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To cite this article: Tuan Q. Nguyen & Henning-H. Kausch (1998) GPC Data Interpretation
in Mechanochemical Polymer Degradation, International Journal of Polymer Analysis and
Characterization, 4:5, 447-470, DOI: 10.1080/10236669808009728
INTRODUCTION
* Paper presented at the International GPC Symposium '96, September 8-1 I, 1996,
San Diego, CA, USA.
Corresponding author.
447
448 T.Q. NGUYEN AND H.-H. KAUSCH
THEORETICAL BACKGROUND
4.5E-1 -
4.OE-1 -
3.5E-1 -
3 CE-I -
2 2.5E-1 1
.c
2.OE-1 -
1SE-1 -
1.OE-1 -
5.OE-2 -
1.2E-6 -
1 .OE-6 -
8.OE-7 ~
-r 6.OE-7 -
3
4.OE-7 -
Molecular weight, M
O.OE+O 2.OE+5 4.OE+5 6.OEt5 8.OE+5 1.OE+6 1.2E+6 1.4E+6 1.6E+6 1.8E+6 2.OE+6
Molecular weight, M
0
1,
s/2
&kcj)
S
central Gaussian
- 0- A -sl2 - j S
0 s/2 S
FIGURE 5 Some commonly encountered scission probability distribution functions:
(a) random scission, (b) central scission with Gaussian distribution, and (c) parabolic
distribution with kcha,n ends = 5.5 kcenter( k ( j ) is the individual scission rate constant for
the jth bond and s the maximum number of bonds in the polymer chain).
454 T.Q. NGUYEN AND H.-H. KAUSCH
jth bond and s the maximum number of bonds in the polymer chain.
Case (a) with equal probability for bond fracture corresponds to
random scission. The truncated Gaussian distribution function (b) is
typical for mechanochemical degradation, whereas the parabolic dis-
tribution function (c) which favors near chain end reaction is encoun-
tered in some hydrolytic degradation (kchain ends and kcenterare scission
rate constants for bonds situated at the chain ends or at the polymer
center, respectively).
In consideration of the complexities which have been enumerated, it
is obvious that some data processing scheme must be formulated
before pertinent mechanistic information could be extracted from
the experimental chromatograms. Basically, solving the “inverse”
problem, that is numerical determination of the parameters to describe
experimental MWD, consists of three stages:
( 1 ) Selection of a coherent degradation scheme. Careful planning of
the experiments is necessary to derive the maximum information
from the system under investigation.
(2) Mathematical description of the degradation scheme to derive a
theoretical MWD. Three techniques are currently available for this
purpose: (i) exact analytical solution, (ii) integration of chemical
kinetics differential equations, and (iii) Monte Carlo simulation.
This step constitutes the main computational efforts and a brief
account of the merits and disadvantages of each technique will be
examined below.
( 3 ) Comparison of the calculated MWD with experimental results. If
a good fit between the predicted and the experimental data is
obtained, the task is concluded and a physicochemical interpreta-
tion is given to explain the results from molecular considerations.
Otherwise, an alternative degradation mechanism must be devised
and the procedure repeated.
scheme (I):
ni+j + a1 + nj (1st scission event)
I 1
n[ (1= 1 , i - 1) n, (2nd scission event)
I
etc. (3rd scission event)
K j is the global scission rate constant for species with degree of poly-
merization i and r is the maximum degree of polymerization present in
the sample. For most practical purposes, it is sufficient to consider a
limited number of rate constants averaged over a "quasi-monomeric''
unit containing a multiple of the true repetitive units. A value of Y in
the range of 100-200 is normally satisfactory for a faithful description
of the polymer MWD.
The first term on the right-hand side of Equation (1) describes the
decrease of concentration of ni as a result of bond scission. However,
n j is generated if a polymer ni+,iis split at bondj or at bond (i - j ) . This
is taken into account by the second production term.
It is convenient to rewrite Equation (1) in a matrix n ~ t a t i o n : " ~ ]
MECHANOCHEMICAL POLYMER DEGRADATION 451
iio=c.cr (4)
Starting from the bottom with the single term (- Ckr,j), a recurrent
formula can be obtained for the successive values of Ci,i
x A r , j . C k , j =A j l j . C i J i = r , r - 1, ... (5)
i= 1
Experimental
Chemicals
The polystyrene samples are narrow molecular weight standards from
Polymer Laboratories (Shropshire, UK) with M , (MW at peak
maximum) in the range of 50 x 103-8.5 x 1O6g/rnol. The dispersity
index, Mw/Mn,is < 1.05 for molecular weights below 4 x lo6 but
increases to 1.20 for the highest molecular weight polymer. Chemicals
are from Fluka AG (Switzerland). Decalin is a mixture of 58% trans,
+
4 1% cis-decahydronaphthalene 1% tetrahydro naphthalene as deter-
mined by gas chromatography.
Degradation Experiments
Polymer solutions were prepared by dissolving 20 ppm of PS in decalin
with 100ppm of Galvinoxyl@. The excess of Galvinoxyl@ (systematic
MECHANOCHEMICAL POLYMER DEGRADATION 459
name: 2,6-di-tert-butyl-4-[(3,5-di-tert-butyl-4-oxo-2,5-cyclohexa-dien-
1-ylidene)-methyl] phenoxyl) served a dual purpose: to prevent radical
recombination and to end-tag the degraded chains for subsequent
spectrophotometric titration (section below). Irradiation was per-
formed in a thermostated vessel with an ultrasonic horn at a power of
20 W and a frequency of 20 kHz (Branson Sonifier@model 250). After
a predetermined period of ultrasonication, a small volume was with-
drawn, the solvent evaporated and the polymer analyzed for MWD.
Some typical results are shown in Figures 6 and 7 (R is the relative
standard deviation defined in Equation (1 1) below).
Molecular weight distribution of the virgin and degraded polymers
was determined by GPC on a Waters 15OCV equipped with a triple
detection scheme (differential refractomer, on-line viscometer and UV
absorption). Axial dispersion in the GPC columns was calibrated with
the recycling technique.'251True molecular weight distribution was
then recovered from the GPC tracing using a reshaping algorithm
0 min
PS 110 k
0s
1'2E*61
1.OE-6
I .-.
y 120 s
M, molecular weight
FIGURE 7 Change in experimental MWD with irradiation time for a 2.2 x lo6
polystyrene. All the data are corrected for axial dispersion; one example of an uncor-
rected curve is shown for the pristine sample.
described by Ishige et al. after smoothing the data to decrease the level
of
1.5
4.2 4.4 4.6 4.8 50 52 5.4 5.6 5.8 6.0 6.2 6.4 6.6 6.8 7.0
log WMm)
with x = 1.9 and Mlim= 30,000; Mlimis the limiting MW below which
no chain scission would be observed regardless of the degradation
time.
Above 2.2 x lo6, the degradation rate becomes almost independent
from A4 and the slope of the plot in Figure 8 leveled off to nearly 0.
This sudden change in the slope, surprising at first thought, is in fact
expected on physical grounds: the degradation rate cannot increase
indefinitely with M but should reach some limiting level for a given
sonication power.
Comparing Figures 6 and 7 reveals that the bond scission pattern
depends on the initial polymer MW (Mo). Chains are essentially
462 T.Q. NGUYEN AND H.-H. KAUSCH
broken into halves at low Mo, into quarters at intermediate MW, and
into multiple short fragments (down to M0/32) in the highest MW
range. Any coherent degradation scheme should account for this
observed trend.
Mathematical Modeling
-
before this system could be resolved. Symmetry condition for linear
chains reduces the unknown by a factor of 2:
scission on the final MWD is shown in Figure 9. The best fit to the
experimental data for the 2.2 x lo6 PS was obtained with the following
repartition: 56% of the degradation by single scission, 27% by
quaternary scission (M0/4) and 17% by third-order scission process
(Mo/8). For the highest MW range, 4.34 x lo6 and 8.5 x lo6, chain
halving was practically absent whereas simultaneous scission up to the
fifth-order (fragments with M”Mo/32) have to be included for a
correct representation of the degradation results. Differences between
degradation Schemes I and I1 are emphasized in Figures 9 and 10
where the weight fraction of different fragment populations are calcu-
lated and plotted for the 2.2 x lo6 PS sample. Without multiple scis-
sion, short fragments are created by consecutive reactions and can
only be found for extended degradation times.
30 s
PS 2200k
w3
wo
zb
M, molecular weight
--
initial macromolecule:
Elution volume, ml
Physicochemical Interpretation
r, prn
FIGURE 12 Strain rate distribution during a cavity collapse sketched for different
implosion times. Full collapse occurs at t = 0; r is the distance from the cavity center.
468 T.Q. NGUYEN AND H.-H. KAUSCH
250 3.E+6
2w
Z.Et6
E, 150 ..
g5
9 -
10
0
c ,c
$ 1w g
v)
l.E+6
0.€4
-20 -18 -16 -14 -12 -10 -8 6 -4 -2 0
time. us
FIGURE 13 Temporal evolution of the bubble radius (left ordinates) and strain-rate
maximum (right ordinates) during implosion collapse.
CONCLUSIONS
Acknowledgment
The authors wish to express their gratitude to the Swiss National Fund
for continued financial support.
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