity and the sec-
ond-order transition temperature, and so gives rubbery polymers.
Influence of Aromatic Groups o n Melting Points of Polyesters,
Polyamides, and Polyurethans
Table V shows the effect of aromatic groups on the melting points of poly-
esters. For comparison, the melting points of aliphatic polyesters containing a
equal number of carbon atoms are given. The difference may be regarded a5 due
to the aromatic ring structure. The two phenylene groups in 7 produce an appreci-
able increase in melting point, but when the carboxyl groups are attached directly
to the aromatic nucleus as in 1, 3, and 5 the effect is much greater. The melting
point of 1 is above the point at which decomposition sets in, and the true melting
point is probably higher than this; the melting point of the hexamethylene glycol
ester has, therefore, been given for comparison. All the polymers in Table V are
fiber-forming, though 1 presents special dificulties owing to decomposition.
Table VI shows the effect of aromatic groups on polyamides. Similar effects
are observed, and hLere again the effect of terephthalic acid with the carboxy groups
attached directly to the aromatic nucleus is outstanding.
Table VII gives similar information on polyurethans. Some cycloaliphatic
rings are included, and these also raise the melting points.
All the aromatic and cycloaliphatic rings so far considered are of the symmet-
rical p,p’ class. The effects of lack of symmetry are startling. Carothers pre-
pared polyethylene o-phthalate in several different ways in attempts to obtain it in
a4 Brit. Pat. 573,482.
Boyer and Spencer, Advances in Colloid Science, Vol. 11. Interscience, New York, 1946.
88 D. A. Harper, W. J. S. Naunton, R. J. W. Reynolds, and E. E. Walker, “A review of
Poly-condensation Rul)bers,” Section 10, XIlh Intern. Congr. Pure Applied Chem., 1947.

Volume 3, NO. 5 (19488) 619

 R. H I L L A N D E. E. W A L K E R

TABLE V
INFLUENCE ON MELTING
OF AROMATICGROUPS OF POLYESTERS~
POINTS
Formula
number Repeating unit M.P.. OC. Footnote

1 -CO . o e O . 0 (CHZ)ZO- 346 37

2 -CO. (CH.JlZ. CO.O(CH&O- (estd.) 87 -

214 31

4 -CO. (CHz)lz.CO .O(CH&. 0- (estd.) 76 -

6
5 -CO
-CO
.O
1
- C O . O(CHZ)ZO-
(CH&. CO .0(CH2),.O- (estd.)
256
61-64
32
-

7 -CO. CH~OCH,. co .o.CH, 0 CHz .0- 146 30

8 -CO. (CHz)8~CO-O(CHz)s~O-
(estd.) 70 -

a All polymers fiber forming.

TABLE VI
INFLUENCE GROUPSON MELTING
OF AROMATIC OF POLYAMIDES"
POINTS
Repeating unit M.p., OC. Footnote

350 (decomposes) 30

235 18

-CO .CH, O m 2 co
. .NH ( c H ~ )NH-
~~. 242 17

-CO.(CH~)~.CO.NH(CH~)~O.NH- 194 18

Z . .N H (C&)6NH-
-CO ( C H , ) ~ O ( C H Z )CO 280-290 7

-CO(CHz)s. CO .NH .CHz

-CO
0
. (CHz)8*CO .N H .(CH2)S.NH-
CHz.NH- 268

197
17

18
a All polymers fiber forming.

a crystalline form, but he failed completely. In 1940, Whinfield and Dickson,

working in the research laboratories of the Calico Printers' Association, found that
the glycol esters of the symmetrical terephthalic acid were crystalline and that the
high molecular polymers could be spun and cold drawn to give strong fibers.
Table VIII gives the melting points and fiber-forming properties of the
ethylene glycol esters of the isomeric phthalic acids, the diphenylene dicarboxylic
acids, and the naphthalene dicarboxylic acids. No comment is needed since the
table is self-explanatory and demonstrates clearly the importance of symmetry.
a7 Brit. Pat. 588,497.

620 Journal of Polymer Science

 POLYMER CONSTITUTION AND FIBER PROPERTIES

TABLE VII
OF AROMATIC
INFLUENCE GROUPSON MELTINGPOINTS
OF POLYURETHANS

-
Repeating unit M.P.. OC. Footnote

-0. (CHz)3-c,)-(CHz)3. 0.CO .NH ( C H Z )NH

~ . .CO- 240 7

-0. (CHZ),o. 0.CO .NH (CH,)s.NH * CO- 135-138 23

(m.p. for 12-6 polymer not available)

)-(CHz)z. 0 .CO .NH (CH2)s* NH .CO- 208-212 23

160" 23

218-221 23

151-153 23
a Starts to melt at, 160"
b Interpolated from 68 polymer (152') and 108 polymer (136").

Details of this work, which was carried out in these laboratories, will be published
in the near future.
Among all these polymers containing aromatic groups, ethylene terephthalate
polymer is outstanding. Its melting point is high enough to withstand all ordinary
textile processing, and it is low enough for melt spinning. It is capable of yielding
high-tenacity fibers, and these fibers withstand hydrolysis by boiling water. This
last property is surprising in view of its ester character and must be attributed
mainly to its highly crystalline character and its low water absorption.
Ring structilres probably affect the crystallite melting point in various ways.
They are less fle>ible than the aliphatic chains they replace and this alone should
tend to raise the melting point. Aromatic rings probably contribute directly to
interchain cohesive powers; furthermore, when attached directly to the polar
groups as in the terephthalates, the total effect is enhanced. These positive effects
may be counterhalanced or more than counterbalanced by poor packing in the
crystal lattice if the configuration of the cyclic group is such as to give a low degree
of symmetry.
Influence of -0-, -S-, and -NR- Links on Properties
of Polyesters and Polyamides
Tables IX and X show the effect of -0- and -S- links on polyamides and
polyesters, respectively. The ether links, when attached only to aliphatic carbon
chains, lower the melting points considerably. In the case of the low-melting
aliphatic polyesters they eliminate crystallinity altogether and tend to give rubbery
polymers. Even diethylene terephthalate is noncrystalline and rubbery. Only
one example of the aliphatic -S- link is available, and this appears to have very

Volume 3, No. 5 (1948) 621

 TABLEVIII
EFFECTS
OF SYMMETRY.
ETHYLENE
GLYCOL OF AROMATIC
ESTERS ACIDS
DIBASIC
structure crystallinity M.p., "C. Fiber-forming propertien Footnote
-
Highly crystalline 256 Excellklht fiber - forming 32
U 1:4 properties

Noncrystalline 102-107 Spinnable; some slight signs 30

of cold drawing in high
molecular polymers
1:3
Noncrystalline LOW None 21
0 /1: 2\

Hghly crystalline 346 Spinnable with difficulty ow- 37

ing to high m.p.
-00-
Hexamethylene gly- Highly crystalline 214 Good 37
col ester of above
acid
Glassy polymer 156 Poor, slight signs of draw- 30
ability
00 Glassy polymer 132 None observed 30

'a
bi;
c
1
w

f
ul
e
c TABLE
VIII (Continued) h3
2! 0
w F
li.
I.UYL""uI
structure Lryatai-Enizy M.p. 'C. Fi'ber-;uruius prupen ti.8 ..-*.-
Highly crystalline 255-260 Good 38
2
$
n
0
2:6
m Crystalline 226-230 Spins and cold draws 38
5H
Y
4
U
s
Not markedly crystalline 220 Spinnahle; some indications 38
z
of drawability !
U
i
2: 7
zed
Noncrystalline 170 None observed 38
5
9
0 8
10
UnpubZuhed work, carried out in the Research Laboratories of Imperial Chemical Industries Ltd., by G . J. Cooke, H. P. W. Huggill, and
g
A. R.Lowe. F1
CP
 TABLEIX
EFFECT
OF -0- AND OF POLYAMIDES
-S- LINKSON PROPERTIES
Repeating unit M.p., OC. Spins Cold draws Footnote
-NH *
. (CH2)3 0. (CH2)r 0* * (CH2)a* NH * CO * C O - 160 Yes Alleged t o form good bristles 7
little affected by moisture,
and stable t o boiling water
([tll = 0.76)
-NH. (CHz)ioNH.CO.CO *- 229 YeS Yes 39
(M.P. for next higher even homolog likely to be a few
degrees lower)
-NH(CHZ)a.O.(CHz)8.NH*CO(CH2)d.C0- 190 Yes Yes 40
-NH(CH2),.NH*CO(CH,), .CO- 209 Yes Yes
-NH (CH2)2* 0. (CH2)2.0* (CHz)zNH.CO . (CH2)4CO- 160 Yes Yes; water-soluble ([q] = 0.73) 41
-NH(CH2),.NH*CO. (CH2)4’CO- 235 Yes Yes 18
-NH (CH2)bNH* CO * CH2.0. CHz CO- - 130 Yes Yes 42
-NH(CHz)6NH.CO. (CH2)a.C e 198 Yes Yes 18
-NH(CH2)6NH.CO. (CH2)a.S.(CHz)a*CO- 200 Yes Yes 40
-NH(CH2)e.NH.C0. (CHZ),CO- (estimated) 205 - -

39iBrit. Pat. 503,376.

3 40,Brit. Pat. 487,734.
4U 4 1 Brit. Pat. 562,370.
D Brit. Pat. 520,262.
%
Ld
g.
1
I
 TABLE X
OF -0-
EFFECTS AND -S- LINKSON PROPERTIES
OF POLYESTERS
Formula
number Repeating unit [q] M.p., OC. Spins Cold draws Propertiea Footnote
1 Low - - Syrup becoming rubbery 30
with increasing M. W.
2 >45" - - Should be typical fiber
former

3 LOW - - Syrup becoming rubbery 31

with increasing M. W.
4 116 Yes Yes Typical fiber-forming 30
polymer
Yes
5 220 Yes (slight) Crystalline 31
(Amorphous polymer
melts a t 136 "C.
6 -co. o . s . ( I > . c o . 0. (CH2)2.0- - 190-200 Yes Yes 43

1 152 Yes Yes Horny; low order of crys- 43

tallinity

8 170 Yes Yes Crystalline 31

9 190 Yes Yes 43

10 240 Yes Yes Crystalline 44

a Melting point of this ester is riot available. It should be a few degrees higher than that of the trimethylene glycol ester (m.p. +45"C.).
43 Unpublished work, carried out in the Research Laboratories of Imperial Chemical Industries Ltd., by G. J. Cooke, J. T. Dickson, H. P. W.
IIuggill, and A. R. Lowe.
4 4 Brit. Pat. 579,462.
 TABLEXI
POLYAMIDES
AND POLYURETHANS
CONTAINING
BASIC-NR- LINKS
Formula
number Repeating unit 1111 M.P.. 'C. PrOpertiSS Footnote

/cHz* CHt\
1 -NH(CH~)~*NH.CO.CHZ*N N CHz * CO-
. 0.41 168 Spinnable; soluble in al- 45
\ / coho1 and dilute ace-
CH**CH* tic acid

/CH2-CHn\
2 -NH(CH~)~.O.(CHZ)~.O*(CH~)ZNH.CO.CH~.N N.CH*.CO- 0.54 115 Spins and cold draws; 45
\ / soluble in water and
CHz.CH2 alcohol
CH:
202 Dyes with acid wool col- 7
ors so rapidly that re-
tarders must be used

Very soluble in water 41

/CHz'CH2 \
5 -O*CHz.CHz*N N .CHz * CHz * 0* CO * NH * (CH2)eNH CO- 165 Gives basic fibers which
\ / dye with wool and di-
E(, CHz*CHz rect cotton colors
4 4 Brit. Pat. 543,426.
p1

F
1
 POLYMER CONSTITUTION AND FIBER PROPERTIES

little effect. Aliphatic ether links render the polymer more sensitive to moisture,
and an accumulation of such links may render the polymer soluble in water. They
also increase the dubility of the polymer in oxygenated organic solvents. Aro-
matic or partially aromatic ether links do not increase water sensitivity; in many
cases, they raise the melting point.
Number 7 of Table X is low melting, but it is noncrystalline or nearly so. If
it could be obtained in a crystalline form like Number 5 it would probably melt a t a
much higher temperature. The effect of sulfur links (-S-) seems to be relatively
small.
Ether links probably exert two opposing influences on the melting point. The
ether link possesses greater cohesive power than the -CH2-- group it displaces.
On the other hand. it is believed to render the molecule more flexible (see page 617).
Probably the second influence predominates in an aliphatic chain, while the first
predominates in close proximity to an aromatic group.
Table XI shows the effect of -N-CH3- and -N< links on the melting
points and other properties of polyamides and of one polyurethan. In this case,
owing to the disturbing effects of the piperazine ring structures and the methyl
groups, it is not possible to assess separately the effect of the basic nitrogen link of
the melting points. The over-all effect of the piperazine ring in (1) is to lower the
melting point when compared with decamethylenesebacamide (m.p. 209"C.),
while the melting point of the polyurethan ( 5 ) is raised slightly as compared with the
polyurethan from decamethylene glycol and hexamethylene di-isocyanate (m.p.
154"C., estimated). Since the general effect of ring structures is to raise the melting
point, one is led to believe that the nitrogen link lowers the melting point in much
the same way as the oxygen link.
According to I. G. Farbenindustrie,' the following diamines :
.
NHz (CH2)-N- -
(CH2)s NHz
AH3
NH2. (CHr)rN-(CHs)p*NH2
I
CH*

/CH2.CHz
NH2 ( C H i ) r N
\
h--(CHt)sNH2
/
CHz.CH2

by interaction with di-isocyanates, give fiber-forming polyureas possessing good

affinity for wool dres.
The most important effect of the basic nitrogen link is that it renders the
polymers readily dyeable with acid colors. It also tends to make the polymer solu-
ble in acid. It increases solubility in organic solvents, and, in conjunction with
-0- links, may render the polymer completely soluble in water.
Components containing basic nitrogen need not be used to the extent of 100%
in order to give improved dyeing properties. Small quantities interpolymerized
with other components produce a very marked effect.
The quantity of an acid dye taken up by commercial nylon yarn under normal

Volume 3, No. 5 (1!348) 627

 R. H I L L A N D E. E. W A L K E R

dye-bath conditions is strictly limited by the number of basic -NH, end groups
present.4B In normal yarn there is less than one of these groups present for every
two molecules of polymer (0.06 milliequivalent). By using a basic instead of an
acid end-group stabilizer, this can be increased considerably. The use of 0.02
mole of a special basic end-group stabilizer :7
CHZ-CH,
\
I
CHz-CHz
/N(CHe)G.NH2

which contains a tertiary basic group as well as the basic amide-forming group, leads
to a significant improvement in dyeing properties.
Other properties of a polymer may be affected by modification of the end
groups. Thus, for instance, replacement of the acetic acid viscosity stabilizer by
o-hydroxyphenoxyacetic acid increases the durability of the fiber on exposure to
sunlight from two to three times.47
Influence of Active Substituents in the Polymer Chain
The preparation of condensation polymers having reactive side chains offers
special difficulties since there is a strong tendency for the side chain to react giving
cross-linked, three-dimensional polymers. Such polymers are insoluble, infusible
gels or rubbers, and cannot be spun into fibers. Fusible high molecular polyamides
can be prepared from diamines and dibasic acids, or from amino acids which contain
a hydroxyl group removed by at least 5 atoms from the nearest carboxyl group, or
by at least 3 atoms from the nearest amino group.48 The polymer from hexa-
methylenediamine and 6-hydroxyhendecanedioic acid ( [ q ] = 1.05) melts at 160-
165"C., spins, and cold draws. The hydroxyl group increases the water sensitivity
of the polymer and offers a point of attack for further chemical reaction. Thus, for
instance, the polymer can be cross linked by reaction with di-isocyanates. Poly-
mers containing a hydroxyphenyl substituent can be coupled with diazo compounds.
The polyamide from 6-hydroxyhendecanedioic acid and triglycoldiamine ( [q ] =
0.77) melts at 156"C., spins, and cold draws. It is soluble in water and strong
pliable films can be cast from the aqueous solution.
The polyamide from 4-ketopimelic acid and hexamethylene diamine begins
to soften a t 180"C., but, unlike most polyamides, melts over a range of 30-50°C.
This may be an advantage for a plastic, but, for a fiber, it would probably be un-
desirable. Its interpolymers with caprolactam are soluble in glycol ethers.
This concludes the discussion of the effects of chemical constitution on fiber-
forming properties. The whole of the published information on fiber-forming con-
densation polymers has been reviewed by the authors, and a very large proportion
of it has been included in this paper together with some higherto unpublished infor-
mation.
Work on interpolymers has been excluded except in the case of certain ni-
46 R. H. Peters, J . Soc. Dyers Colourists, 61, 95 (1945).
47 Brit. Pat. 568,688.
48 Brit. Pat. 544,649.

628 Journal of Polymer Science

 POLYMER CONSTITUTION AND FIBER PROPERTIES

trogen-substituted polyamides. The melting points of polymers depend t o some

extent on the manner in which they are determined, the different workers adopt
different methods; moreover, impurities and the products of side reactions (if not
removed) may affect the melting points. However, the effects of chemical consti-
tution on melting points are so large that errors arising from these sources are rela-
tively unimportant. Positive statements that a polymer is fiber-forming may gen-
erally be regarded as reliable, but negative statements may mean merely that at-
tempts to form fibers have been unsuccessful.
On the whole it is believed that the conclusions drawn are fairly reliable, but
i t is realized that they do not go very far. The fiber technologist is interested in a
multitude of mechanical properties such as tensile strength, transverse strength,
modulus a t different extension, handle, and drape; but for reasons which have been
given, these cannot be correlated with chemical structure a t the present time.
Such information must be obtained the hard way by detailed studies of spinning
conditions and aftertreatments for individual polymers.
Synopsis
The chemical structure of a large number of linear condensation polymers is correlated with
their ability t o assume a polycrystalline form possessing the right degree of thermal stability, and
with the possession of fiber-forming properties. Certain structures lead to the absence of crystal-
linity and of fiber-forming properties, while, under certain conditions, a low degree of crystallinity
or. its complete absence leads to polymers possessing rubberlike properties, which may form highly
elastic threads. Some properties of fibers such as solubility, sensitivity t o moisture, and certain
dyeing characteristics, can be correlated t o some extent with chemical structure. These effects
are considered on the basis of the introduction of various polar links and ring structures, according
t o regular patterns, into the polymethylene chain (polythene). The ether (-Cb-) and ester
(-CO.O-) links lower the crystallite melting point to such an extent that some polymers con-
taining them are completely noncrystalline a t normal room temperatures. Urethan (-0.CO.-
NH-), amide (-CO.NH-) and urea (-NH.CO.NH-) links raise the crystallite melting point
t o an extent which increases in the order named. Most other polar links raise the melting point.
The introduction into the aliphatic chain of ring structures, particularly aromatic rings directly
attached t o polar groups, raises the crystallite melting point, but in this case symmetry exerts an
over-ruling effect. A low degree of symmetry may lower the melting point and eveneliminate
crystallinity entirely t o the detriment of fiber-forming properties. Inert side chains lower the
melting point considerably, and in some cases render the polymer completely noncrystalline a t
normal room temperatures.

RBsumd
La composition chimique d’un grand nombre de polycondensats lin8aires est en relation
ktroite avec l’aptitude que prBsentent ceux-ci b former une substance polycristalline, posskdant
une stabilitk thermique suffisante, et avec I’existence des propriktks nkcessaires B I’8tirement en
fibres. Certaines structures entrainent une absence de cristallinitk e t de proprikt8s fibreuses;
d’autre part, dans certaines conditions, un faible degr8 de cristallinitk ou son absence totale rend
possible la formation de polymbres semblables au caoutchouc, qui peuvent alors servir B la produc-
tion de filaments trBs klastiques. D’autres propriktks des fibres, telle leur solubilitk, leur sensibilit8
I’humiditk et certaines caractkristiques de teinture sont kgalement tributaires, du moins en
partie, de la composition chimique. Ces effets sont Btudiks en se basant sur l’introduction de dif-
f8rents groupes polaires et de cycles, suivant une p8riodicit8 dkterminke, au sein d’une chaine
polymkthylbnique. Les groupes Bthers (-0-) et esters (-CO-0-) diminuent le point de
fusion des cristallites, b tel point que certains polymbres sont totalemen; d6pourvus de cristallin-
it8 A temperature de chambre. Les groupes ur6thanes (-O--CO-ihH-), amides (-CO-

Volume 3, No. 5 (1948) 629

 R. H I L L A N D E. E. W A L K E R

NH-) et ur6ides (-NH-C&-NH-), au contraire, augmentent le point de fusion progressive-

ment d’apr8s leur ordre prhit6. La plupart des autres groupes polaires augmentent le point de
fusion 6galement. L’introduction, dans la chafne aliphatique, de cycles, principalement de
noyaux aromatiques attach& directement aux groupes polaires, augmentent &dement le point
de fusion des cristallites, mais en ce cas-ci, La sym6trie de 1’6ddifice exerce l’effet dominant. Un
faible degr6 de sym6trie peut abaisser le point de fusion. voire meme, &miner entihrement la
cristallinit6 au detriment des propri6t6s fibreuses de la substance. Les chafnes lat6rales apolaires
diminuent le point de fusion considerablement, et peuvent, dans certains cas, occasionner une
absence totale de cristallinite 8. temperature de chambre.
Zusammenfassung
Die chemische Struktur einer grossen h z a h l von linemen Kondensationspolymeren wird in
ihrer Eigenschaft, polykrystallie Form mit dem richtigen .Grad von thermischer StabilitTt
anzunehmen, und in ihrer Eigenschaft, Fasern bilden zu kbnnen, in Zusammenhang betrachtet.
Gewisse Strukturen fiihren zur Annabme einer Abwesenheit von Kristallinitat und Faserbildungs-
vermiigen; andere zeigen unter gewissen Bedingungen einen niedrigen Kristallisationsgrad oder
seine komplette Abwesenheit,die zu gummi&nlichen Eigenschaften fuhrt-namlich hochelastische
Faeden. Einige Fasereigenschaften, wie Liislichkeit, Feuchtigkeitsempfhdlichkeit und gewisse
Faerbeeigenschaften k6nnen mit der chemischen Struktur in Zusammenhang gebracht werden.
Diese Effekte werden auf der Basis der Einfiihrung von polaren Gruppen und Ringstrukturen in
die regelmlssigen Netzebenen in die Polymethylenkette (Polythen) erklirt. Ather (U )
und
Ester- (-CO.O) bindung erniedrigen den Kristallitschmelzpunkt so sehr, dass einige polymere
Ester oder Ather bei Zimmertemperatur viillig amorph sind. Urethan- (--O.CO.NH-), Amid-
(-CO.NH-), und Harnstoff- (-NH.CO.NH-) bindungen erhiihen den Kristallitschmelzp~t
in der obengenannten Reihenfolge. Ringschliessung in aliphatischen Ketten, besonders unter
Bildung von aromatischen Ringen an polaren Gruppen, erhiiht den Schmelzpunkt; aber Symme-
trieeinfluss ueberlagert diesen Effekt. Geringe Symmetrie kann den Schmelzpunkt erniedrigen
und die Kristallinitat vsllig zum Verschwinden bringen, unter Unterdriickung von jeglichem
Faserbildungsvermtigen. Neutrale Seitenketten erniedrigen den Schmelzpunkt betrachtlich
und machen manchmal das Polymer bei Zimmertemperatur viillig amorph.

Received January 21,1948

630 Journal of Polymer Saiener