A Study of Intramolecular Reaction and Gelation during

Non-linear Polyurethane Formation

J. L. Stanford and R. F. T. Stepto
Department of Polymer and Fibre Science, The University of Manchester Institute of Science and Technology, Manchester M60 IQD,England

Intramolecular reaction and gelation in reactioas of a poly(propy1ene oxide)triol and

hexamethylene di-isocyanate in benzene at 70 have been investigated. The numbers of
ring structures formed in the pre-gelation region have been evaluated from cryoscopic
measurements of M, and overall extents of reaction of isocyanate groups. It is found that
intramolecular reaction increases with initial dilution, and a t a given dilution is a maximum for equimolar concentrations of reactive groups. Again, at a given initial dilution,
more intramolecular reaction occurs than for linear polymerisations. Various ways of presenting the results are discussed, and one of them in particular, the extent of intermolecular reaction, pch, as a function of overall extent of reaction of the minority group, p ,
gives useful linear relationships. Also, by combining gelation and intramolecular reaction
in terms of plots of pch vs. p , a distinction can be drawn between what may be termed the
chemical and physical gel points. Finally, values of the Flory-Huggins interaction parameter, x,have been determined from the cryoscopic data. These show fairly normal behaviour - they are generally less than 0.5 - with some dependence on the density of
hydroxyl groups and the proportion of polyoxypropylene units present. Such behaviour
is in sharp contrast with that found previously for poly(ethy1ene-oxide)/hexamethylene
di-isocyanate systems.

1. INTRODUCTION
Intramolecular reaction in non-linear polymerisations has
been investigated mainly in terms of extents of reaction at
the gel point. 1-4 However, consideration of merely a
single point in the polymerisation process allows only a
limited interpretation of the intramolecular reaction which
occurs throughout the course of a p ~ l y m e r i s a t i o nand
,~
limits understanding of the molecular structure of the network which may be formed subsequent to the gel point.

A previous paper has presented total ring fraction data

pertaining to intramolecular reaction during irreversible,
linear polyurethane formation, where ring structures, once
formed, cannot participate further in the polymerisation
process. These data have been analysed according to various
theoretical approaches, Jacobson-Stockmayer-Kilb
t h e ~ r y kinetic
,~
analysis,6 cascade t h e ~ r yand
, ~ rate
t h e ~ r y and
, ~ are
~ ~now reasonably well explained. Total
ring fraction data, or even better data on the distribution of
ring sizes in a polymerising system,'" are necessary for a
complete understanding of polymerisation processes.
Hitherto, even total ring fraction data has not been available for non-linear polymerisations.
In comparison to the linear case, intramolecular reaction
during non-linear polymerisation produces ring structures or
loops attached to branched molecules, which themselves
still have the opportunity to react intermolecularly. Nevertheless, the principle relating to the experimental determination of intramolecular reaction during linear and nonlinear polymerisations is the same, viz. that the relation between overall extent of reaction and number of molecules is
affected by the proportions of inter- and intra-molecular
reaction occurring. With intramolecular reaction, the loss of
a pair of functional groups produces no change in the number of polymer molecules in the system. This is not so with
intermolecular reaction, where one molecule is lost to the
system for every pair of groups reacted. Hence, one can
evaluate the amount of in tramolecuiar reaction from
determinations of the number of molecules (related to inter124

molecular reaction) and the overall extents of reaction of

functional groups (related to intermolecular and intramolecular reaction).
The present paper presents data on intramolecular reaction
up to and including the gel point in reactions between a trio1
and a di-isocyanate to form non-linear polyurethanes. As
previously, reactions were carried out at 70" in bulk and in
benzene. The amounts of intramolecular reaction at different extents of reaction were determined for reactions
carried out at different initial dilutions and different ratios
of components. The suitability of the polyurethane-forming
reaction for the study of intramolecular reaction has been
discussed previously in detail,5 and the amounts of intermolecular and intramolecular reaction were again determined from measured values of overall extents of reaction
(p) and number average molecular weights (Mn), using similar techniques to those already r e p ~ r t e d . ~ ~
The total ring fraction and gelation results are here discussed
in a qualitative manner and comparisons are made with the
previous data from linear polyurethane systems. In addition, the essentially equilibrium cryoscopic technique employed for the determination of M, enabled values of the
Flory-Huggins interaction parameter x,to be determined.
These x values are also reported and compared with those
from the linear system^.^

'

2. EXPERIMENTAL
Purification of Materials
Benzene was used as solvent both for the polymerisations
and the subsequent cryoscopic analyses, and was purified
and stored as described previously.
Hexamethylene di-isocyanate (HDI) was purified by fractional distillation under reduced pressure as described elsewhere l 2 (molecular weight of fraction used 168.2, theory
168.2).
THE BRITISH POLYMER JOURNAL, JUNE 1977

Niax Trio1 (LG56), manufactured by Union Carbide Corporation, is a propylene oxide adduct of glycerol and has the
structural formula

where k, the number average degree of polymerisation for

each branch, is approximately equal to 17. Two batches of
LG56 were dried by azeotropic distillation with benzene
and their equivalent weights were determined by quantitative acetylation of the hydroxyl groups as described by
Hopkins et aL2 Further analysis by cryoscopy gaveM,,
values for each batch and comparison ofM, values with
corresponding equivalent weights gave a ready estimation of
the number average functionality
of the triol. The
results are given in Table 1.

u,,)

Table 1. Characterisation of triol

Batch

Equivalent Weight'
(EW) g equiv-'

M i g mol-'

fn (=M,/EW)

1
2

1007 2
1011 t 2

3016
2985

2.99
2.95

t Units expressed as g equiv. rather than g (mot OH)-'

* Reported accuracy f 1%

Once purified, the HDI and LG56 were stored under anhydrous conditions at about -20".
Polymerisation reactions and gelation procedure
A detailed account of the apparatus and experimental procedure has been given elsewhere s and only a resume is presented here. All reactions were conducted at 70 f 0.1",
with continuous stirring and in sealed flasks to give anhydrous conditions. Samples were withdrawn intermittently
from reaction mixtures, and were titrated for -NCO groups
remaining to give the overall extents of reaction. Other
samples were also removed and stored at -20" until required for subsequent cryoscopic analysis. Extents of reaction at gelation were determined via extrapolation of
conversion-time plots to the gel time, which was taken as
that time at which the reaction mixture cIimbed the stirrer
of the reaction flask.' The reactions, which were spontaneous (i.e. no added catalyst), did not follow simple order
kinetics but displayed an apparent order between one and
two.
Table 2 summarises the initial concentrations and ratios of
reactants for the polymerisations studied. Where appropriate, p c , the extent of reaction of the minority group at
gel, is given. Due to intramolecular reaction, gelation was
not observed in the more dilute systems with r f 1, expt.
2.3-2.5 and 3.3., 3.4. In the absence of such reaction,
gelation would be expected as r lies in the range
~25r52.
1i

Subsidiary experiments
During the previous investigation subsidiary experiments
were carried out as a check on possible systematic errors in
T H E BRITISH POLYMER JOURNAL, JUNE 1977

Table 2. Initial concentrations and ratios and gel points.

r = [NCOI ,/[OH1
W/W%

[NCOIo

[OHIO

Expt

reactants

equiv kg-'

equiv kg-'

1.1
1.2
1.3

bulk

70
50

0.9073
0.6397
0.4485

0.9173
0.6408
0.4490

1.4

40

0.3929

0.3652

1.5

30

0.2741

0.2738

2.1
2.2

bulk

70

1.3223
0.9161

0.8797
0.6159

2.3
2.4
2.5

50
40
30

0.6602
0.5280
0.4065

0.4392
0.3526
0.2711

3.1
3.2

bulk

70

0.6236
0.4230

0.9375
0.6352

3.3
3.4

58
40

0.3641
0.2494

0.5470
0.3750

Pc

0.989 0.765
0.998 0.780
0.999 0.799
k0.002
1.076 0.842
k0.003
1.001 0.831
f0.004
1.503 0.945
1.488 0.9495
t0.002,
1.503 1.497 1.499 111.503 0.925
111.502 0.946,
kO.002,
1/1.503 1/1.503 -

the experimental procedures and hence in total ring fraction

data as a function of overall extent of reaction. Similar subsidiary experiments were carried out here.
(0 Loss of solvent. Under the experimental conditions
employed less than 1% per week occurred. The shortest experiment took 3 days and the longest about 5
weeks. Hence, the losses made negligible differences
to concentration evaluated on the basis of weights of
reactants and initial weight of solvent.
(ii) Extent of reaction in stored samples. The concentrations of -NCO groups in samples removed from reaction mixtures were determined immediately and
also following cryoscopic analysis. Between the
determinations, the samples were stored at -20" for
up to 4 months. This was the case for samples from
experiment 1.1 and the difference between the extents of reaction for each sample was never greater
than 0.002. Experiment 1.1 was the fastest reaction
and in all other experiments the changes in p on
storage were negligible.
(iii) Side reactions during polymerisations. Possible side
reactions occurring during linear polyurethane formation using poly(ethy1ene oxide) (PEO) diols and HDI
have been discussed previously. It was assumed that
similar side reactions would occur in the present poly(propylene oxide) (PPO) triol/HDI systems. Side reactions appeared to be less significant for the present
systems; for reactions with excess isocyanate (r = 1.5)
less than 7% reaction of isocyanate groups in excess of
that required for complete reaction of hydroxyl
groups occurred. This may be compared to the 10%
found for the linear systems at approximately the
same value of r.

125

Cryoscopic analysis
The cryoscopic determinations of M, were carried out as
l1 Freezing points were measured using a thermistor having a sensitivity of 118 S2/"C. In comparison with
the linear systems, generally higher values of M, were
measured. The highest value of M, successfully measured in
the present work was about 7000, at which molecular
weight the accuracy was probably less than the f 1% quoted
previously. For the non-linear polymers studied here, the
range ofM, values which could be measured was limited by
solubility rather than by the sensitivity of the apparatus.
However, no phase separation was observed in the course of
obtaining the results presented in this paper. Given a polymer sufficiently soluble in benzene at about 5" it is expected that the present apparatus could be used for molecular
weights in excess of 10,000.
3. RESULTS
Number average molecular weights
Assuming Flory-Huggins' theory for dilute solutions, cryoscopic data can be analysed according to the equation

Here, 0 = loglo (r/ro),with r and ro the thermistor resistances at the freezing points of solution and solvent, respectively. W1 and W2, are the weights of solvent and solute in
the cryoscopic cell, k is the apparatus constant (established
using a standard solute),M1 is the solvent molecular weight,
and p 1 and p2 are the densities of solvent and solute.
M, was evaluated according to equation (1) from linear
least-squares analysis of (0Wl/kW2, W2/W1) data points.
Examples of plots of 0Wl/kW2 vs W2/Wl are shown in Fig.1
for expt 3.1. These plots are typical in terms of their linearity and the scatter of experimental points about the leastsquares lines. The uncertainty in values of the intercepts
(= l/M,) was less than k 1%, as quoted p r e v i o u ~ l y . ~
In the work on linear POE-based polyurethanes in b e n ~ e n e , ~
an alternative method for evaluating M, was also employed.
This gave M, as the limiting value of the apparent molecular
weight at a finite concentration, MA , through the equations
M A = kW2/@W2

(2)

and

M, = lim MA ,
o-a

and plots of MA vs. 0 were found 'to be linear, giving values

ofM,, to within 1% of the values obtained through equation (1). In contrast, the present non-linear, PPO-based
polyurethanes showed markedly curvedMA us. 0 plots as
shown in Fig.2, and these could not be used to obtain reliable values of M, . The behaviour of the present systems is
in fact more characteristic of the general dilute solution
properties of polymers, both in terms of the curvature of
the plots in Fig2 and the values of x which can be obtained
from the plots in Fig.1. These points are discussed later.
Presentations of total ring fraction data
The titrations and the cryoscopic measurements carried out
on samples withdrawn from reaction mixtures yielded, in
126

I
1

I
2

3
102 (W*/WI )

I
6

Fig.1 Plots of @ W l / l c W 2 versus W ~ / W for

I expt 3.1. Numbers 1
to 6 with the individual plots refer to samples withdrawn at increasing extents of reaction.

the first instance, values ofM, and p a , the overall extent of

reaction of isocyanate groups. In the present paper these
are used to provide three alternative presentations of what
may be termed total ring fraction data. These are in terms
of (i) N,, the number fraction of ring structures, (ii)M,,
and (iii) pch, the extent of intermolecular reaction of the
minority component, as functions of p , the overall extent
of reaction of the minority group. It is perhaps appropriate
to mention here that pch and p are in fact the 01 and 0 introduced earlier by Gordon and Temple.6
(i)N,.
This has been used previously in the context of
linear polymerisations.s-7~9~lo*l 3 For non-linear systems
the definition of N , has to be generalised somewhat from
that used hitherto. This arises because in a non-linear system molecules containing ring structures may be able to
partake in further reaction. The occurrence of ring structures is illustrated in Fig.3. (a) shows a molecule not capable of further reaction, which contains two pairs of groups
which have reacted intramolecularly, giving rise, in this case,
to two ring structures of the smallest size possible (onemembered). (b) shows part of a molecule in which only
one pair of functional groups has reacted intramolecularly
to give a two-membered ring structure.
To define N,, let X be the total number of molecules and Z
be the number of ring structures (or the number of pairs of
groups which have reacted intramolecularly) at extent of reaction p a . Let N,, a n d N b be the initial numbers of moleTHE BRITISH POLYMER JOURNAL, JUNE 1977

This may be compared w i t h e , the value expec(ii) M,.

is
ted in the absence of intramolecular reaction, where
given by the standard equation

Mo,=

)(

fbr ' f a

f b r ' f a - fafbrpa

Ma/fa
l/fa

'

Mb/(fbr))

(.,)

I/Cfbr>

(iii) Pch. This may be compared with p just as M , is compared with ME. The advantages of using pch and p rather
than the more ovious M , and fl, will become apparent
later. Also, p - pch = p r , the corresponding extent
of intramolecular reaction.
With respect to A groups, the extent of intermolecular reaction, p m h , can be defined using the following arguments.
The number of ring structures, I , is obtained from equations
(4) and (5) as

0.4

0.8

1.2

1.6

2.0

2.4

lo3
Fig.2

Plots ofMA versus 0 for the same data as in Fig.1.

cules in an Rlf,+ RBfi type polymerisation. Assuming

only intermolecular reaction, every pair of groups reacted
results in the loss of one molecule. f a N g , pairs of groups
have reacted at p a and the number of molecules expected is
Na t N b - f a N , p a . The difference between X and this number is the number of ring structures, that is

Z is also equal to the number of A groups (or B groups) reacted intramolecularly and subtraction of I from the total
number of A groups reacted (= f&Japa) gives an expression
for the number of A groups which have reacted intermolecularly, namely

(9)
Division of expression (9) by the initial number of A groups
(= faNa)gives

Xis determined from M , as

which can be written
where Mu and M b are the molecular weights of RAf, and
Thus the number fraction of ring structures (=Z/X)
is given by the equation

RBfb.

Pach =

("
fa

L,

fbr

( )-:

where x n is the number average degree of polymerisation

given by the equation

For reactions with r < 1, p c h = p a & . For reactions with

r > 1, pch = P b c h , which is readily obtained from equation
( 1 1 ) and the relationship r = P b c h / P & , (= p b l p , ) .

Fig.3 Examples of ring structures in an RA2 + RB3 type ~ 0 1 ~ merisation. (a) Pentamer with functional groups completely reacted.
(b) Part of a continuing molecule.

THE BRITISH POLYMER JOURNAL, JUNE 1977

The primary data obtained from the experiments, namely,

values of M, and p , for the various samples withdrawn
from the polymerisations listed in Table 2 , will, for reasons
of space, not be given in tabular form in the present paper.
Instead the presentation will be in graphical form in the
127

0.

0.6

r = 1.0

0.5

0.E

0.4

0.4

111.5

1
Nr

0.3

Nr

3.4/

/P

0.3

0.2

0.2

0.1

0.1

0
V.V

".L

0.2

V.0

Fig.4 Number fraction of ring structures, Nr, versus extent of

reaction, p, for r = 1.
o - expt 1.2, 70% monomers;
0 - expt 1.1, bulk;
0 - expt 1.3,50% monomers;
o - expt 1.4,40% monomers;
- expt 1.5,30% monomers.

0.6

0.4

0.8

Fig.6 Nrversusp, f o r r = 1/1.5.

= - expt 3.1, bulk; a - 3.2, 70% monomers;
- expt 3.3,58% monomers; 0 - expt 3.4,40% monomers.

linear

0.6

Expt. 3

[NCOI 0 + (OH1 0

0.5

1 equiv kg-

0
r = 1.5
0.4

0,

Nr

0.3
0

Nr

0.2

0
0.1

0.2

0.4

0.6

0.8

Fig.5 Nr versus extent of reaction of minority group, p , for r = 1.5.

A - expt 2.1, bulk;
L, - expt 2.2, 70% monomers;
A - expt 2.3,50% monomers;
A - expt 2.4,40% monomers;
A - expt 2.5, 30% monomers.

128

Fig.7 Nr versus p, for experiments at same initial concentrations

([NCO] + [OH] 0 2 1 equiv kg-I).
0 - expt 1.3, r = 1, 50% monomers, [NCO] 0 + [OH] 0 = 0.8975
equiv kg-' .
a - expt 2.4, r = 1.5,40% monomers, [NCO] 0 + [OH] 0 = 0.8806
equiv kg-'.
- expt 3.3, r = l / l S , 58% monomers [NCO] 0 + [OH] 0 = 0.9111
equiv kg-' .
x - Stepto and Waywell,' HDI/poly(ethylene glyc01)200, expt 3,
r = 1, 10% monomers, [NCOIo + [OHIO= 1.0616 equiv kg-'.

THE BRITISH POLYMER JOURNAL, JUNE 1977

k 6
E
0

r'

0.2

0.4

0.6

0.8

1 .o

Fig.8 M , versusp, for r = 1. Legend as for Fig.4 except

- expt 1.3, ---- no rings, and * - gel point.

course of the discussion in terms of N,, M,, and P c h , as previously indicated. The primary data may be obtained
directly from the authors, if so desired.
4. DISCUSSION

Effects of dilution and ratio on intramolecular reaction

The data from experiments at the three values of r are
shown in Fig.4, 5 and 6, in terms of the variation of N , with
p . For the experiments in Fig.4, nominally at r = 1 , the
abscissa may be taken as p a or p b , except for expt 1.4, for
which r was somewhat greater than 1, and (papb)" was
employed.
The curves in each of the figures show that, as expected,
ring formation increases markedly with p and with dilution
at a given ratio of reactive groups. The behaviour shown
follows qualitatively that found for linear system^,^ but
larger values of N,. occur. This and the effect of the ratio onN,
are clearly illustrated in Fig.7 where data from experiments
at approximately the same concentrations of reactive groups
are compared. There are three experiments from the present
work and one from Stepto and W a y ~ e l l .Comparing
~
first
the two curves for r = 1 (expt 1.3 and 3), about three times
as many ring structures were formed in the non-linear as
compared to the linear polymerisation, at least over the
more limited range of p accessible in the non-linear case
prior to gelation. This excess occurs despite the fact that
the value of v, the number of bonds in the smallest ring
which can form, for the non-linear system is about four and
a half times larger than that of the linear system (1 15 cornpared to 25.2), and the polyoxypropylene chain of the nonlinear system is intrinsically less flexible than the polyoxyethylene of the linear system.
The effect of the ratio on N, in the present work can be seen
from curves 1.3,2.4 and 3.3. in Fig.7. Maximum intramolecular reaction occurs when r = 1, and from curves 2.4
and 3.3, N , at r = 1.5 is slightly greater than N , a t r = 1/ I S .
Some of the difference between these two curves must be
attributable to the slightly differknt values of [NCO] 0 +
THE BRITISH POLYMER JOURNAL, JUNE 1977

[OH] for the two experiments - the larger value giving less
ring structures. Similar results were also found for linear
polymer is at ion^,^ at least over the range of r of interest
here. However, gelation studies have shown that intramolecular reaction is not necessarily symmetrical in r and
l/r at a given initial concentration, with more rings forming
at r > 1. Fig12 (later) shows that on the basis ofp,h there
is still a distinction between the results of expt 3.3 and 2.4.
Further investigation of the effects of the ratio of reactive
groups on intramolecular reaction in linear and non-linear
polymerisations is obviously required.
The second way of presenting the effects of intramolecular
reaction is shown in Fig.8, as the variation ofM, w i t h p for
polymerisations at r = 1. (A similar representation is also
possible on the basis of x, versus p . ) The dashed curve for
no ring structures is a plot ofMO, YS. p a , according to equation 7. The use ofM, has the advantage that comparisons
with a curve for no ring structures can be made. For example, at the ideal gel point (p = 0.707), M , for the bulk reaction is only about 2/3 o f M i . However, reactions for
different values of r cannot be compared in this way as M",
(or x:) is a function of r.
Presentation of intramolecular reaction in terms of pch
This is shown in Fig.9 to 12. pch was evaluated by means
of equation 1 1, as described previously. Fig.9 to 1 1 give
pch as a function of p for the reactions at r = 1, 1.5, and
1/1.5, respectively (cf. Fig.4 to 6). In these figures, data
from some of the experiments listed in Table 2 and shown
in Fig.4 to 6 have been omitted for clarity. Fig.12 shows
the same results as Fig.7, illustrating the effects of changing
r and making a comparison with a linear system. With the
use of pch there exists a datum line, p!& = p , which is shown
as dashed in Fig.9 to 12, corresponding to the case of no
ring structures, and the difference pEh - pch = p r is the extent of intramolecular reaction.
Overall, the behaviour of the plots in Fig.9 to 12 mirror, in
their own way, those in Fig.4 to 7; intramolecular reaction
increases with p and with dilution, and at a given initial concentration it decreases as r moves away from unity, and is

0.8

r = 1.0

**12k1.4
I1
0

0.6

PA. = P / /

*15

I
0.8
1 3
P

Fig.9 Extent of intermolecular reaction, p c l l , versusp, for r = 1.

Legend as for Fig.4. ---- no rings. * - gel points.

129

1.c
/

[NCOI 0 + [OH] 0 e 1 equiv kg-

0.8

0.6
Pch

0.4

0.2

0
0
Extent of intermolecular reaction of minority group, pch.
* - gel

versus p . for r = 1.5. Legend as for Fig.5. ---- no rings.

points.

less for a linear system. However, the plots of pch versus p

are more critical of the experimental data than those ofN,
versus p . In the former, the plots must start at the origin
and the value of (l-l/xn) in equation 11 can be very small
at the beginning of a reaction. Thus, the experimental
points from expt 1.3 in Fig. 12 show some errors on the
basis of pch but not on the basis of N,, the usual method of
lo, l 3 (cf. Fig.4 or 7).
presentation
Concentrating on Fig.9 to 11, an interesting new feature
emerges, namely, the direct proportionality between pch
and p . For all the systems (except expt 1.3), this proportionality appears to hold in the pre-gelation region, to within experimental error, over the ranges of values of p studied
experimentally. Such a relationship has important consequences. Once the variation of the slopes of the lines
s-7391

1 .o

,* ..*3.1

r = 111.5

0.8

0.6
Pc h

0.4

0.2

0
0

0.2

0.4

0.6

0.8

Fig.11 pch versusp, for r = 1/1.5. Legend as for Fig.6.

rings. * - gel points.

130

0.4

0.6

0.8

1 3

Fig.10

0.2

---- no

Fig.12 pch versus p , for experiments at same initial concentrations.

([NCO] + [OHIOe 1 equiv kg-). Legend as for Fig.7. ---- no
rings. * - gel points.

with initial concentration and ratio of reactants has been

established it is an easy matter to predict the amount of
intramolecular reaction as a function of dilution, ratio and
overall extent of reaction for a given polymerisation. The
plot of Stepto and Waywells results in Fig.12 indicates
that proportionality also occurs in linear systems. It will
be interesting to see if the various calculations of total ring
fractions 6-9, l2, l4 show it to be of general validity.
In Fig.9 to 1 1, for the systems which gelled, the lines
through the experimental points have been extrapolated to
the gel points, assuming proportionality extends that far.
Notice that the values of pch at gel, p C bc , so obtained tend
to decrease with initial dilution below the ideal values shown
on the datum lines, indicating that increasing proportions of
the ring structures formed do contribute to network formation. Also, the difference between pch,c and the ideal value
at zero rings p:kc [= (1 /2r)% for r < 1, or ($2) for r > 1]
is approximately directly proportional to the number of ring
structures which do contribute, while p - Pch is directly proportional to the total numberof ring structures. It may be that
linear extrapolation beyond the range of the data is not justified. However, any deviations from linearity which do occur
would be expected to cause a decrease in slope, on the basis
that the chance of intramolecular reaction would a prion be
expected to increase with molecular complexity, that is, with
extent of reaction. The fact that direct proportionality
between pch and p is observed means that contrary effects,
such as an increase in average size of possible ring structures
with molecular complexity, are operating. Accepting that
pch. is less than p$,, means that the chemical criterion for
incipient infinite structure is not necessarily the overall criterion for incipient network formation. Both the detection
of gelation and the properties of networks depend to some
extent on physical entanglements. Thus, the difference
can be taken as a measure of the
between pch and
proportion of links which are chemically but not physically
wasted.
Beyond the ge1 point, p c , plots of pch us p still have a meaning but only with respect to the sol fraction. In these terms,
and with no rings, the path of the reaction is described by
THE BRITISH POLYMER JOURNAL, JUNE 1977

12
PEG200 '

10

I
I

X
6

4.

I
/

/
HDI + PEG200 /

HDI + LG56
0

0.2

0.4
0.6
( 1 - pb)

0.8

gel fractions will be terminated by groups of the majority

type and psol = 1, assuming that the sol fraction still contains structural units from the minority component. With
ring structures occurring, a sol fraction will remain at complete reaction consisting of molecules with and without ring
structures, with fully reacted groups at all r (cf Fig.3(a)) and
with unreacted groups at r # 1, and pch,sol need not be zero
or unity at complete reaction.

CONCLUSIONS

It is hoped that the data presented in this paper will provide

a sound basis for the understanding of intramolecular reaction in non-linear random polymerisations. The present
discussion has been purely qualitative, but it is intended
that quantitative interpretations will follow later, in terms
of cascade theory,15 kinetic analysis and rate t h e ~ r y and
,~~~
work in this direction is already underway.l6$l 7 However,
even in qualitative terms it is apparent that the use of total
ring fraction data coupled with gel point data is an important tool for an understanding of intramolecular reaction and its
effects on network formation. Also,pch has proved to be a
useful quantity whose possibilities, it is hoped, will be explored in other publications.

_ _ _ _ HDI + poly(ethy1ene glyco1)200, Stepto and Waywell. t

5.

HDI + LG56,present work;

- r = U1.5.

In the previous investigation of intramolecular reaction in

linear PEO-based polyurethanes values of x were obtained
from the cryoscopic data. This has also been done in the
course of the present work from plots such as those in Fig. 1.
In both cases the values of x so obtained refer to infinite
dilution in benzene at about 5".
Extremely high values of x were found for all the linear systems studied, with x principally a function of the concentration of residual hydroxyl groups on the molecules in the
polymerising mixture. These results are shown as the
dashed curve in Fig.13, where x from the present non-linear,
PPO-based polyurethanes are all seen to be less than 0.5.
The effects of hydroxyl groups are obviously not dominant
in the present systems, and benzene is shown to be a better
solvent for the polyoxypropylene chain than for the polyoxyethylene chain. The effects of chain branching or the
somewhat larger values of x, in the present systems, both
of which would increase x,are negligible on the scale of x
values in Fig.13. The high values of x for the PEO systems
are consistent with data of Lakhanpal et al. l 8 In contrast,
Booth and Devoy 19,20 have obtained values of x in the
range 0.1 to 0.3 for linear PEO/benzene and PPO/benzene
systems at about 60". Their values are for a higher temperature, and they do not refer to infinite dilution. They do
not reflect the vast differences found here between the two
types of system. With reference to Fig.13, systems at
(1 - p b ) G 1.o correspond most closely to normal hydroxylterminated solutes.
In spite of the marked difference in behaviour for the PEO
and PPO systems, the effects of residual hydroxyl group
concentration are present in the results for the latter systems. In Fig.14, x,on an expanded scale, is seen to increase
with 1 - p b . In addition, the results show an interesting
separation into three groups corresponding to the three
values of r used, the value of x decreases at a given value of
(1 - pb), as the proportion of propylene oxide units increases. This second trend is in the opposite sense to that
expected on the basis of the hydroxyl groups alone.

Fig.13

x versus fraction of hydroxyl groups unreacted, 1 - b .

0

- r = 1.

A, A

- r = 1.5.

the line p!h = p . Before the gel point, p increases from zero
to p z (=( 1/2r)" or (r/2)"), and after the gel point, p
(= p,,) moves in some direction along the line pEh = psol,
whilst the overall consumption of the minority group (in
sol and gel) is increasing to unity. If r = 1, then psol returns
to zero at complete reaction with no sol fraction remaining.
If Y f 1 , then at complete reaction molecules in the sol and

0.5 -

0.4

X
0.3

0.2

0.1

fm
01

0.2

0.4

0.6

0.8

(1 - pb)

Fig.14

x versus 1 - pb. HDI + LG56. Legend as for Fig. 13.

THE BRITISH POLYMER JOURNAL, JUNE 1977

THERMODYNAMIC SOLUTION PROPERTIES

131

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1

3
4

5
6
7

132

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THE BRITISH POLYMER JOURNAL, JUNE 1977