Polymer Degradation and Stability 9 (1984) 155-165

Thermal Degradation of Polyether-Urethanes: Part 1

Thermal Degradation of Poly(Ethylene Glycols) Used in
the Preparation of Polyurethanes

Norman Grassie & Gilberto A. Perdomo Mendoza*

Department of Chemistry, University of Glasgow,
Glasgow G12 8QQ, Scotland, Great Britain

(Received: 17 October, 1983)

ABSTRACT

Poly(ethylene glycols) with molecular weights of approximately 1000

and 1500, which are commonly used in the preparation of polyether-
urethanes, have been thermally degraded and a detailed analysis made of
the volatile products using, principally, ir and mass spectrometry, glc and
GC-MS. These products have been accounted for in terms of a concerted
radical mechanism initiated by random scission of C--O and C - - C bonds
in the polymer chains. Two products, water and ethylene glycol, are more
probably formed in independent reactions at chain terminal structures.

INTRODUCTION

In polyurethanes, as in other classes of polymers, there are problems of

degradation associated with processing and with ageing or deterioration
during commercial exploitation. However, the fire hazard associated with
the use of this technologically important group of materials has attracted
much more publicity in recent years and the dangerous inflammability
and the evolution o f large volumes of smoke and toxic fumes are clearly

* Present address: Departamento de Quimica, Universidad de los Andes, Merida 5101,

Venezuela.
155
Polymer Degradation and Stability 0141-3910/84/$03.00 © Elsevier Applied Science
Publishers Ltd, England, 1984. Printed in Great Britain
156 Norman Grassie, Gilberto A. Perdomo Mendoza

associated with degradative stability. In order to help overcome these

problems it is obviously important to have as much information as
possible about the products and mechanisms of the degradation processes
which occur in polyurethanes as well as about the modes of action of the
additives or reactives which have been applied as fire retardants.
This theme has been pursued recently in these laboratories. Polymers
do not burn. It is the volatile products of degradation which do so. Thus it
is important to understand the nature of thermal degradation and Grassie
and Zultiqar x have studied the products and mechanism of thermal
degradation of a model polyurethane. They have also extended this to a
detailed study of the changes brought about by the presence of
ammonium polyphosphate (APP), 2 a common fire retardant for
polyurethanes. Additive fire retardants of this kind may, of course, be
lost from the polymer by evaporation or solvent elution. For maximum
efficiency it is also important to match their appropriate properties with
those of the degrading polymer so that they are available 'in the right
place at the right time'. To overcome some of these problems it would
seem logical to incorporate the fire retardants into the actual chemical
structure of the polymer--in which case they are described as 'reactives'
rather than 'additives'. Polyurethanes with a similar basic structure, but
incorporating phosphorus-containing groups similar to those in APP,
have therefore been synthesised and their degradation reactions
investigated. 3 - 5
Commercial polyurethanes are most frequently based on polyesters and
polyethers. A typical polyester urethane has already been studied 6 and
this and subsequent papers continue the theme by reporting on polyether-
urethanes (PEU).
The thermal degradation of polyether-urethanes is complex since the
structure contains both polyether and diisocyanate segments. To
facilitate the interpretation of experimental results, analysis of the
behaviour of the polyether segment in isolation is desirable. This paper
thus deals with the thermal degradation of poly(ethylene glycols) (PEG)
with molecular weights of approximately 1000 and 1500. Lower
molecular weight materials, such as PEG 200 and diethylene glycol, were
not suitable for detailed study because of their high volatilities at
degradation temperatures. Nevertheless, preliminary experiments in a
closed system suggested that a similar degradation pattern is involved.
Madorsky and Strauss ~ studied products, rates and energies of
activation of the thermal degradation of some PEGs. Other studies s
 Thermal degradation of polyether-urethanes: Part 1 157

investigated the mechanism and the relative stabilities of the C - - O and

C ~ C bonds. Radical mechanisms were proposed and have been
confirmed recently. 9'1°

EXPERIMENTAL

Materials

Poly(ethylene glycols) (PEG 1000 and PEG 1500, BDH Ltd) were
purified by dissolving in warm anhydrous ether and sufficient anhydrous
methanol to effect complete solution. Crystallisation occurred on cooling
to - 10 °C. This procedure was repeated several times. On account of the
hygroscopic nature of the poly(ethylene glycols) they were stored under
vacuum in bottles which were placed in a desiccator containing
phosphorus pentoxide.
Molecular weights were measured by the end group method outlined by
Sorenson and Campbell 11 and by Vapour Phase Osmometry using a
Mechrolab 301A Vapour Phase Osmometer. Values of 1030 and 1550
were obtained using End Group Analysis and of 870 and 1315 using
Vapour Phase Osmometry.

Analytical techniques

Infra-red spectra were recorded either on a Perkin-Elmer 257 or on a Pye

Unicam SP3-300 grating infra-red spectrometer. Poly(ethylene glycols)
were analysed in chloroform solution. Depending upon their physical
state, products of degradation were analysed in chloroform solution, in
KBr pellets, in thin films or in the gas phase in a cell with NaCI windows.
A mass spectrometer model AEI MS12 with micromass 2SB console
was used to assist identification of products of degradation. A Micromass
QX-200 instrument directly coupled to the SATVA apparatus was used to
analyse volatile products with molecular weights less than 200.
Volatile products of degradation cannot always be efficiently separated
by means of SATVA. A better separation was achieved using a Perkin-
Elmer F-11 flame ionisation gas chromatograph with various column
packings (10 % Microwax in Chromosorb, 5 % free fatty acid phase in
Chromosorb, SP 2250 Scot column, 33 % dimethyl sulpholane on fire
brick). Samples were dissolved in either ethyl acetate or diethylether.
158 Norman Grassie, Gilberto A. Perdomo Mendoza

An AEI MS 30 mass spectrometer interfaced with a Pye Unicam 104

gas chromatograph, via a single stage glass jet separator (GC-MS) was
found to be a powerful tool for the identification of products.
TG curves were obtained using a D u P o n t 990 Thermal Analyser and
DSC traces using a D u P o n t 910 instrument. In both cases, 3 - 6 m g
samples were programmed from ambient to 500°C at 10 ° min-1
Thermal Volatilisation Analysis (TVA) and Sub-Ambient TVA
(SATVA) have been devised and described in detail by McNeill. 12-14

\\ \
-\

-80
\:,,, \
\
i
I
|
i
I
i
-60
i
I
, t.

ii,
|
|
-40

i
|

/
i I

"E -20
u

es

e-
,',:,, \
Temp. °C.
Fig. 1. T G traces f o r P E G 1000 a n d P E G 1500. P E G 1000; - - , under vacuum;
..... , u n d e r n i t r o g e n : P E G 1500; . . . . , under vacuum; ....... , under nitrogen.
 Thermal degradation of polyether-urethanes: Part 1 159

RESULTS

Thermal analysis

TG
The T G traces in Fig. 1 demonstrate that weight loss occurs in one step
during thermal degradation. It begins at 280-290°C under nitrogen,
slightly lower under vacuum, and there is negligible residue at 450 °C.

DSC
As shown in Fig. 2, DSC traces show three main endothermic transitions.
These are at 62, 110 and 382°C for both PEG 1000 and PEG 1500.

TVA
TVA traces for PEG 1500, which are virtually identical with those for
PEG 1000, are illustrated in Fig. 3. Evolution of volatile material is
detectable at about 325°C and occurs in a single step, reaching a
m a x i m u m rate at 366 ° which is generally consistent with the T G and DSC
data.
The 0 ° and - 4 5 ° C traces, on the one hand, and the - 7 5 ° C and
- 100°C traces, on the other, are almost coincident, while the - 196°C
trace indicates that a substantial fraction of non-condensable products is
formed. A viscous yellow-brown 'cold ring' fraction, volatile at
degradation temperatures but involatile at ambient temperature, is also
formed and the residue, after heating to 500°C at 10°Cmin -1, is
negligible.
No volatile products were recorded above 410°C.

Analysis of products of degradation

Products were analysed in three fractions--products 'non-condensable'

at - 1 9 6 ° C , volatile at ambient temperature but 'condensable' at
- 1 9 6 ° C and the 'cold ring' fraction. PEG 1000 and PEG 1500 gave
identical results.

Non-condensables
This fraction was collected in a closed system. Methane, ethane and traces
of carbon monoxide were identified by infra-red spectroscopy and mass
spectrometry.
160 Norman Grassie, Gilberto A. Perdomo Mendoza

0
X

I0
"0

~pj ,y0 3p ,p
Temp.°C.
Fig. 2. DSC trace for PEG 1500. Under nitrogen.
 Thermal degradation of polyether-urethanes: Part 1 161

ne
._>

,-v, 3J)O 4,~0

Temp.°C.

Fig. 3. TVA traces for PEG 1500. Trap temperatures: --, 0 °C; ....... , - 45 °C;
, -75°C;- ....... , - -I00oc; ...... , - 196°C.

Condensables
The SATVA trace in Fig. 4 indicates five major fractions. Each fraction
was isolated for further analysis using the ir, MS, glc and GC-MS
techniques.
Formaldehyde, ethylene oxide, propane and butane were the main
components of fraction 1. The amorphous and highly insoluble white
solid which formed on the walls of the sample container was identified as
paraformaldehyde from which formaldehyde was formed on heating at
180-200 °C. Acetaldehyde was identified in fraction 2.
Fractions 3, 4 and 5 were analysed separately but absolute
identification of all the components was difficult because of the small
yields and low volatilities. However, methoxyacetaldehyde, ethoxyacet-
aldehyde and water and ethylene glycol were identified as the main
productsin the respective fractions, together with traces of many other
low molecular weight hydroxyl, carboxyl, carbonyl and ethereal
compounds.

Cold ring
This fraction was removed from the reaction tube with chloroform and an
infra-red spectrum recorded. Hydroxyl, carbonyl and ether absorptions
suggest low molecular weight fragments with terminal structures
incorporating carbonyl groups as well as hydroxyl groups.
162 Norman Grassie, Gilberto A. Perdomo Mendoza

..% -196
".t

'%

'.,..
" ' . .% 3 4

"",,, .
'-...

6
%
I-
I
Time,mln.

Fig. 4. SATVA trace of condensable products from the degradation of PEG 1500
heated to 500°C at 10°min -1.

DISCUSSION

Interest in the mechanism of the thermal degradation of polyethers has

been focused upon the stability of the C - - O and C - - C bonds which
constitute the main chain 7 and, in particular, whether degradation starts
at the C ~ C bond in the ~ position to the C - - O bond or at the C - - O bond
itself.S It has been deduced that a radical chain mechanism is involved
which is initiated at random along the length of the chain.
In addition to this main process, it seems that other, quite separate,
reactions could occur at chain ends and elimination of water between
pairs of hydroxyl end groups to give ethereal linkages seems more likely
than elimination of water from a single chain end to give alkene. The
former would account for the high molecular weight residue which is
formed when low molecular weight polyethers are distilled. However, this
reaction must be relatively unimportant since the infra-red spectral
measurements demonstrate that the hydroxyl group concentration
 Thermal degradation of polyether-urethanes: Part 1 163

(3300-3500 cm-t) does not change significantly during the degradation

process.
It seems unlikely that initiation of the radical chain process would be
initiated by scission of C--H bonds, as previously suggested,1 o in view of
the fact that C--O and C--C bonds are weaker. The mechanism
presented, in which initiation by both C--C and C--O bond scission is
represented, accounts for all the products observed in the degradation of
PEG 1000 and PEG 1500.
The polymer chain may break at random at either C--O or C--C
bonds and the formation of ethylene oxide may be explained in
terms of progressive depolymerisation of the terminal oxygen radical.
The terminal carbon radical from C--O scission may eliminate
acetaldehyde or lead to hydrocarbons and methoxy- and ethoxyacet-
aldehyde in the reaction sequence (Scheme l) which is represented as
occurring through a five-membered ring transition state. The methane,
ethane, propane and butane can all be accounted for in terms of hydrogen
abstraction and combination reactions of the methyl and ethyl radicals.
Acetaldehyde and ethylene oxide will be in thermal equilibrium at the
degradation temperature so that the relative proportion of these
compounds is not indicative of the relative importance of C--O and
C - ~ bond scission.
Two important products of degradation, water and ethylene glycol, are
not mentioned in the reaction scheme. These are most probably formed in
chain terminal reactions. Thus, water would be eliminated from p~irs of
terminal hydroxyl groups and ethylene glycol by hydrogen abstraction
following C--O chain scission near chain ends.

~.CH2_O_CH2__CH 2 _ O H heat, -~.CH2" + "O~CH2--CH2--OH

H~
abstraction

HO~CH2~CH2--OH

The chain fragments which constitute the cold ring fraction would be
liberated when reactions of the type represented in the reaction scheme
(Scheme 1) occur in the polymer chain in close proximity. The fact that
loss in weight occurs at lower temperatures under vacuum conditions
compared with a nitrogen atmosphere reflects the fact that these chain
fragments will diffuse more readily from the polymer under vacuum
 I
I
~ O ~ C H 2--CH2--O I+CH2ITCH2--O~

~ O ~ C ' H E ~ H 2 + 0 - ~ H 2 ~Z'H 2 O ~ CH2--O~CH2~CH2--O~

/O N
O + (~H2 ~CH2--O CH2~CH2 + O ~ H 2 ~ T H 2 - - O ~ CH2~O +(~H2~CH2--O~ CH 2 CH--CH2--O~
\O / "'H/

CHa--O~CH~EH2--O~
H2~/O~cH ~H O~
H2C . . . . . . H
/
\ (~H 3 + O = = C H - - C H 2 - - O ~

C H 3 ~ H 2 -O ~ H - C H 2 -O~
1
HYDROCARBON
1
CH 3 CH 2 + O===CH~ H 2 - - O ~

O==CH ~CH 2 O~CH~+ O = = C H ~ H 2 - - O ~ H 2 ~ H 3

HYDROCARBON
Scheme !. Radical-chain mechanism of degradation of PEGs. (Products identified are underlined.)
 Thermal degradation of polyether-urethanes: Part 1 165

conditions. Similarly, although the degradations of P E G 1000 and P E G

1500 are otherwise identical, the slightly lower threshold degradation
temperature of P E G 1000 is probably a reflection of the fact that, due to
its lower molecular weight, s h o r t e r - - a n d therefore more volatile---chain
fragments will be formed a little earlier in the degradation process.

REFERENCES

1. N. Grassie and M. Zulfiqar, J. Polym. Sci., Chem. Ed., 16, 1563 (1978).
2. N. Grassie and M. Zulfiqar, Developments in polymer stabilisation--1
(Scott, G. (Ed.)). Applied Science Publishers Ltd, London (1979).
3. N. Grassie and D. H. Mackerron, Europ. Polym. J., 16, 113 (1980).
4. N. Grassie and D. H. Mackerron, Polym. Deg. and Stab., 5, 43 (1983).
5. N. Grassie and D. H. Mackerron, Polym. Deg. and Stab., 5, 89 (1983).
6. N. Grassie, M. Zulfiqar and M. I. Guy, J. Polym. Sci., Chem. Ed., 18, 265
(1980).
7. S. L. Madorsky and S. Strauss, J. Polym. Sei., 36, 183 (1959).
8. A. B. Blyumenfeld and B. M. Kovaskaya, Vysokomol. Soyed., AI2, 633
(1970).
9. E. Bortel and R. Lamot, Makromol. Chem., 178, 2617 (1977).
10. E. Bortel, S. Hodorowicz and R. Lamot, Makromol. Chem., 180, 2491
(1979).
11. W. R. Sorenson and T. W. Campbell, Preparative methods of polymer
chemistry (2nd edn). Interscience (1968).
12. I. C. McNeill, J. Polym. Sci., A-l, 4, 2479 (1966).
13. I. C. McNeill, Europ. Polym. J., 6, 373 (1970).
14. I. C. McNeill, L. Ackerman, S. N. Gupta, M. Zulfiqar and S. Zulfiqar, J.
Polym. Sci., Chem. Ed., 15, 2381 (1977).