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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.
'
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
u,,)
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
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 Samples were withdrawn intermittently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
[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 -
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
I
1
I
2
3
102 (W*/WI )
I
6
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
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
RBfb.
Pach =
("
fa
L,
fbr
( )-:
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.
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
0.6
0.4
0.8
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
128
k 6
E
0
r'
0.2
0.4
0.6
0.8
1 .o
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
[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
129
1.c
/
0.8
0.6
Pch
0.4
0.2
0
0
Extent of intermolecular reaction of minority group, pch.
* - gel
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
130
0.4
0.6
0.8
1 3
Fig.10
0.2
---- no
12
PEG200 '
10
I
I
X
6
4.
I
/
/
HDI + PEG200 /
HDI + LG56
0
0.2
0.4
0.6
( 1 - pb)
0.8
CONCLUSIONS
5.
Fig.13
- 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
131
References
1
3
4
5
6
7
132
9
10
11
12
13
14
15
16
17
18
19
20
160.
Temple, W. Makromole,k. Chem., 1972, 160, 277.
see, for example, Gordon, M. and Ross-Murphy, S. B., Pure
Appl. Chem., 1975,43,1.
Stanford, J. L.; Stepto, R. F. T., to be published.
Richardson, K. A.; Stepto, R. F. T., to be published.
Lakhanpal, M. L.; Singh, H. G.; Sharma, S. C. Indian J. Chem.,
1968, 6 , 436.
Booth, C.; Devoy, C. J., Polymer, 1971, 12, 309.
Booth, C.; Devoy, C. J., Polymer, 1971, 12, 320.