Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION
United States Patent No. 3,403,036, describes polymer
compositions containing as fire retarding agen~s, Diels-
Alder adducts of a halogenated cyclopentadiene and poly-
unsaturated cycloaliphatic compounds. Ac1ducts disclosed bythe patentees are the diadducts of 1,5-cyclooctadiene,
dicyclopentadiene, cyclopentadiene and bicycloheptadiene.
It has now been found that the diadducts of halogenated ~`
cyclopentadienes and the compound bicyclononadiene exhibit
unexpectedly superior proper~ies in certain polymer applications.
The superior properties include fire retardant efficiency and
lower afterglow, and the polymer compositions have improved
heat deflection properties and tensile and flexural properties
over similar polymer compositions containing the DielsAlder
diadducts known in the art as fire retardant additives.
SUMMARY OF THE INVENTION
:, .
Fire retardant polymeric compositions are provided
which comprise a polymer and an effective fire retardant
proportion of the Diels-Alder diadducts of a halogenated cyclo-
pentadiene and bicyclononadiene. The compounds of the
invention have the formula:
.. ~'"
: - 2 -
'
,
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X~X
X X ,
wherein X is selected from the group consisting of bromine,
chlorine, and fluorine, Y is selected from the group consisting
of bromine, chlorine, fluorine, alkyl of 1 to 10 carbon atoms,
alkyloxy wherein the alkyl group contains 1 to 10 carbon atoms, ;
; haloalkyl and haloalkyloxy wherein the alkyl groups contain 1
to 10 carbon atoms and halo is fluoro, chloro, or bromo.
The preferred fire retardant additive compound of the
in~ention is the Diels-Alder diadduct of hexachlorocyclo-
pentadiene and bicyclo(4.3.0)nona-3,7-diene. The chemical name
for the compound is 1,2,3,4,6,7,8,9,12,12,13,13-dodecachloro-
1,4,4a,4b,5,5a,6,9,9a,10,10a,11a-dodecahydro-1,4:6,9-dimethano-
11 H-benzo(b) fluorene.
DESCR.IPTION~OF THE EMBODIMENTS
The additive compounds of the invention are prepared by ~ ~
reacting bicyclononadiene with halogenated cyclopentadienes ~ -
~` of the formula:
'~ X x '~
1.. ,.. , ~ y
-. ~,
X X .. ,~ -
- 3 - ~
~" "
: :
.. , , . , ,.......... . . ; :
: ... , : , ~ ,. . .
:- - . , . . .
1~?79L483
wherein X and Y are as defined above. The diadduct of bi-
cyclononadiene and hexachlorocyclopentadiene is disclosed
at J. Gen. Chem. of the U.S.S.R. 29 page 3552 (1959).
Halogenated cyclopentadienes suitable for use in the
preparation of the adducts descxibed above include hexa-
halocyclopentadienes, such as hexachlorocyclopentadiene,
hexafluorocyclopentadiene and hexabromocyclopentadiene, mono-
alkyl-pentahalocyclopentadienes, such as l-methyl-pentachloro-
cyclopentadiene, l-ethyl pentabromocyclopentadiena~ l-hexyl
pentafluorocyclopentadiene, l-decyl pentachlorocyclopentadiene;
dialkyltetrahalocyclopentadienes such as l,l-dimethyl tetra-
chlorocyclopentadiene, l,l-dibutyl-tetrachlorocyclopentadiene,
l-methyl, l-hexyltetrabromocyclopentadiene, l,l~dinonyl-tetra-
fluorocyclopentadiene, l,l-didecyl tetrachlorocyclopentadiene;
: 15 alkoxy halocyclopentadienes such as l-methoxy-pentachloro
~ and l,l-dimethoxy tetrachlorocycloF)entadiene, l-hexoxy penta-
bromo-, and l-hexoxy, l-octoxy tetrabromocyclopentadiene,
l-decoxy-pentachloro- and l,l-didecoxy-tetrachlorocyclopen~a-
diene, l-ethoxy-pentafluoro- and l-ethoxy, l-butoxy-tetra-
fluorocyclo~entadiene; monohaloalkyl halocyclopentadienes
such as l-chloromethylpentachlorocyclopentadiene, l,l-bis
(chloro~methyl) tetrachlorocyclopentadiene, l~romoethyl-
pentabromocyclopentadiene, l,l-bis(bro=ohexyl) tetrachloro-~ -
cyclopentadiene, l-fluorodecyl pentafluorocyclopentadiena,
25 l,l-bis-(fluorodecyl) tetrafluorocyclopentadiene, l-chloro-
. methyl, l~bromopropyl tetrabromocyclopentadiene. The prefer-
: red halocyclopentadiene is hexachlorocyclopentadiene.
The adduction step is preferably in liquid phase reaction.
. ' ' :,'
_ ~,, _
.
Although the reactants may be combined directly, the reaction
is preferably carried out in the presence of a solvent.
The solvent can be an excess amount, over the stoichlo-
metrical proportion, of the halocyclopentadiene reactant or
a solvent which is inert to the reactants and the reaction
product may be used. Preferably, the solvent should boil
above about 90 degrees Celsuis. Suitable nonreactive
solvents include toluene, xylene, nitrobenzene, methyl-
cyclohexane, perchloroethylene, acetylene tetrachloride and
the like.
The temperature employed in the adduction step can range
from about 75 degrees Centigrade to about 200 degrees Centigrade,
although temperatures outside this range can be used. Pref- ;
erably, the adduction reaction is effected at about 85 de~rees
to about 170 degrees Centigrade. The time required for the ad-
duction to go essentially to completion may vary according
to the reactivity of the halocyclopentadiene, the presence
or absence of solvent, the temperature of the reaction, etc.
Generally, a reaction period between about 5 and 100 hours
will suffice, but preferably from about 10 to 48 hours.
The reaction is preferably and conveniently carried ~-
out under atmospheric pressure conditions although super-
atmospheric pressures may be used, and on occasion may be
preferred, especially when one of the reactants is of low
reactivity and/or high volatility. ~enerally, when super-
atmospheric pressure is used, autogeneous pressure will
: .
-~ suffice althou~h pressures of from 1.1 atmospheres to 100
atmospheres or more can be used.
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The polymers embraced within the scope of this invention
include the h~mopolymers and copolymers of unsaturated alipha-tic,
alicyclic and aromatic hydrocarbons. Suitable monomers are
ethylene; propylene; butene, pentene; hexene; heptene;
octene; 2-methylpropene-1; 3-methylbutene-1; 4-methylpentene-1;
4~methylhexene-1; 5-methylhexene-1; bicyclo-(2.2.1)-2-heptene;
butadiene; pentadiene; hexadiene; isoprene; 2,3-dimethyl-
butadiene-1,3; 2-methyl-1,3-pentadiene; 4-vinylcyclohexene;
vinylcyclohexene; cyclopentadiene; styrene and methylstyrene,
and the like. Polypropylene, ABS polymers, polystyrene
and high impact or rubber-modified polystyrene are
especially useful polymers. High impact polystyrene is a
heterophase polymer with a rubbery polymer dispersed as
small globules in a continuous matrix of polystyrene. The
amount of rubber present by volume may be as low as 10 to
15 percent in medium impact grades and range as high as 40
percent in extra hlgh impact types. The rubbery polymer
used with the polystyrene is usually an elastomer with
residual unsaturation, for instance, polybutadiene or a
styrene-butadiene rubb~r. These toughened grades of
polystyrene can be made by mechanical mixing of the
rubber and the polystyrene on a two-roll mill or
extruder. Common manufacturing techniques involve solution- ~
graft polymerizatlon processes although some special ;
grades are made by blendlng polybutadiene latex or
mechanical mixing with the polystyrene which can be
made by the processes of mass, suspension, solution, ionic,
or emulsion polymerization. The graft polymerization
process s~arts with dissolving the rubber in styrene
monomer, the rubber solution is then fed to the polymer-
ization vessels. Other polymers useful in the practice of the
~7~
invention are disclosed in U.S. Patent 3,403,036.
The polymers of the invention can be in various
physical forms, such as shaped articles, for example, molding,
sheets, rods and the like; fibers, coatings, films and fa~rics,
and the like.
The halogenated Diels-Alder adducts in the present com-
position are desirably incorporated in the po]ymeric materials
in an effective fire retardant amount. Generally, halogenated
Diels-Alder adducts in the amount of from about 2 to about 50
percent by weight of the polymeric composition and desirably
from about 5 to about 40 percent by weight of the polymeric
composition and preferably from about 10 to 35 percent by
weight are mixed with polymeric composition. Improved fire
retardance can be provided by incorporating metallic compounds
wherein the metal is selected from the group consisting of
antimony, arsenic and bismuth, in the polymeric compositions
in the amount of about 1 to about 30 percent by weight of
said polymeric composition, preferably about 2 to 25 percent.
Antimony oxide is the antimony compound that is pre-
sently preferred for use in the present invenkion. However, ~
many antimony compounds are suitable. Suitable antimony com- ~-
pounds include the sulfides of antimony, salts of the alkali
: .
metals of Group I of the Periodic Table,antimony salts of ;~-
organic acids and their pentavalent derivatives and the esters
of antimonious acids and their pentavalent derivatives. It is
convenient to use sodium antimonite or potassium antimonite
when it is desired to use an alkali metal salt of the antimony
. ,. ~
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.' ,: . - . ~ . ............................... .
:
for compositions of this invention. U.S. Patent 2,996,528
discloses suitable antimony salts of organic acids and their
pentavalen-t derivatives. Compounds of th:is class include
antimony butyrate, antimony valerate, antimony caproate,
antimony heptylate, antimony caprylate, antimony pelargonate,
antimony caprate, antimony cinnamate, antimony anisate and
their pentavalent dihalide derivatives. Likewise, the esters
of antimonious acids and their pentavalent derivatives dis-
closed in U.S. Patent 2,993,924 such as tris(n-octyl) anti-
; lO monite, tris(2-ethylhexyl) antimonite, tribenzyl antimonite,
tris(beta-chloroethyl) antimonite, tris(betachloropropyl)
antimonite, tris(beta-chlorobutyl) antimonite and their
pentavalent dihalide derivatives. Still other suitable organic
antimony compounds are the cyclic antimonites such as tri-
methylol propane antimonite, pentaerythritol antimonite and
glycerol antimonite. The corresponding arsenic and bismuth
compounds can also be employed in particular the oxides of
arsenic and bismuth.
The components comprising the compositions of the instant
invention can be mixed by any one of several methods. The
additives can be lntroduced in~o the polymer whlle the latter
is dissolved in a suitable solvent. This procedure is espec-
ially useful when it is desired to mix the additives during
the polymer manufacturing process. When the polymer is sub-
sequently recovered from the solvent, the additives areintimately mixed ~7ith the polymer. Usually, the additives
are mixed with the polymer in the molten state at temper-
atures that can range from the melting point to the decompo-
sition temperature of the polymer, e.g., from 70 to 600degrees centigrade. Alternatively, the addi-tives and
polymer are dryblended in the finelydivided state so that an
intimate mixture is obtained upon subsequent molding or
extrusion.
The following examples are intended to illustrate the
invention, but are not intended to limit the scope of the
invention. In these examples, as well as in the specifica-
tion and claims, parts and percentages are by weight and
temperatures are given in degrees Centigrade unless other-
wise specified.
Example 1 Preparation of Diadduct of Bicyclononadiene -~
(A) To 1230 grams (4.5 moles) of hexachlorocyclopentadiene
. . .
which were heated to 150 degrees centigrade were added over
a period of two hours, 180 grams of bicyclo(4.3.0)nona-3,7
diene (1.5 r,loles) dissolved in 410 grams of hexachlorocyclo-
pentadiene. The reaction mixture was heated at about 150
degrees centigrade for twelve hours and then cooled to
. .
precipitate a solid product. About 752 grams of solid product
were filtered off the reaction mixture and the solids were
.;
refluxed with xylene and filtered and washed with benzene to
provide 542 grams or product having melting point of 338-340
degrees Centigrade.
(B) To 1230 grams (4.5 moles) of hexachlorocyclo-
pentadiene heated to 160 degrees centigrade were added drop-
wise over a period of two hours a solution of 180 grams of
bicyclo(4.3.0)nona-3,7-diene (1.5 moles) dissolved in 410
grams of hexachlorocyclopentadiene. The reaction mixture
was heated at 160-170 degrees centigrade for 12 hours and
.. . .
~ 9 ~
,. , , ., , ... , ... , ., .:, : :. .- ,
then cooled to precipitate a solid product. The solid
product was filtered from the reaction mxture and washed
four times with 300 milliliters of acetone to provide 696
o
grams of a product having a melting point of 339-342 C.
The resul-ting 694 grams of product was refluxed with 500
milliliters of xylene for one hour, cooled, filtered and
washed with xylene.
(C) The product of Example 1 (B) was combined
with -the solid product of Example l(A). The combined products
were refluxed with xylene, cooled, filtered and washed with
benzene to provide 912 grams of purified
1,2,3,4,6,7,8,9,12,12,13,13-dodecachloro-1,4,4a,4b,5,5a,6,-
9,9a,10,lQa,lla-dodecahydro-1,4:6,9-dimethano-11 H-benzo(b)
fluorene.
Example 2
27 parts of the diadduct of hexachlorocyclopentadiene
and bicyclononadiene prepared as described in Example l(C) were
compounded with 13 parts of antimony trioxide and 60 parts
of polypropylene and molded into test specimens which were sub-
jected to tests for fire retardancy and mechanical properties.The results of these tests are shown in Table I, together with
the results of similar tests made with the diadducts of hexa-
chlorocyclopentadiene and dicyclopentadiene and 1,5-cyc]oocta-
diene, respectively, and a control test with polypropylene
alone. The test results show that the compound of the
invention~was superior with respect to heat dè~lection data.
Example 3
18 parts of the diadduct of hexachlorocyclopentadiene and
bicyclononadiene prepared in Example 1 (C) were compounded
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with 6 parts of antimony trioxide and 76 parts of ABS
polymer (slendex 101) and molded into test specimens which
were subjected to fire retardancy tests and mechanical
tests and shown to have the pr-operties se~ forth in Table
II. Also shown in Table II are the results of similar
tests made with the diadducts of hexachlorocyclopentadiene ~ -
and dicyclopentadiene and 1,5-cyclooctadiene, respectively,
and control tests with ABS polymer alone.
The adduct compound of the invention is seen to be
superior with respect to fire retardant efficiency and
tensile strength.
Example 4
Fifteen parts by weight of the diadduct of hexachloro-
cyclopentadiene and bicyclononadiene prepared in Example l(C)
were compounded with 5 parts of antimony trioxide and 80 parts
of polystyrene and molded into test specimens which were
subjected to tests or fire retardancy and mechanical properties.
The results of these tests are shown in Table III together
with the results of similar tests with respect to molded
specimens of polysty~ene containing the diadducts of
hexachlorocyclopentadiene with dicyclopentadlene and
1,5-cyclooctadiene~ respectively, and control tests with
polystyrene alone.
The additive compound of the invention is seen to be
superior with respect to afterglow properties and tensile
" . ,
strength and flexural properties. The adduct of the invention ~:
is seen to be superior to the diadduct of 1,5-cyclooctadiene
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.~ith respect to impact strength.
Beneficial results are obtained by incorporating
the diadduct of Example l(C) in high impact rubber-modified
polystyrene.
It will be apparent to those skilled in the art that
.lany variations and modifications of the inventi.on can be made
without departing from the spirit and scope of the invention,
the foregoing specification and examples are intended to be
illustrative and not to limit the invention.
- 18
- . :
