Polymer Degradation and Srahiliry 54 (1996) 117-124

0 1996 Elsevier Science Limited

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ELSEVIER PII: SO141-3910(96)00035-3 0141-3910/96/$15.(X)

Grafting to achieve flame retardancy

Charles A. Wilkie, Masanori Suzuki, Xiaoxing Dong, Cyarthur Deacon,

Jayakody A. Chandrasiri & Thomas J. Xue
Department of Chemistry, Marquette University, P. 0. Box 1881, Milwaukee, WI 53201-1181, USA

Vinyl monomers, such as methacrylic acid, may be grafted onto styrene-

butadiene copolymers, SBS, or onto acrylonitrile-butadiene-styrene terpoly-
mer, ABS, by either a photochemical process or chemical initiation. The
amount of grafting is similar using both procedures. Vinyl monomers may not
be grafted onto poly(ethylene terephthalate), PET; rather the vinyl monomers
homopolymerize within the PET and form a semi-interpenetrating network.
All of these copolymers have been analyzed by TGA and TGA-FTIR. For
SBS and ABS, the grafted char-former serves to retain the base polymer.
There is little difference in the degradation pathway between the grafted and
the virgin polymers. Homopolymerization of methacrylic acid within the PET
matrix has no effect on the degradation of PET. When one attempts to convert
the methacrylic acid contained within the PET into its sodium salt, the entire
sample is hydrolyzed. There is good reason to think that the addition of a
surface layer of a good char-former onto a polymer will improve the thermal
resistance of the polymer. 0 1996 Elsevier Science Limited

1 INTRODUCTION occurs before that of the polymer and an

adherent, thermally-insulating coating is ob-
The thermal degradation of a polymer consists of tained, the same char-former may be useful for a
three essential steps: (1) breakdown of the variety of polymers. There will, however, be
polymer to produce small molecules which may some variability based upon the ability to graft
escape to the gas phase; (2) burning of these onto different polymers.
molecules, a process which inherently involves The polymers that have been studied include
radicals; and (3) feedback of thermal energy from acrylonitrile-butadiene-styrene terpolymer, ABS:
the flame to the polymer to continue the process. styrene-butadiene copolymers, SBS and K-resin;
Intervention in all three of these steps has been and poly(ethylene terephthalate), PET. In this
used as the basis for the development of flame paper a review of recent work on grafting and
retardants. thermal analysis of the grafted copolymers will be
In this laboratory we have been focusing for presented together with some new work on the
some time on char-formation and the inherent thermal analysis of PET and SBS and K-resin. In
ability of char to prevent the feedback of thermal order to evaluate the efficacy of grafting for flame
energy and hence to prevent thermal degrada- retardancy, a comparison of the different systems
tion. This has been accomplished most often by will be presented.
an additive approach in which one designs an
additive that will interact with the degrading
polymer and favor the formation of char. Since 2 EXPERIMENTAL
each polymer is different, a different additive
package is required for each system. A more 2.1 Materials
general approach may involve the addition of a
surface coating of a char-former to a polymer. The ABS resin used in this study was supplied b)
We have recently become interested in delivering the Japan Synthetic Rubber Company Ltd; il
such a surface coating by graft copolymerization. contained 15 wt% acrylonitrile, 40 wt% buta.
As long as the degradation of the char-former diene and 45 wt% styrene. The polybutadiene
117
118 C. A. Wilkie et al.

was prepared by emulsion polymerization and aqueous solutions of monomer to cause grafting;
then grafted with a styrene-acrylonitrile copoly- this is the procedure that has been developed by
mer in which the acrylonitrile content was 25.6%; Geuskens.‘.’ The effects of time, temperature,
the ABS was 55% grafted. The SBS block concentrations of monomer and anthracene, time
copolymer was supplied by Shell as Kraton of irradiation and identity of monomer have been
D1102 and contains about 75% butadiene while studied.3-” Methacrylic acid, acrylic acid and
K-resin was supplied by Phillips Petroleum as acrylamide have been grafted onto ABS while
KR@l, containing about 25% butadiene. Films methacrylic acid and acrylamide have been
with thickness between 0.03 and 0.05 cm were grafted onto SBS and K-resin. For all grafting
prepared by thermal compression at 150°C at a reactions herein described the graft yield is
pressure of 4750psi. The PET films used in this defined as the difference between the mass of
study were Mylar films received from E.I. polymer before and after reaction divided by the
DuPont de Nemours Co. These films are supplied initial mass.
by DuPont as 100% poly(ethylene terephtha-
late); infrared spectroscopy confirms this. Two 2.3 Chemical initiation of grafting onto ABS
films were used, Mylar 200A, 50 pm in thickness
and Mylar-48A, 12 pm in thickness. Unless ABS was placed in chloroform solution contain-
otherwise noted, the 50 pm films were used in ing benzoyl peroxide and acrylic acid and
these studies. maintained at a suitable temperature. The effects
Methacrylic acid (MAA), methyl methacrylate of time, temperature and concentrations on the
(MMA), styrene, vinyl acetate, anthracene, addition of acrylic acid to ABS have been
benzoyl peroxide and hydrogen peroxide were studied.”
supplied by the Aldrich Chemical Company.
Azobisisobutyronitrile was supplied by Eastman 2.4 Addition of monomers to poly(ethylene
Kodak. As-supplied MAA and MMA contain an terephthalate)
inhibitor to prevent polymerization: this is
removed by passing the material through a PET films were suspended in aqueous solutions
column, also supplied by Aldrich. containing monomer and initiator at a suitable
Infrared spectra were obtained on a Mattson temperature. The initiators that have been used
Galaxy Fourier Transform infrared spectrometer. include azobisisobutyronitrile, AIBN, benzoyl
Thermogravimetric analysis was performed on an peroxide, BPO, hydrogen peroxide and transition
Omnitherm 1000 TGA. TGA-FTIR was per- metal salts such as Co(Acac),, V’+ and Crht . The
formed using a Cahn TGA interfaced to a effects of swelling of the PET, concentration of
Mattson Galaxy Fourier transform infrared monomer and initiator, time, temperature and
spectrometer. Cone calorimetry was performed identity of monomer and initiator have been
per ASTM E 1354-92 using a Stanton studied; monomers that have been studied
Redcroft/PL Thermal Sciences instrument at include methacrylic acid, methyl methacrylate,
25 kW/m’ in the horizontal orientation. The styrene and vinyl acetate.7,H
samples were 0.25 in. thick and were mounted
using the edge retainer and wire grid. Exhaust
flow was set at 24 l/s and the spark was 3 RESULTS AND DISCUSSION
continuous until the sample ignited.
3.1 Grafting onto ABS
2.2 Anthracene photosensitization of grafting
onto ABS, SBS and K-resin The reason for studying grafting is to learn
effective ways in which to deliver to the surface
The compressed films were placed in a of a polymer a material which will char at
methanolic solution of anthracene, and anthra- temperatures lower than the degradation tem-
cene was allowed to migrate into the films. When perature of the underlying polymer and thus offer
anthracene-containing films are photolyzed, sing- thermal protection to that polymer. We began
let oxygen is produced which yields hydroper- our investigations using sodium methacrylate and
oxides in the butadiene region of the polymer. sodium acrylate as the char-former to be
The hydroperoxidized polymers were heated in delivered to the polymer. Both of these materials
 Grafting to achieve flame retardancy
degrade in a TGA experiment to produce about
60% char, and the char consists of sodium
carbonate and elemental carbon.‘,” Unfortun-
ately, an effective process has not yet been
discovered for the delivery of significant quan-
tities of sodium (meth)acrylate to the polymer;
the only process currently available is to graft
methacrylic acid onto the polymer and convert
that to the sodium salt by soaking in aqueous
sodium hydroxide.
Other monomers which offer a high char yield
should also be useful and will be required. It is
necessary to match the degradation temperatures
of the polymer to that of the char-former, i.e. the
char must form before the polymer has
significantly degraded; this is an important design
feature of this mode of flame retardance.
Grafting onto ABS has been accomplished
both by the anthracene route of Geuskensle5 and
by chemical initiation using BP0 as the initiator
in chloroform solution.6 The anthracene sen-
sitized formation of singlet oxygen is suggested to
cause the formation of hydroperoxides at an
allylic position in the butadiene region of the
polymer; this has never been proven. In the case
of the chemical initiation, the results favor an
interpretation in which addition of monomer
occurs across the double bond of the butadiene.6
The olefinic C-H stretching frequency is lost
upon grafting and there are significant changes in
the region of the C-H out-of-plane bending
vibrations. In addition, AIBN is also able to
effect this grafting reaction. It is well known that
AIBN is unable to cause the removal of a
hydrogen atom to generate a radical site so this
also argues for addition across the double bond.
The success of the grafting reaction appears to
depend upon the solubility of the monomer in
the ABS film. Since the solubility increases with
increasing temperature, the graft yield also
increases. The solubility of the monomer in the
polymer film has a very important role in the
grafting process. The graft yield of acrylic acid is
at least 15 times lower than has been observed
with methacrylic acid under comparable condi-
tions; the solubility of acrylic acid, as measured
by the infrared absorption of the carbonyl, is
one-third to one-fourth that of methacrylic acid.5
One would anticipate that the concentration of
anthracene would have a profound effect since
this controls the number of hydroperoxides which
may be obtained. As long as there is some
anthracene present, the graft yield appears to be
119
independent of anthracene concentration.
Geuskens’ found that the concentration of
hydroperoxides is 150 times greater than that of
anthracene; a small amount of anthracene gives a
large number of sites for grafting so, at modest
graft yields, even a small amount of anthracene
will produce a significant amount of grafting.
The photochemical grafting process is con-
venient for small scale reaction but a process
using chemical initiation would offer some
advantages. The reasoning that has been used is
that the monomer and initiator must have some
solubility in the polymer. Chloroform was chosen
as the solvent because it will swell ABS and this
should permit the migration of monomer and
initiator into the polymer. The graft yields are
comparable to those observed for the photo-
chemical process, the maximum graft yield for
both acrylic and methacrylic acid is about 140%.
The graft yields are similar when the grafting
reaction is initiated with BPO; one may graft up
to about 140% of methacrylic acid onto ABS by
either the photochemical or chemical initiation.
The graft yields are significantly larger for both
SBS and K-resin4 than observed with ABS; it is
possible to increase the mass of an SBS film by
2500% while K-resin increases by 1500%. When
some iron is present the increase in mass is even
larger, up to 6000% for SBS and 2000% with
K-resin; the effect of iron is apparently to offer
another means of initiation of grafting, redox.
There is a serious question at these graft yields as
to the identity of the polymer. The larger graft
yields for SRS are believed to be due to the much
larger amount of butadiene that is present in the
polymer; this permits a much higher concentra-
tion of hydroperoxides, and hence more sites on
which to graft. The graft yield increases with
concentration of monomer and temperature, as
observed for ABS. The graft yield is also quite
dependent upon the concentration of anthracene,
unlike the ABS system where there is no
dependence upon this variable. This may not be
of any significance because of the great
differences in graft yield; there does not appear
to be a dependence on anthracene concentration
when grafts onto ABS and SBS and K-resin are
compared at similar graft yields.
3.2 Addition of monomers to poly(ethylene
terephthalate)
Modification of poly(ethylene terephthalate),
120 C. A. Wilkie et al.

PET, fibers by graft polymerization has been question is whether all of the underlying polymer
studied by many authors.“-“’ The reaction has (ABS, SBS or K-resin) completely degrades or
been initiated by high energy radiation” Is or by whether some remains behind in the non-volatile
chemical means using initiators such as benzoyl fraction. In order to ascertain this it is necessary
peroxide,“+‘8 hydrogen peroxide’“-*’ and transi- to determine what the amount of char should be
tion metal ions.22-26 Vinyl monomers that have based upon the amount of grafted material.
been used include styrene,2’.27 vinylpyridines2”.” Samples of the grafted acid and samples in which
and acrylics. 12,15,1x.1’),21~25,2’).30 the acid has been converted to its sodium salt by
We have used H202, BPO, AIBN, Co(Acac),, treatment with sodium hydroxide have been
Crh+ and V’+ as initiators to effect the add-on of examined. Polymethacrylic acid gives a residue of
methacrylic acid, methyl methacrylate, styrene 5% which is non-volatile at 800°C; when the free
and vinyl acetate.‘.’ No grafting occurs in these acid is converted to the sodium salt by treatment
systems, rather the monomer is homopolymer- with aqueous sodium hydroxide the residue is
ized within the PET network to give a 13% while the homopolymer of sodium meth-
semi-interpenetrating network. One may separ- acrylate gives a residue of 55%. The value of
ate the two components of this chemically 13% is taken as the theoretical because this is the
induced blend by dissolving the PET in hot pathway used to prepare the sodium salts of the
phenol; this removes the matrix in which the grafted copolymers. The results of the TGA
homopolymer is contained so that it may also be analysis for grafted ABS are shown in Table 1.”
dissolved. The fact that they may be separated by One notices that the presence of as little as 1%
solubility is proof that there is no chemical causes an increase in the amount of non-volatile
interaction between the two components. residue. The amount of residue increases up to
The extent of the add-on depends on the about SO% graft yield, hereafter a further
swelling level, concentration of monomer and increase in the amount of grafted material seems
initiator, and temperature. The factor which to show no further increase in amount of char.
appears to be most important in determining the The char layer must be retained to be thermally
amount of add-on is the solubility of the insulating, a thicker coating is apparently no
monomer and initiator in the PET film. The advantage and is likely to be less adherent.
greatest amount of add-on is observed for Grafted acrylic acid and its sodium salt are less
styrene, followed by methyl methacrylate, meth- effective than the methacrylic system. One should
acrylic acid and vinyl acetate; this is exactly the anticipate that an acrylic would be more effective
order of solubility of the monomers in PET. The since there is less organic material to be
initiator which is most efficacious is BPO, volatilized than in methacrylic acid. In fact, the
followed by AIBN with the inorganics the least TGA of the homopolymer of sodium acrylate
effective. gives a 60% residue non-volatile at 800°C while
A rather surprising result is that when PET
films that have been grafted with methacrylic acid
are treated with sodium hydroxide the films Table 1. TGA results for MAA and NaMAA grafted ABS
completely dissolve at room temperature and
terephthalic acid may be quantitatively recovered ‘MMAA TGA residue ‘X NaMAA T(;A residue
at 800°C XI 800°C
upon acidification. The homopolymer of meth-
acrylic acid provides a wick to move the sodium Actual Theoretical Actual Theoretml
hydroxide throughout the PET so that every
surface is bathed in base. The time to hydrolysis
depends upon the concentration of base and the
amount of add-on.

3.3 Thermogravimetric analysis of grafted ABS,

SBS and K-resin

The work on ABS has been previously

reported’.” but it is included here to compare
with the SBS and K-resin results. The significant
 Grafting to achieve flame retardancy 121

polyacrylic acid gives a residue of 13% and the polymethacrylic acid and 13% expected from its
salt prepared by treatment of the polymeric acid sodium salt prepared by treatment of the
with sodium hydroxide gives 36% residue.’ These polymeric acid with sodium hydroxide, were used
increased residues for the graft layer do not to calculate the theoretical values. The same
translate into a graft copolymer with improved results are presented in graphical form in Figs 1
thermal resistance. The actual residue for the and 2. Figure 1 shows the actual and theoretical
grafted acid is never as large as that expected amount of non-volatile residue produced in a
based upon the amount of material which has TGA experiment for grafted SBS and K-resin
been grafted. For the sodium salt the theoretical while Fig. 2 relates the same information after
residue is 7.6% while the actual is 15% at 10% conversion to the sodium salt. The great
graft yield; this is significantly better than what is similarity between SBS and K-resin is most
seen for sodium methacrylate at the same graft evident in these figures. There appears to be little
level. As the graft level increases, the theoretical difference between the residues found for SBS
and actual values come closer together than seen and K-resin and those found for ABS. The
in the methacrylate system. The most significant residues found for the grafted acid exceed the
difference is in the adherence of the graft layer to theoretical values at all temperatures but show
the polymer. The methacrylic system is quite some variability; methacrylic acid provides some
adherent while the acrylic is much less adherent minimal protection for SBS and K-resin in the
and may be observed to easily flake off the same way as observed for ABS. For the sodium
polymer. salt the amounts of non-volatile residue are
The TGA results for grafted SBS and K-resin uniformly higher, as should be expected because
are presented in Table 2; the same values used the salt gives a higher residue, and show a
above for ABS, 5% residue expected from smooth increase up to about 40% graft yield
where the same maximum as found for ABS is
observed. The TGA curves for SBS and an SBS
Table 2. TGA residue for MAA and NaMAA grafted SBS
sample which has been grafted with 60%
and K-resin
methacrylic acid, then converted to the sodium
Grafted SBS salt, are shown in Fig. 3. The degradation of the
Weight % MAA Theoretical NaMAA Theoretical
grafted sample begins at quite low temperature
grafted residue MAA residue NaMAA
residue residue because of the presence of the free acid. The
main degradation step is initiated at about
0 0 0 0 0
the same temperature which may indicate that
10 3.1 0.5 8.7 1.3
20 4.6 1.0 13.6 2.6 the poly(sodium methacrylate) and SBS degrade
30 4.3 1.5 16.0 3.9 independently; the presence of the char layer
40 3.9 2.0 25.1 5.2 must serve to retain the SBS.
50 4.5 2.5 16.5 6.5
60 5.8 3.0 18.9 7.8
70 4.3 3.5 23.9 9.1 3.4 TGA-I!TIR studies
80 4.8 4.0 22.1 10.4
90 4.5 4.5 25.4 11.7
100 5.9 5.0 27.2 13.0
A comparison of the volatiles that are evolved
from the base polymer, ABS, SBS or K-resin,
Grafted K-resin
Weight % MAA Theoretical NaMAA Theoretical
grafted residue MAA residue NaMAA
residue residue I l K-resin
+ theoretical
0 0 0 0 0
10 4.2 0.5 3.5 1.3
20 4.6 1.0 13.9 2.6
30 3.8 1.5 19.8 3.9
40 4.7 2.0 21.6 5.2
50 5.3 2.5 14.5 6.5
60 5.9 3.0 17.5 7.8
70 6.6 3.5 9.8 9.1
80 5.6 4.0 17.6 10.4
W MAA
90 7.8 4.5 12.8 11.7
100 5.1 5.0 18.4 13.0 Fig. 1. Actual and theoretical TGA residues (SOO’C) for
MAA grafted SBS and K-resin.
122 C. A. Wilkie et al.

that a comparison may be made. It is difficult to

compare the two systems since ABS is 20%
grafted while SBS and K-resin are 10% grafted.
s In all cases the grafted samples show an
9
z improvement in the various measureable para-
d
meters. One is usually most concerned about the
heat release rates in cone calorimetry studies; for
grafted ABS the peak heat release rate is about
I
I20 71% lower than observed in virgin ABS, for SBS
% NaMAA 10% of grafted monomer lowers the rate by 25%.
Fig. 2. Actual and theoretical TGA residues, (SOO’C) for The time to peak heat release is also important:
NaMAA grafted SBS and K-resin. this is more than doubled for ABS and increased
by about 35% for SBS. There are relatively
minor improvements in all parameters for SBS
with the corresponding material that has been and K-resin and major improvements for ABS.
grafted with methacrylic acid and converted to This may be due to the differences in the amount
the sodium salt leads to the conclusion that the of added material or to some as yet unknown
same gases are evolved in each case. For grafted differences in the systems.
ABS, the evolution of gases commences some
90-100°C higher than for the virgin polymer. For
3.6 Thermal analysis of PET samples
grafted SBS and K-resin, the gases are evolved at
containing polymethacrylic acid
only slightly higher temperatures for the grafted
than the ungrafted samples. There is apparently
no chemical interaction between the graft layer It has been noted above that the degradation of
and the underlying polymer upon pyrolysis and polymethacrylic acid produces a residue so it is
the char only serves to retain the underlying possible that this mixture of polymers may be
polymer. more thermally stable than PET. The materials
have been analysed by TGA-FTIR and the
3.5 Cone calorimetry non-volatile residues that were obtained were
examined by infrared spectroscopy. Samples
The cone calorimetry results for ABS have been containing 0, 19 and 50% polymethacrylic acid
previously published3’ but are repeated here in were examined. The TGA curves for the three
Table 3 along with those for SBS and K-resin so samples are superimposable so the presence of

4
0 200 300 400 500 600 700 800
Temperature (“C)

Fig. 3. Thermogravimetric analysis curves for SBS and grafted SBS. The heating rate is 2O”C/min.
 Grafting to achieve flame retardancy 123

Table 3. Cone calorimetry results for virgin and grafted SBS and K-resin

% NaMAA % NaMAA % NaMAA”

on SBS on K-resin on ABS

0% 10% 0% 10% 0% 21%

Time to ignition (s) 180 221 245 33.5 285 460

Peak heat release rate (kW/m*) 991 741 590 544 901 259
Time to peak HRR (s) 405 550 504 735 530 1130
Time to burnout (s) 465 f 571 630 r 829 670 t 1400 +
Energy output through r s (kJ) 1620 1170 1555 990 1700 150
Mass loss rate (mg/s) 183 160 154 125 170 40
Percent mass loss through t s 84 51 88 45 83 5
Specific extinction area (m’/kg) average through I s 1263 1218 1169 1119 790 620
Extinction area (total smoke) m2 produced through t s 67 43 69 38 49 3

polymethacrylic acid has no effect on the polymer, there is no additional improvement.

degradation. The infrared spectra of the evolved There is some maximum effective thickness and
gases are identical for all three samples. This is anything in addition to that does not increase
not surprising because the products that one efficacy. TGA-FTIR experiments have identified
expects from the degradation of polymethacrylic that the role of the char-former is simply to
acid are hydrocarbon fragments and oxides of retain the underlying polymer. The same gases
carbon, the same products seen in PET are evolved from virgin polymer and grafted
degradation. Infrared spectra of the non-volatile polymer so there is no chemical interaction that
residue from the degradation of PET and PET changes the degradation pathway of the polymer.
containing polymethacrylic acid are identical. Rather the role of the char-former is simply to
Since the degradation of polymethacrylic acid physically prevent the evolution of the base
produces elemental carbon and the diffuse bands polymer.
from a small amount of carbon will not make any The cone calorimeter data shows an improve-
significant contribution to the total infrared ment in all parameters for all three polymers.
spectrum, it should be expected that the spectra The greatest improvement is for ABS but this
would be the same. may be due to a difference in quantity of graft
layer. It does appear that this procedure is
3.7 Comparison of different systems potentially of great importance for flame
retardation of polymers.
The grafting of monomers onto ABS, SBS and An important feature is the adherence of the
K-resin occurs by a similar process for all three coating to the polymer. It might be anticipated
polymers. Much more methacrylic acid may be that the monomer is attached by covalent bonds
added to SBS and K-resin. K-resin and ABS to the polymer and must adhere. The long
contain similar amounts of butadiene so the polymer strands that are grafted must interact
explanation does not lie in the butadiene content; not only within themselves but also with the base
we feel that the monomer is much more soluble polymer by Van der Waals interactions in order
in SBS and K-resin and this is the reason for the for good adherence to occur. Adherence cannot
much larger graft yields. Solubility is perhaps the be predicted and it is an important variable that
most important parameter in the grafting of a must be considered.
monomer to these polymers, the more soluble Grafting of methacrylic acid onto SBS causes a
the monomer is in the polymer film the greater complete change in the physical properties of the
the graft yield. No grafting occurs onto PET. If polymer since one is adding a hard material onto
one considers the structure of the polymer and a rubbery phase. It would be unlikely for this to
the difficulty of removing a hydrogen atom from have any practical application. On the other
that structure, this is the expected result. hand, the addition of methacrylic acid to a hard
The thermogravimetric analysis shows that material like ABS may prove to be practical.
some of the polymer which would normally be Mechanical properties have not been examined
volatilized is retained at high temperature. When for the grafted samples and this is necessary for
more than 50% has been grafted onto the base practical application.
124 C. A. Wilkie et al.

4 CONCLUSION 12. Telado, G. C., Munari, S. & Calgari. S.. Chim. Ind.
(Milan), 52 (1970) 759.
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Kenkyusho Nempo, JAERI, 5026 (1970) 63: Chem.
mers is a reasonable approach to flame Ahstr. 74 (1971) 127342~.
retardancy. There is a possibility that this may 14. Okada, T., Suzuki,
Y. & Sakadura, 1.. Nippon
lead to a general scheme for flame retardancy if Genshiryoku Chosa Hokoku, JAERI, 5018 (1968) 5:
Chem. Ahstr. 70 (1969) 116147~.
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16. Shalaby. S. E., Bayzeed, A. M. & Hebeish, A.. .I. Appl.
not effective; for reasons that have not as yet
Polym. Sci., 22 (1978) 1359.
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