Note: Descriptions are shown in the official language in which they were submitted.
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FIRE RETARDA~T POLYMER COMPOSITIONS
The present invention relates to fire retardant poly-
mer compositions comprising an interpolymer of styrene, maleic
anhydride and a copolymerizable brominated comonomer such as
tribromophenyl acrylate, which have been ormulated with a
halogenated fire retardant additive, a metal oxide and a smoke
suppressant.
Polystyrene and styrene-maleic anhydride copolymers
are well known and are widely used in the prior art. Polymers
which are prepared using a comonomer such as acrylonitrile with
the styrene and styrene-maleic anhydride polymers are also
known in the art. These polymers tend to burn readily and are
not generally recommended for use in those applications requir-
:;
ing fire retardant polymers.
There exists a need in the art for styrene based
molding compositions which can be made fire retardant, and should
added toughness be desired, a suitable rubber may be added.
This need is accented by the increasing number of laws and
regulations relating to the fire retardant properties of poly-
mers used as molding compositions inthemanufacture of furniture,
such as radio and television cabinets, tables, chairs, appliance
housings, and other related uses.
The above need in the prior art is fulfilled by
fire retardant compositions of the present invention which
comprise:
(A) from 48 to 94 percent by weight based on the total weight
of the molding composition of a polymer or rubber modified
polymer which isthe interpolymerization product of:
(1) from 55 to 90 percent by weight of a styrene monomer;
(2) from 5 to 25 percent by weight of a maleic anhydride
monomer; and
(3) from 5 to 20 percent by weight of a brominated monomer
- 2 -
selected from the group consisting of bromophenyl
acrylates, bromophenyl methacrylateS bromophenylneo-
pentyl acrylate and bromophenylneopentyl methacrylates,
with the proviso that the amount of bromine in the
polymer is at least 3 percent, preferably 6 percent,
by weight; wherein the amount of rubber in the polymer
is in the range of from 0 to 30% by weight of the
; polymer;
~B) from 3 to 12 percent by weight based on the total weight
of the molding composition of a metal oxide;
(C) from 3 to 25 percent by weight based on the total weight
of the molding composition of a smoke suppressant which
is selected from the group consisting of smoke suppressing
hydrates, carbonates and borates; and
lS (D) from 0 to 15 percent by weight of a brominated aromatic
fire retardant additive.
The styrene-type monomers used in the present
invention include styrene, alpha-methylstyrene, and halogenated
styrenes such as o-, p-, and m-chlorostyrenes, o-, p-, and m-
bromostyrenes, etc. The amount of st~rene type monomer used
in the present invention is from 55 to 90 percent by weight
based on the weight of the total polymer composition. Up to
30 percent by weight of the styrene monomer may be replaced
by monomers such as acrylonitrile, me-thacrylonitrile, methyl-
methacrylate, etc.
The amount of maleic anhydride used in the present
invention is in the range of from 5 to 25 percent by weight,
preferably 7 to 20 percent by weight based on the total polymer
composition~ The maleic anhydride monomer used may be replaced
in whole or in part by monochloromaleic anhydride and bromo-
maleic anhydride. The dichloromaleic anhydride was found to be
unsuitable because of excessive brittleness in the polymer which
s~
also had poor processability. The maleic anhydride monomers
used contribute to lower smoke levels for the polymer, raise
the heat dlstortion temperature of the polymer and reduce
the tendency o~ the polymer to drip during the flame tests.
The brominated comonomers which are copolymerized
with styrene and maleic anhydride include brominated phenyl
acrylates, brominated phenyl methacrylates, brominated neo-
pentyl acrylates and brominated neopentyl methacrylates
wherein the monomer contains from 1 to 5 bromine atoms per
molecule. The preferred brominated monomers include tribromo-
phenyl acryl~te~ tribromophenyl methacrylate, tribromoneopentyl
,
acrylate and tribromoneopentyl methacrylate.
The amount of brominated monomer used is selected
so as to provide an interpolymer with a bromine content of
at least 3 percent, preferably 6 percent, by weight. In order
to obtain this minimum bromine level, it will be necessary to
use brominated monomer in amounts in the range of from 5 to
20 percent, preferably 10 to 20 percent, by weight when using
the preferred tribromo monomer. Preferably, the total amount
of halogen in molding compositions prepared from the inter-
polymers of the present invention is at least 10 percent by
weight. This amount of halogen can be due solely to the
brominated monomers used. Alternately, at least ~ percent by
weight of the halogen can be due to the brominated monomers
used and the balance can be contributed by halogenated fire
retardant additives or halogenated rubber modifiers as is
described in greater detail below.
The use of a brominated comonomer insures dis-
persion of the bromine throughout the polymer composition and
avoids the problems encountered when trying to obtain a uniform
dispersion of fir2 retardant additives into the polymer composi-
tion. Moreover, when using the comonomer approach there is
~o~ss~
more latitude for the use o~ additives in the polymer ~or
specific purposes without losing too much of the polymer
properti~s.
The polymers of the present invention are pre-
pared by conventional mass or solution polymerization tech-
niques. Aqueous polymex~zation methods are not used because
the water would hydrolyze the anhydride group.
The polymers of the present invention may be
further modified with various additives in order to enhance
fir~ retardant properties and/or smoke evolution properties.
A description of the preferred additives is set forth below.
HALOGEN ADDITIVES
The polymers of the pxesent invention may be
formulated with additives which provide additional halogen
content to the polymer composition. These halogenated fire
retardant additives are generally well known in the art. The
preferred additives are those which contain one or more bromine
atoms attached to an aromatic nucleus. One such class of these
compounds may be represented by the following general formula:
~ 6
R4 ~ \~ O R
R3 R2
in which Rl is an aromatic group which may be brominated and/or
chlorinated or a straight chain or branched alkyl group con-
taining from 2 to 12 carbon atoms and may contain an O~ group,
and R2 to R6 stand for a member of the group consisting of
hydrogen, chlorine and bromine, said ether containing at least
three bromine atoms attached to an aromatic group.
Examples of suitable diaromatic ethers containing
bromine attached to the nucleus are tribromodiphenylether,
tetrabromodiphenylether, pentabromodiphenylether, hexabromodi-
phen~lether, tribromochlorodiphenyletherj tribromodichlorodi-
~55~7
phenylether, tribromotrichlorodiphenylether, tetrabromodi-
chlorodiphenylether and decabromodiphenylether. The halogen
atoms of these diaromatic ethers may be distributed in any
arrangement on the aromatic rings.
~xamples of suitable aromatic-aliphatic ethers are
the 2-ethylhexyl-, n-octyl, nonyl-, butyl-, dodecyl-, and
2,3-dioxopropyl ethers of tribromophenyl, tribromochlorophenyl
and tribromodichlorophenyl. The most preferred compound is
- decabromodiphenyl ether.
Other aromatic bromine compounds are described in
U.S. Patents 3,833,538 issued September 3, 1974; 3,849,369
issued November 19, 1974; British Patent 1,372,120 issued
October 30, 1974; West German publications 2,328,517 published
January 10, 1974; 2,328,520 published January 10, 1974 and
2,328,535 published December 20, 1973, all issued to Michigan
Chemical Corporation. Other suitable aromatic bromine com-
pounds are well known to those skilled in the art or will
become obvious upon reading the present specification.
The amount of halogenated fire retardant additives
is in the range of from 0 to 15 percent by weight, preferably
4 to 12 percent by weight in order to provide an additional
amount of halogen to the composition.
SYNERGISTS
~i Examples of synergists used in combination with
the halogens in order to obtain improved fire retardant proper-
ties include metal oxides such as Sb2O3, Bi2O3, MoO3, SnO2,
WO3, and the like. The preferred metal oxidè is Sb2O3. These
metal oxides (especially antimony oxide) function as synergists
in improving the efficiency of the halogen in imparting flame
retardancy to the above-mentioned polymers. The amount of
metal oxide used with the polymers of this invention will be
from 1 to 15 percent by weight, preferably 3 to 12 percent by
~ - 6 -
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weight, based on the total weight of the formulated composition.
`SMOKE SUPPRESSANTS
The polymers of the present invention may be
further modified with smoke suppressants in order to enhance
; 5 fire retardant properties and/or smoke evolution properties.
Examples of smoke suppxessants would include hydrates, carbon-
ates and borates such as alumina trihydrate, aluminum hydroxide
` sodium carbonate hydrate, magnesium carbonate, hydrated mag-
nesia, hydrated calcium silicate, hydrated calcium borate,
calcium carbonate, and magnesium borate. One of the preferred
smoke suppressants is dawsonite [Na Al CO3(OH)2] which is
available commercially from Alcoa. Mixtures of the above
smoke suppressants are also effective. The amount of smoke
suppressant used in this invention will be from 3 to 25 percent
by weight, preferably from 5 to 20 percent by weight based on
the total welght of the formulated composition.
In addition to acting as smoke suppressants, the
~ magnesium carbonate and/or magnesium borate are also believed
`l to react with the sodium oxide generated by the dawsonite
.
thereby keeping the sodium oxide from reacting with and tying
up the fire retarding halogens. Thus, when~using small amounts
of the carbonate or borate, e.g., from 3 to 15 percent by
welght based on the formulated composition, in combination
~ with the dawsonite, more of the halogen in the composition will
i 25 be more readily available to function as a flame retardant.
~ Alternately, when using dawsonite and other such componds, one
'I can increase the amount of halogen used in order to compen-
sate for that which may be tied up by the dawsonite.
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C-08-12 032~
The preferred 6moke suppressant system i9 a combination of magnesium
carbonate and dawsonite wherein the ratio of magnesium carbonate to dawsonite
iB at least 1:1.
RUBBER MODIFIERS
For added toughness, the polyFers of the present invention may contain from
O to 30 percent and more preferably rom 5 to 20 percent by weighe of a
synthetic or natural rubber component. Examples of the rubber components
include polymers and copolymers of butadiene, isoprene, chloroprene, as well
as other rubbers such as nitrile r~*bers, epichlorohydrin rubbers, acrylate
rubbers, natural rubbers, and'rubbery ethylene-vinyl aceta~e, ethylene-
propylene copolymers snd chlorinated polyethylene. The rubber component is
used to strengthen or toughen the interpolymer of styrene/maleic anhydride
and tXe brominated comonomer. The percent rubber referred to above is that
of the rubber substrate based on the total polyme~ composition.
lS The rubbery component may be incorporated into the matrix polymer
by any of the methods ~hich are well known to those skilled in the art, e.~.,
direct polymerization of monomers, graf~ing the styrene, maleic anhydride and
brominated monomers and mixtures thereof onto the rubbery backbone, forming a
polyblend of a rubber graft polymer with a matrix polymer, etc.
The preferred rubber components are epichlorohydrin rubbers,
polychloroprene rubbers and chlorinated polyethylenes.
,
The polychloroprene rubber component preferred for use in the pre-
sent invention is polychloroprene or a copolymer of-chloroprene and at lesst
one other mono~er such as butadlene, acrylonitrile, methacrylonitrile~ styrene,
ring substltuted halostyrene, alpha-hal~ostyrene, ring substituted alkyls~yrene,~ alpha-alkylstyrene, vinyl chloride, etc. The amount of comonomer used is in
the range of O ~o 20 percent based on the weight of polychloroprene rubber
copolymer.
Chloroprene rubbers are commercially available a8 solid rubber~,
rubber latices ~also referred to as emulsions) and solutions T~le preferred
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C-08-12-0329
polychloroprene rubbers used in the present invention are ~hose in solid form
or in organic solvent solutions as those in latex form must be recovered from
the latex and dried prior to use. The chloroprene rubber used is crosslinked
either be~ore or during processing in order to maintain it~ particulate nature.
Chloroprene rubbers are available from the E. I. duPont de Nemours and Company,
Wilmlngton, Delaware and from Petro-Tex Chemical Corporation of Houston, Texas.
The preferred epichlorohydrin rubbers are polyepichlorohydrin and
copolymers of epichlorohydrin with alkylene oxides such as e~hylene and pro-
pylene oxides. These rubbers are available commercially as Hydri* Elastomers
from B. F. Goodrich Chemical Company.
The rubber component is selected to provide a balance of good phys-
ical properties such as impact and gloss. Ungrafted rubber can be used in the
present invention. However, polychloroprene rubber, which has been grafted
with a polymer composition similar to that used for the matrix polymer, is
preferred because the grafted rubber provides better dispersion of the poly-
chloroprene.in the polyblend. This provides better impact strength and fire
retardancy properties.
PolychIoroprenes are conventionally grafted by dissolving or dis-
persing the rubber in the monomers to be grafted onto the polychloroprene.
The percent of monomer grafted onto the rubber is in the range of from
about 10 to 100 percent by weight with 10 to 50 percent being most preferred
to insure compatibility and good gloss. The percent graft is defined as the
weight percent of monomers grafted onto the rubber particle, based on the
weight of the rubber, e.g., 100 grams of rubber grafted with lO0 grams of
monomer has 100 percent of grafted monomers. Preferably, t~e grafted rubber
- has a particle size in the range of from 0.1 to 20 microns, more preferably,
1 to lO mirrons for optimum gloss and toughness.
~ he type and amount of ~onomers desrribed above in reference to the
preparation of the matrix polymer are used in the grafting polymerization of
~: 3a the rubber component. It is desirable to use halogenated comonomers in the
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C-08-12-0329
graft polymerization of the rubbers when these are used to prepare the matrlx
polymer.
TEST PEl~OCEDURF.S
Underwriter's Labora~ UL-94 Test tl~
Fire retardant properties are measured using the "Test for Flamm-
ability for Plastlc Materials - U~-g4", September :L7, 1973. The test is
carried out on test specimens 15.2 x 1.3 x 0.32 ~n. ~en other sample
thicknesses are used the stated thickness is given.
The te6t specimen is supported from the upper end, wi~h longest
dimension vertical, by a clamp on a ring stand so that the lower end of the
~pecimen i5 1 c~. above the top of the burner tube. The burner is then placed
remote from sample, ignited, and ad~usted to produce a blue flame, 1.9 cm. in
height.
The test flame is placed centrally under the lower end of the test
specimen and allowed to remain for 10 seconds. The test flame is then with-
drawn, and the duration of flaming or glowing combustion of the specimen noted.
If flaming or glowing combustion of the specimen ceases wi~hin 30 seconds
after removal of the test flame, the test flame is again placed under the
speclmen for 10 seconds immediately after flaming combustion of the specimen
stops. The test flame is again withdrawn, and the duration of flaming com-
bustion of the specimen noted.
If the specimen drops flaming particles or droplets while burning
in this test, these drippings shall be allowed to fall onto a horlzontal
layer of cotton fibers (untreated ~urgical cotton) placed one foot below the
test specin~en. Significantly flaming particles are considared to be those
capable of igniting the cotton fibers.
~1) The numerical flame spread ratings reported herein
are not intended to reflect hazards presented by
the presently claimed polyblends or any other
materials under actual fire conditions.
~LO~iS5;~7
C-08-1~-0329
The duration of flaming or glowing combustion of vertical specimens
after application of the test flame, average of five specimens (10 fla~e
applications) shall not exceed 25 seconds (maximum not more than 30 seconds),
and the portion of the specimen outside the clamp shall not be completely
burned in the test.
~aterials ~hich comply with the above requiremen~s and do not drip
any flaming particles or droplets during the burnin~ test will classify as
V-l according to the nomenclature used in the UL-94 test.
Materials which comply with the above requirements, but drip flaming
particle3 or droplets ~hich ignite cotton fibers will classlfy as V-2 accord-
ing to the nomenclature used in the UL-94 test.
Class V-O i9 given to materials wherein the duration of flaming
averages less than 5 seconds under the conditions sbove with no ignition
burning more than la seconds.
SMOKE EVOLUTIO~ TESTS
The method used for measuring smoke evolution is that describ~d in
D. Gross, J. J. Loftus, and A. F. Robertson, "Method for Measuring Smokè from
Burning Materials'7, Symposium on Fire Test Nethods - Restraint and Smoke,
1966, ASTM STP 422, Am. Soc. Testing Mats., 1967, p. 166.
The follo~ing examples are set forth in illustration of the present
invention and are not to be construed as a limitation thereof. Unless other~
wise indicated all parts and percentages are by weight.
EX~PLES 1 to 4 ~Control)
Examples 1 to 4 illustrate the effect of various amounts of maleic
an~ydride on the smoke evolution in styrene-maleic anhydride copolymers during
fire xetardant tests. The polystyrene and styrene-maleic anhydride (SMA) co-
polymers testsd are prepared by conventional ~echniques. These polymers are
then formulated as follows:
--10--
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C-08-12-0329
`- Polymer 77 parts
Antimony Oxide 4 part~
Decabromodiphenyl Oxide 9 parts
Dawsonite 5 parts
Magnesium Carbonate 5 parts
100 parts total
The decabromodiphenyl oxide is a conventional fire retardant addi-
tive, which is available commercially as Dow FR-30~ rom the Dow Chemical
Company. The antimony oxide is a synergist for the decabromodiphenyl oxide.
The dawsonite and magnesium carbonate are smoke suppressants.
The ingredients are compounded on a mill roll at temperatures in
the range of 160 to 195C. and then compression molded into test specimens
using temperatures in the range of 175 to 195~C. and pressures of about 4000
; to 5000 p9i (281 to 351 kg/sq.cm.). The molded-specimens are then tested for
flame and smoke properties using the tests described above. The results o$
these tests are tabulated ln Table I below.
TABLE I
SUMMARY OF CONTROL EXAMPLES 1 to 4
% Maleic
Anhydride UL-94 Dripping
Example in Polymer Dm (1~ RatinR Behavior AFOT (2)
1 Poly- 0 550(284~ Fail Drips 35
styrene ~eavily
2 SMA 7 518(226) Fail Drips 35
Slightly
3 SMA 14 472(213) V-O None 2
4 SMA 21 330(162) V-O None 2
- (1) The first number is under flaming while the
second number in parenthesis is under non-
flam~ng (smoldering~ conditions.
(2) Approximate flame out times.
Referring to Table I above, as the amount of ~aleic anhydride i~-
creases from 0 to 14 percent, the UL rating and approximate flame out times
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G-08-12-0329
(AFOT) become significantly better. In this regarcl the polystyrene of
Example 1 and the styrene-maleic anhydride copolymer of Example 2 which only
contain 7 percent by weight of maleic anhydride should be compared with
Examples 3 and 4 which contain 14 and 21 percent of maleic anhydride. In
S addltion, there is less smoke evolved and less tendency for the polymer to
drlp when using increasing amounts of maleic anhydride.
~ 11 of the above samples contain 9 parts of a decabromodiphenyl
oxide fire retardant additive9 which provides 7.4 percent bromine to the com-
position. Even at these bromine levels Examples 1 and 2 f~l the UL-94 test.
However, it should be noted that when Example l was repeated without the
dawsonite it passed the UL-94 test but dripped heavily and gave off greater
amounts of smoke. Moreover, the use of halogenated fire retardant additives
instead of halogenated monomers may result in non-uniform properties because
of the problem of obtaining a uniform dispersion of the additives in the
polymer.
EXAMPLE 5
Thi8 example illustrates a method for the preparation of the inter-
polymers of the present invention wherein a brominated monomer is inter-
polymeri~ed with the styrene (S) and maleic anhydride (MA). A mixture of 71
parts of styrene, 14 parts o maleic anhydride and 15 parts of 2,4,6-tribromo-
phenyl acrylate are stirred gently under a nitrogen blanket until the maleic
&nhydride and ~ribromophenyl acrylate are dissolved in the styrene monomer.
The resulting solution is transferred to pyre~ test tubes which are stoppered
and placed in an oil bath. The solutions are polymerized for 48 hours at
2S 80C. followed by polymerization at 105C. for 72 hours. It should be noted
~hat when using larger amounts of maleic anhydride, lower polymerizatlon
temperatures are used in order to obtain better control of the reaction. The
polymer is then ground, soaked in methanol for 24 hours, Piltered and dried.
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EXAMPLE ~
Example 5 i8 repeated here except that trlbromoneopentyl meth-
acryla~e i9 used in place o the tribromophenyl acrylate used in ~xample 5.
Th~ polymers prepared ln Examples 5 and 6 above, whlch have halogen
5 contents o about 7.9 percent by weight and t~ree di~ferent polymers used as
control sample~, are formulated as follows:
Polymer 86 parts
Antimony Oxide 4 parts
Da~sonite 5 parts
~agnesium Carbonate 5 parts
lQ0 parts total
The first control sample is the polystyrene homopolymer o~ Example
1. The secont control sample is a copolymer of styrene and tribromophenyl
acrylate (S/TBPA) and the thlrd sample is a copolymer of styrene and tribromo-
neopentyl methacrylate (S/TBNPA~, each containing 75 percent by weight ofstyrene and 25 percent ~y weight of the brominated monomer. The second and
. ~
third control sample~ have bromine contents of about 13 percent by weight.
Th~ samples are formulated and tested as outlined above. The results of these
tests are tabulated in Table II belo~.
TEST II
SUMMARY OF TESTS ON EXAMPLES S and 6
.
UL-94 Dripping D~
Example (1) Ratln~ AFOT (2) Behavior Flaming Non-Flamin~
1st control FailBurns Drips 462 255
Heavily
2nd con~rol V-2 2 Drips 445 20S
253rd control V-2 2 Drips 505 225
~-0 2-3 None 464 178
6 ~-0 2-2.5 None 509 177
(1) ls~ control - polystyrene; 2nd contrQl - S/TBPA 75/25;
3rd control - S/T~NPA 75/25.
~2) Approximate flame out tlmes.
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C-08-12-0329
Referring to Table II above, Examples 5 and 6 have a higher UL-94
rating (V-0~ than the second and thlrd control sa~ples (V-2)~ notwithstanding
the fact that the control samples contain 25 perclent by weight of the bro~i-
nated monomer as compared to the 15 percent by ~eight in ExampleR 5 and 6.
Moreover, ~xamples 5 and 6 do not drip whereas th~e control samples do. Note
further that the samples listed in Table II above, do not contaln any addi-
tlonal fire retardant additive. This illustrates the improved properties
which are obtained with the interpolymers of the present invention.
EXA~LES 7 and 8
These examples illustrate the use of a chlorinated rubber with the
interpolymers of the present invention. A high impact polystyrene (HIPS)
sample is included for control purposes. The interpolymers used in Examples
7 and 8 are the same as those used in Examples 5 and 6, respectively.
Seventy-six parts of these polymers are compounded with 10 parts of Hydrin*100,
a polyepichlorohydrin homopolymer which is available commercially from
B. F~ Goodrich Company. The rubber component is shredded and mill rolled with
~ the matrix at temperatures in the range of from 160C. to 195C. The mill
- rolled samples are ground and formulated with 4 parts of antimony oxide, 5
parts of dawsonite and 5 parts of magnesiu~ carbonate. The rubber modified
compositions of Examples 7 and 8 contain 7.9 percent bromine and 3.8 percent
chlorine for a total halogen content of 11.7 percentr The formulated samples
are then compression molded and tested for flame and smoke properties. The
results of these tests are tabulated in Table III below.
*Trad~ mark
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~ABLE III
SUMMARY OF EXAMPL~S 7 and 8
HIPS
Polymer (1) Control Example 7 Exam~le 8
UL-94 Test Fails V-O V~O
S AFOT (seconds~ Burns
Dm (Flaming) 600 420 460
(~on-flaming) ~0 191 181
Dripping Drips None None
(1) XIPS - polystyrene contains about 9 percent by
weight of a grafted bu~adiene styrene rubber.
Ex mple 7 - S/MA/tribromophenyl acrylate 71/14/15
pexcen~ by weight.
Example 8 - S/MA/tribromoneopentyl methacxylate
71¦14/15 percent by weight.
The data in Table III above indicate that the terpolymers of the
present invention, which are compounded with a chlorinated rubber and other
additives, have a UL-94 rating of V-O and an approximate flame out time of
1 second. In additlon, these samples have better impact properties than com-
parable non-rubber modified polymers.
29 EXAMPLES 9 to 11
A matrix polymer ls prepared which contains 78 percent by weight o
styrene, 7 percent by weight of maleic anhydride and 15 percent by weight of
tribromophenyl acrylate using ~he general procedures outlined above. This
matrix polymer is then for~ulated and tested for fire and smoke properties.
The formulations and test result~ are tabulated in Table IV below.
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TABLE IV
SUMMARY OF EXAMPLES g to ll
COMPOSITIONS
Parts of Example 9 E~ample 10 Exam~le 11
S Matrix Polymer 65 53.9 53.9
Hydrin 100 16 16 13.5
: Butadiene Rubber (1) ~ 13.2 13.2
Sb23 4 4 4
MgCO3 10 lQ 7.5
. ~
' ~ 10 Dawsonite 5 0 5
,
.~ Decabromodiphenyl oxide 0 2.9 2.9
Bromine Content ~% by weight) 6.1 7.4 7.4
Chlorine Co~tent ~ 9' 6.1 6.1 5.1
, Total Halogen content C% by 12.2 13.5 12.5
`: weight)
~; ; 15 (1) Gra~ted with about 100 percent by weight of styrene.
******
TEST RESULTS
UL-94 V-O V-O V-O
AFOT (seconds)
; Dm (Flaming)435 452 469
~Non-flaming) 253 345 281
Referring to Table IV above, ~xamples 10 and 11 illustrate the use
f~a butadiene-styrene type rubber in combinat~on with a chlorinated rubber
without adversely effecting the flame retardant properties of these 8y8tem8.
- EXAMPLE 12
: The general procedure of Example 5 is repeated here to prepare an
i~terpolymer which contain~ 70 percent by wei~ht of styrene~ 10 percent by
weight of maleic anhydride and 20 percent by weight of tribromophenyl acrylate.
.
~; ' '' '
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EXAMPL~S 13 to 17
The interpolymer prepared in Exa~ple 12 above i8 ~ormulated and
tested for fire retardan~ properties. The formulation and test results are
tabulated in Table V below.
TABLE V
SUMMARY OF FORMULATIONS AND TEST RESULTS
_ _ FOR EXAMPLES 13 to 17
Ex~m~le (1) 13 14 15 16 17
Polymer 68 63 68 63 $~
Epichlorohydrin rubber 1,6 16 0 0
Chloroprene rubber 0 0 16 16 16
Antimony oxide 6 6 6 6 6
Magnesium carbonate 5 10 5 10 15
DawsonitP 5 5 5 5 5
X Bromine 8.43 7.81 8.437.81 7.19
% Chlorine 6.13 6.13 6.406.40 6.40
UL-94 V-O V-O V-~ V-O V-O
AFOT (seconds) ~ 1 C 1 ~ 1 C 1 G 1
Dm (Flaming) 407 397 399 403 388
(Non-flaming) 200 290 250 370 288
Drlpping Behavior None None None None None
~1) Numerical values for co~ponents of ~he formulations
are parts by weight.
Referrlng to Table V above, the epichlorohydrin rubber used ln
Examples 13 and 14 i8 the Hydrin 100 reerred ~o above~ The polychloroprene
rubber used is a solid neoprene rubber obtained from E. I. duPont de Nemours
and Comp2ny. The UL-94 tes~s indicate ~he good flame retardant properties
ehat are obtained with the compositions oF the present invention.
EXAMPLE 18
The general procedure of Example S is repeated here to prepare an
in~erpolymer which contains 90 percent by welght of styrene, 5 percent by
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C-0~ 0329
weight of maleic ~nhydride and S percent by weight of trlbromophenyl acrylate.
EXAMPLES 19 ~o 22
The polymer prepared in Example 18 above is formulated and tes~ed
for fire retardant properties. The formulations and test results are tabu-
lated in Table Vl below.
TABLE V~
_ .
SUMMARY OF FORMULATIO~S AND TEST RESULTS
FOR EXAMPLES 19 to 22
~ . .
Example (l?` 19 20 21 22
Polymer . 69 69 62 62
Epichlorohydrin rubber 16 O 16 0
Chloroprene rubber O 16 O 16
; Antimony oxide 5 5 5 5
Magnesiu~ carbonate S 5 5 5
Dawsonite 5 5 5 5
Decabromodlphenyl oxide a o 7 7
~ Bro~ine 2.142.14 7.737.73
X Chlorine - 6.1~6.4 6.13 6.4
UL-94 Fails Pails V-O V-O
AFOT (seconds) ~ 30 ~ 30
Dm ~Flaming) 546 429 443 458
(Non-flaming) 362 361 372 383
Dripping Behavior None None None None
~l) Numerical values for components of the ~ormulation
are parts by weight,
~xamples 19 and 20 in Table Vl ~bove show the need for having at
- least 3 and preferably 6 percen~ by weight bromlne in the lnterpolymers of the
present invention. ~hen using the lower level of 5 percent by weight of a
~rominated monomer, the pa~ti~ular monomer used should have a bro~l~e content
which would supply the minimum requirement. Alt~rnately, an external source
of bro=ine must be u~ed.
'
'
18
~6iSS~
The polymers of the present invention are useful
:~ for preparing a wide variety of molded objects such as radio
and television cabinets, applianca housings~ parts and
components for vehicles, furniture and other related items.
S Polymers of the present invention may be further
modified with conventional additives and adjuvants such as
fillers, plasticizers, U.V. stabilizers, heat stabilizers,
antioxidants, etc. Care should be taken when formulating or
compounding the polymers of the present invention so as not
to adversely effect the flammability and/or smoke evolution
propertles of th polymers of the present invention.
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