Note: Descriptions are shown in the official language in which they were submitted.
~ 8CH-1946
.
This invention is directed to a flame retardant
polycarbonate composition and in particular an aromatic
pol~carbonate conta~ning in admixture therewith a particular
flame retardant additive which may be the metal salts o~
either mono~eric or polymeric aromatic suLonates, or mLxtures
thereof.
Wlth the increasing concern for safety, ~here is a
positive move towards providing safe materials for public and
household use. One particular area of need is that of providing
flame resistant or flame retardant products for use by the
ùltimate consumer. As a result of this demand, many products
are being reguired to meet certain flame retardant criteria
both by local and federal government and the manufacturers of
such products. One particular set of conditions employed as
a measuring standard for flame retardancy is set forth in
Underwriters Laboratories, Inc. Bulletin 94. This Bulletin
sets forth certain conditions by which materials are rated for
self-extinguishing characterlstics.
In the art, there are many known flame retardant
addi~ves which are employed by mixing with products to render
such materials self-extinguishing or fla~e retardant. Such
~lame xetardant additives have been known to be employed in
; a~ounts of 5 to 20 weight percent in order to b0 e~fective in
extinguishing burni~g of those products which are combustible.
It has also been found that such amounts can have a degrading
effect upon tha base product to be rendered flame retardant,
resulting in the losses of valuable physical properties o~
the base product. This is particularly so when employing known
flame r~tardant additives with the base product polycarbonate
resins. Many o* these known additives have a degrading effect
upon the polymer.
It has now been surpri~ingly discovered t:hat an
/
8CH 1946
4~
aromatic polycarbonate can be made flame retardant by
incorporatin~ with the aromatic polycarbonate minor amounts
of certain additives, which additives are inert and do not
degrade the aromatic polycarbonate. The particular additive
employed herein is unique in that even very minor amounts render
the aromatic polycarbonate ~lame retardant~ The amount o~
the additive employed herein can vary, preferably, from 0.01
to about 10 weight percent based on the weight of the aromatic
polycarbonate.
More specifically, the particular additive of this
invention is the metal salt of either the monomeric or poly-
meric aromatic sulfonates or mixtures thereof. The metal salt
employed in the practice of this invention is either the
alkali metal or alkali earth metal salt and can include mixed
metal salts. The metals of the~e groups are sodium, lithium,
potassium, rubidium, cesium, beryllium, magnesium, calcium,
strontium and barium~
In the practice of this invention, the types of
aromatic sulfonates employed herein may be either the monomeric
form or the polymeric form or mixtures thereof. When first
considering the monomeric form, the metal salt of the substituted
monomeric aromatic sulfonate can best be represented by the
following formula:
~A~ R~0-2 ~ I.
wherein ~ and L~ can, in turn, be independently selected
~rom the following formula:
~S03M)yR~ II.
wherein M is a metal which may be selected from the periodic
table o either an alkali metal or an alkali earth metal, R'
is an aryl radical of 1-4 aromatic rings, and y an integer of
0-10. It is to be understood, however, that in Formula I,
there must be at least one ~1) S03M radicalO
~ 8CH-1946
In Formula I above, ~ is an organic radical of 1-20
carbon atoms and is either alkyl, aralkyl, alkenyl, aralkenyl,
aryl, arylene, alkylene, aralXylene, alkenylene, aralkenylene,
alkylidene, aralkylidene, alkenylidene or aralkenylideneO It
should also be understood that ~R~ can contain halogen substitu-
ents such as chlorine, bromine or fluorine.
As indicated above, Formula I, in its sL~plest form,
can consist merely of ~B3 which in turn would be merely Formula
XI with y being equal to 1. This is where LA~ and ~R~ would be
zero (0). Thus, the simplest formula is a~ follows:
(S03M~
and more specifically
S03Na
Actually, while there are many compounds that meet
the requirements of Formula I and which offer excellent flame
retardant characteristics to an aromatic polycarbonatet the
preferred additive employed in the monomeric form is disodium
naphthalene-2,6-disulfona~eO This has the following formula:
so3~a
NaO3S'~/
Mixtures of the metal salts of the monomeric aromatic sulfonic
acids can be employed herein.
~hen the polymeric form of ~he aroma~ic sulfonate is
employed in the practice of this invention, it can best be
repxese~ted by the following formula:
- 3 -
8CH-1946
æ~
rA ~ ~ ~ m~n rB~n }II.
wherein r~ and ~B3 are independently selected from khe
following formula:
~ SO3M)yR~ IV.
wherein R', M, and y have the same meaning as recited
previously. In addition, the same re~uirement for y is also
applicable. However, it is also under~tood that ~ and ~BJ
units can be randomly selected. In addition, rRl~ LS an organic
radical of 1-20 carbon atoms and is either arylene, alkylene,
aralkylene, alkenylene, aralkenylene, alkylidene, aralkylidene,
alkenylidane and aralkenylidene. In the polymeric form, ~R~
cannot be monovalent as in the case of the monomeric form of
the additive employed herein and described by Formula I above.
In Formula III, the sum of m and n must be at least 4 and can
be as high as 4000. As shown, the selection of m and n can
be random or e~ual or one can be zero (0). In Formula III, R
can also contain halogen substituents as prevîously recited
for [R~ of Formula I.
In the practice of thi~ invention, it is to be under~
~20 ~tood that the polymeric structure can be either a homopolymer,
a copolymer, a random copolymer, a block copolymer or a random-
block copolymer, including mlxtures thereo~. In addition, the
ratio of sulfonated aromatic rings to unsulfonated aromatic
rings can vary from greater than 1 to 1 to as high as that
which is necessary to render the polycarbonate flame retardant.
This may be 1 to 100.
In order to more ~ully and clearly illu~trate the
present invention, the following specific examples are presented.
It is lntended that the examples be considered as illustrative
rather than limiting the invention disclosed and claimed herein.
In the examples, all parts and percentages are on a weight
basie unless otherwise specified~
8OEI-1946
Example I
~ inety-nine (99) parts of an aromatic polycarbonate,
p.repared rom 2,2-b.is~4-hydroxyphenyl)propane and pho~gene in
the presence of an acid acceptor and a moIecular weight regulator
and having an intrinsic viscosity of about 0.57, is mixed with
1 part of a finely ground dehydrated additive listed in Table I
by tumbling the ingredients together in a laboratory tumbler.
The resulting mixture is then ~ed to an extruder which is
operated at aho~t 265C., and the extrudate is comminuted into
pellets.
m e pellets are then injection molded at about 315 C.
into test bars of about 5" by 1/2" by about 1/16-1/8" thick.
The test bars (5 for each additive listed in the Table) are
then evaluated in accordance with ~he test procedure of
Underwriters' Laboratories, Inc., Pulletin UL-94, May, 1971,
Burning Test for Classifying Materials. In accordance with
the test procedure, material~ are classified as either SE-0,
SE-I or SE-II. The results are based on 5 specimens. The
critexia for SE rating per UL-94 is briefly as follows:
"SE-0": Average flaming and/or glowing after removal
of the ignlting flame shall not exceed 5
seconds and none of the specimen3 shall drip
flaming particle~ which ignite absorbent
cottom~
"SE-I": Average flaming and/or glowing after removal
of the igniting flame shall not exceed 25
seconds and the glowing does not travel ver-
tically for more than 1/8" of the specimen
after flaming ceases and glowing is incapable
of igniting absorbent cotton.
"SE-II": Average flaming and/or glowing after removal
of the igniting flame shall not exceed
- 5 -
8CH-1946
~6~
25 seconds and khe specimens drip flaming
particles which ignite absorbent cotton.
In addition, a test bar which continues to burn for more than
25 seconds after removal of the igniting flame is classified,
not by UL-94, but by the standards of the instant invention,
as "burns". Further, UL-94 requires that all test bars in
each test group must meet the SE type rating to achieve the
particular classification~ Otherwise~ khe 5 bars receive the
rating of the worst single bar. For example, if one bar is
classified as SE-II and the other four (4) are classified as
SE-O, then the rating for all 5 bars is SE-II.
The results of the different addi~ives within the
scope of the instant invention are as follows with a control
being the aromatic polycarbonate as prepared above without
the additive of the type set forth herein.
TABLE 1
-- 6 --
8CEI--1946
I ~
.o o
5:L ~
bq ~rl
~a m
,1 ~
~ O
m ~ ~
~ 4~
Ul
o~
3 ~J N
~ 0 HH 1-1 H H H H H H H H H
.,1 ~:: H H H H1~ 1 H H H 1-1 H
I'l Wli~ '1 W W W 1
~; m tnU3 tn u~
~q
P~ ~
In O OO O ~D ~ O ~ O
U~ ~ . . . . . . . . .
~1 ~ ~ ~ ~ D u7 ~ ~ o
O E~
o
P~
E3 ~
.~ o
~ O
O ~O ~ ~ ~ ~ ~ ~ ~ I~ In O _~
~ ~ . I
h 8
,, ~
o
o~
Q) al N ~1 ` I ~H
~) ~ ~ _I d' O
1~ 1 N~ 1 I h
8 o ~o ~ ~ ~
_ ~ ~
, ~ o U , .~ U
o
~, ,, ,, ,,~, o ~ ~ , U
Q ~ O S
~J ~ O O N N I~I-rl1~ O
~ ,~ ~ a. ~ O ~I q~
r~ o:~ ~ Q
3 ~ O O
~ l hr~
o ~ ~o I o o
~ E~l alN N h ~ ~Ql rlI
_I ~ O,s~ ) U
_ o a)(U~D Ql S~1
.) N R ~q ~ UUl
~U ,
~ ~ O ~.rl
~1 r~O ~: O O t~O ,~O ~ O ~O r~
~ O ~ ~ 1 U ~ ) O O
~ u~ 4 C) ~'tS Cl ~ Cl~a a ~ P~ u~
8CH-1946
~ U~
~ ,~ o a H
~ H H H
~ ~a
"m
~1 0 N ~
O E-l O ,I r-l
~
h P .
~ ~ d' In
E ol ~ 5 ~ ~ E
C~
,_ V ~ X
U
S ~ ~ In h I V
g O s~
r~l rl g r
P ~ ~J ~ JJ ~ ~
1 ~ ~ ~ ~ ~ o
.~ , _~ ~ ~ ~ ~ ~O
3 (_) J~ ~ ~D V ~ N . Q) ~ O
In ~ ~ ~ ~ 0 ~ ~ I
O ~ ~ ~ ~ ~ _l ~_
C,) ~ O ~ -~ O ~ . _ ~ O
_I ~ ~ ~ , ~ O ~I bq ~
_~ O U ~ I rl 1 ~ :~ O I ~ I ~O ~) ~ U3 r l ~ ~S
~o m~ ~ ~-,lo ~ "o
~ ~ ~o ~ ~l ~o ~
bq ~ ~ ~ ~n O ~ ~0 ~ 0 ~ O
~ O ~ I p ~-A OI ~ ~ 1 0
q:~ ~a ~ J 1~ a) a) u~ I la at o
~ ~ ~ 3 ~ ~ ~ 3 i' ~ 3
8CH-1946
s~
~rl H H H
~ l l l
W ~ E~l
u~
~q
rl tq
3~
U~ r~l N OD
~
O E~ N r-l r l
O ~I)
~i ~
a~ - i
~ I O _I CO
rl a .
E~ ~
0~ I I ~
r l ID (~
N
r~
~, ~ rU~
l ,~ O ~
_ ~ ) ~ ~1 0 t~
r r l ~ r l a) r~l
, tl~
~ I. : _' ~W U ~d
U I_ I rl 3~ ~I r~l O IC
aJ ,~ ~ U~1 a) O q-l r~l
S ~ s E3 r l
~ I ~ ~--~ o o ~ Q
r~ ~~~ O S l ~3 Ul r l
t: ~ ~ U~ 0 ~ 3 ~ O
~1 ~ O ~ O
a) u u ~ o o ~ o o ~ ,
3 U I ~"~
o O ,~ ~ o ~ ~1
. I ~ ~ O S~
~1 ~ i ~ ) ~1 ~ 1 ~ ri
_ ~1 ~ ~ r l ~ S O ~ 1 0 _I ~
1~ y 3 rl O rl O ~ 0
~ R
~ ~ ~ ~ E~
_~ ~ ~ ~ s~
,1 1 O ~ O ~,~ O ~n
b'~ --, ri E3 0 ~ Id
tQ ~ ~ a
r 14 ¦ ~d 0 Il) U~ U 0 iDU~ Q)
~1 * e~ I 3 ~ n~ ~ 3 * Ql *
.
~ 3 8CH-1946
Ex~ample II
This Example is set ~orth to demonstrate the e~fect
o~ the flame retardant additive~ of this :invention at the
lower limit of 0.01 weight percent based on weight of the
polymer composition.
In preparing the test bars for this Example,
99,99 parts of the polycarbonate of Examp:Le I are mixed with
0.01 weight percent of the additives listed in Table 2
employing the same mixing procedure. Test bars are th@n
molded using the same molding conditions employed in
Example I~ The test bars are subjected to the same test
pxocedure of Example I with the following results;
TABLE 2
-- 10 -
8CH-1946
~ 3
.Y
CJ
.,1 ~ H H H 1-1
tr; m cn cn tn cn
~q ~
IQ ~9 0 ~ ~9
q 7
O E~ ~r~
.
~ o~
~--
~ ~D ~ ao
o ~
~ ~ co ~ ~ o
c)
-~ ~u
~ u~
a~
~ ~ u~
_ ~ ~ rl O IU
~ o o o c~ ~
~ ~ ~ u
u
u~
a) .-1 ~ o
p ~ ~~ ~ ~
~ o
~J ~J N N~ ~ ~ O
rl ~ O
3 ~ o
Q,
. E~~q ~ ~ ~--1
o ~ h ::~
_ N E3 1 ~
~ ,Q 0~ O
~ ~ u ~ ~
.,1 .,1 o o ~
~rl rlO U
tn ~ ~ 3
-- 11 --
-
~ 8CH-1946
Example III
This Example i9 set forth to show the e~fect of a
known, commercially available flame retardant additive.
A.
Example I is repea~ed except that in place of the
additives employed therein, only 1 part 1,2,5,6,9,10 hexabromo-
cyclododecane is used herein. ~he results obtained upon
evaluating ~ive (5) test bars are the same as obtained for the
Control shown in Table 1 above.
B.
Part A. above i8 repeated but using 5 weight percent
of the above additive, namely 1,2,5,6,9,10-hexabromocyclododecane~
The results obtained are the same as obtained ~n Part A. above.
C.
Part A. above is repeated but using 10 weight percent
o~ the above additive, namely 1,2,5,6,9,10-hexabromocyclo-
dodecane. At this level of additive, test bars are rated SE-II.
However, the polycarbonate is badly degraded as evidenced by
severe dark streaking of the molded test bars, whi~h degradation
does not occur with the additives o~ the instant invention.
Example IV
Example III is repeated except that hexabromobiphenyl
is employed herein. The re~ults obtained are essentially the
same as those of Example III.
Example V
Example III is repeated except that the additive
~-~ employed herein is a combination of antimony oxide and a
material which is a mixture of polychlorinated hiphenyl (Aroclo
by Monsanto Company)~ m e proportion of the ingredients of the
additive, employed in this example is based on 3 parts of
chloxine per 1 part of antimony~ ~he results obtained at 1
weight percent and S weight percent amounts axe the sa~e as
8CH-1946
in Examine III.
However, at the higher amount, namely 10 weight
percent, flame retardancy effect is noted but with, again,
severe degradation of the polycarbonate, a~ evidenced by the
substantial reduction ~n the intrinsic viscosity of the molded
test bars. As molded, the intrinsic viscosity of the test
bars with 1 weight percent of the above additive is about 0O50.
The intrinsic viscosity of the molded test bars containing 10
weight percent of the flame retardant additive of this
Example is 0.253. This shows the severe degradation of the
polycarbonate w~en employing this type of well known flame
retardant.
In the practice o~ this invention, aromatic carbonate
polymers are rendered flame retardant by the addition of
certain particular additives which are the metal salt~ of
monomeric or polymeric aromatic sulfonic acids or mixtures
thereof. The amount of the additives employed in the practice
of this invention may vary from 0.01 to up to that amount
which after further increasing does not material increase the
flame retardant properties of the polycarbonate~ This is
generally up to about 10 weight percent basad on the weight
o~ the aromatic carbonate polymer but may be higher. The
amount of the additive to be employed can also be a function
of the degree of flame retardancy desired.
~t is not exactly understood how the additive of
this invention functions ox how such minor amounts can act as
an effective flame retardant fox the aromatic carbonate polymer~
Analysis of the composition of this invention after being
subjected to a fire temperature of about 600C. shows an
unusually high percentage of remaining char. This leads one
to hypothesize that the additive may act as a cross~linking
agent when the aromatic carbonate polymer is subjected to fire
- 13 -
8CH-1946
temperatures. However, it is emphasiæed that this is only
theory and should not be construed as actually occurring.
As indicated previously, the aclditive of the instant
invention comprises the alkali or alkali earth metal salts of
the monomeric or polymeric arom~tic sulfonic acids and includes
mixtures thereoE. While a great number of such salts are set
forth in the tables of the Examples of the instant invention,
these are only a representative sample of the additives o~
this invention. The sodium, calcium, magnesium, potassium,
strontium, lithium, barium, rubidium and cesium salts of other
aromatic sulfonic acid can be employed ~n place of thsse of
the E~amples with the same effective flame retardancy being
achieved. ~he~e other aromatic sulfonates are:
meta-benzenedisulfonic acid, disodium salt
para-benzenedisulfonic acid, dipotassium salt
1,3,5-benzenetrisulfonic acid~ trisodium salt
biphenyl-4-sulonic acid, calcium salt
naphthalene-l-sulonic acid, barium salt
xylene sulfonate, sodium salt
naphthalene-2-~ulfonic acid, strontium salt
naphthalene-2,7~disulfonic acid, disodium salt
naphthalene-1,4,7-trisulfonic acid, trisodium salt
anthracene-2,6-disulfonic acid, sodium-potassium salt
phenanthrene-l-sulfonic acid, magnesium salt
pyrene-1,3,6,8-tetrasulfonic acid, tetrasodium salt
diphenylmethane-4-sulonic acid, calcium salt
1,1-diphenylethane-4,4'-disulfonic acid, disodium salt
2,2-dichloro-1,1-diphenylethylene-4',4''-disulfonic
acid, disodium salt
triphenylmethane-4,4',4''-trisulfonic acicl, trisodium
salt
1,1,2,2-tetraphenylethane-4,4l,4'',4'''-tetrasulfonic
acid, tetrapotassium salt
1uorenedisulfonic acid, dilithium salt
- 14 ~-
~ ~ 8CH-1946
9,1Q-dihydroanthracene-2,7~disulfonic acid, disodium
slat
sulfonated polybenzyl, polysodium salt
sulfonated polystyrene, polysodLum salt
sulfonated polystyrene (crosslillked with divinyl-
benzene), polysodium salt
sul~onated polybiphenyl, polysodium-potassium salt
sulfonated poly ~ di(biphenyl)ethane~, polysodium salt
In the practice of this invention, the additive i9
generally prepared ~y well known methods in the art. For
example, one such well known method involves taking an aromatic
hydrocarbon such as benzene and contacting it with either sul-
furic acid, chlorosulfonic acid, uming sulfonic acid or sulfur
trioxide. These reactions can be carried out at room temperature
or at elevated temperatures such as about 50C. The salt is then
prepared by adding the proper alkaline reagent in suffi~ient
amount to make the neutral salt. me salt is then recovered
by precipitation or by distillation of the solvent.
In the practice of this invention, any of the aromatic
polycarbonates can be employed herein. However, particularly
useful are the aromatic polycarbonates prepared by reactîng a
dihydric phenol, such as bisphenol-A, (2,2'bis(4 hydroxyphenyl)
propane) with a carbonate precursor. Typical of svme of the
dihydric phenols that may be employed in the practice of this
invention are bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis~4-
hydroxyphenyl)heptane, 2,2-(3,5,3',5'-tetrachloro-4,4 t -dihydroxy-
diphenyl~propane, 2, 2Q ( 3,5,3',5'-tetrabromo-4,41-dihydroxy-
diphenyl)propane, (3,3'-dichloro-4,4~-dihydroxyd iphenyl~methane.
Other dihydric phenols of the bisphenol type ara also available
and are disclosed in U.S. patents 2,999,835 - Goldberg, issued
Septemberl2, 1961; 3,028,365 - Schnell et al, issued April 3, 19627
and 3,334,154 - Kim, issued August 1, 1967.
In addition, the reaction is carried out with the
~ 15 -
~ 8CH-1946
carbonate precur~or in the presence of a molecular weight
regulator an acid acceptor and a catalyst. The pre~erred car-
bonate precursor generally employed in preparing carbonate
polymers is carbonyl chloride. However, other carbonate
precursors may be employed and this inclucles other carbonyl
halides, carbonate esters or haloformates~
The acid acceptors, molecular weight regulators and
catalysts employed in the process of preparing polycarbonates
are well known in the art and may be any of those commonly
used to prepare polycarbonates.
As indicated previously, the additive employed
herein can consist of mixtures of the metal salt~. These
mixtures can be mlxtures of the various metal salts of the
monomeric aromatic sulfonic acid or mLxtures of the various
metal salts of the polymeric aromatic sulfonic acids or mixtures
of the metal salts of the monomeric and the polymeric aromatic
sulfonic acids. ~he mixtures have provided certain advantages
such as SE-0 rating of 5 test bars and essentially ~ero number
of drips per test bar.
It will thus be seen that the objects set forth above
among those made apparent from the preceding description are
efficiently attained and since certain changes may be made in
carrying out the above process and in the composition set forth
without departing from the scope of this invention, it is intended
that all matters contained in the above description shall be
interpreted as illustrative and not in a limiting sense.
- 16 -
6C~9~6
SUPPLEL~EMT~RY DISCLO~SURE
In the principal disclosure of my invention thers
are described novel Elame retardant compositions comprising'
aromatic carbonate polymer~ in ad~i~t~re with from about
0.01 to about 10 par-ts by weight per hunclred par-ts of th2
polymer of an additive comprising yiven metal salts of a
sulfonic acid of a defined class~
It has further been found that such additive may be
effective for the above stated purpose when present in a
concentration of as little as 0~001 parts per hundred parts
of the polyrner.
It has still f~lrther been found that when the
additive as defined earlier has a refractive index in the
same range as that of the aromatic carbonate polymer ie.
about 1.54 to 1,65, the aforesaid compositions wherein the
additive is present in about 0.001 to about 2 parts per
hundred parts of aromatic carbonate poly-rner are not onLy
flame retardant but are also non-opa~ue.
,- ~ i
By non-opaque i5 meant that the polycarbonate
compositions and shaped articles produced therefrom ~hich
may be in the form o~ sheet, for example, or merely in the
form of pellets suitable for extrusion, are able to transmit
light. The compositions ma~ vary from translucent to
transparent, depending upon the closeness of the refractive
index of the additive to that o~ the aromatic carbonate polymer.
If the additive at the concentration employed is partially or
totally soluble in the carbonate polyrner, the transpare~cy of
compo3ition and article will n~turally be increased,
The refractive indices of the materials herein
described are determined ~y the immersion method a3 shown in
Physical ~ethods of Organic Chemistry (Weissberger Interscience
Publishers, Vol. I~, 1960, p 1~33).
17 -
~ 8CH-~46
Interscience Publishers, Vol II, 1960, p L433).
A preferred additive for the formula~ion of non-
opaque products which confers excellent fLame retardency is
disodium naphthalene 2,6 disulfonate
NaS03 /~
The non-opaque flame retardent compositioTIs which
comprise this additional aspect of my invention may further
comprise other additives which are commonly employed in the
formulation of non-opaque aromatic carbonate polymer products,
for example pigments, dyes, antioxidants, stabilizers, U~ V.
light absorbers, mold release agents etc~
In order to illustrate the present invention more
fuLly and clearly, both in its general aspect in providing
flame retardent compositions and also in the more specific
and newly disclosed aspect in providing non-opaque flame
retardent compositions, the following additional examples
are presented. All parts and percentages are expressed upon
a weight basis unless otherwise specified. The examples are
not to be considered as limiting the scope of the invention,
this being elsewhere defined,
Example VI
One hundred parts of the aromatic polycarbonates
as in example 1 is mixed with 0.01 part of a finely ground
dehydrated additive as listed in table 3. Test bars prepared
as in example l are subjected to the UL 94 Burning Test, with
the bars oriented in the vertical position. The results are
classified into 3 grades, V-0 - VII, the criteria for the
grades being essentially the same as for those earier given for
the corresponding SE grades~
me test squares are tested for light transmission
in a Gardner XL 10-CDM instrument. The data shows the amount of
- 18 -
106 ~ 8CH~9~6
incident light transmitted by the test s~uares using air as
100% transmission.
The result o an additive withi.n the scope o~ the
.instant invention is as follows with a control being the
S aroma~ic polycarbQnate as prepared above without the additive
o the type set ~orth herein~
' ,
:
- 19 -
~3CEI~946
d1 ~
~n ~ .,~
I ~ ~: H H
~ m
.Q,~
4~ a) _1
o:~
~oi s~
.~
o o ~9
O N
1i3 O
,
.,1 ~q ~
~@
E~
I ~ ~
3~ o ~u
.
,,
to
I ~ ~
,~
a~ ,
~ `
tQ ~ I
5~ ~ ~
~1
o ~ ~
C .~ .~
a
U~
. , o
~ ~ rl O
~ ~i ~ ~
~ 8 1! l
r ~
- 20 ~
.~ 8CH1946
~L~ L~
F~MP~E VXI
-
This Example is set forth to demonstrate the effect
of the additives o thi~ invention at limits of 0.10 parts
per hundred parts of the polycarbonate.
In preparing the test specimens for this Example,
100.00 parts of the polycarbona~e of Example I is mixed with
0.10 parts o~ the additives listed in Table 4 employîng the
same procedure, Test specimens are then moldea using the same
procedure employed in Example I. The test specimens are subjected
to the same test procedure of Example VI with the following
results:
Table 4
- 2~ -
~CEI-19~6
.,
rl
I ~J S-l H H
m P P
I
~q
~rl W
5~ ~
o o
a~ _I
o P
O q~
~s~
G)
. .~
~Q
~ ~ ~ CD
o o
a~
~U~
~I
o
,,
IQ
-1 h
$ ~ ~
-I ~
_ ~ ~ O
1 3 ~ ~
I ~ ~
S~ , ~0
I
~ O ::~
I
~ 1~ ~1 0 In
a~ o
I ~ ~I-rl
C
_ .
~rl ~ q u
C~
i
rl O V-rl
f ~ Q
- 2 2
8CH-~46
EX~MæLE V~III
m is example is set forth to demonstrate the efect
of the additive~ of this invention at limits of 0.20 parts
per hundred parts of the polycarbonate.
In preparing the test specimens for this Example,
100.00 parts of t~e polycarbonate of Exam~le I is mi~ed with
0~20 parts of the additives listed in Table 5 employing the
same procedure. Test specimens axe then molded using the
same procedure employed in Exanple I. The test specimens are
subjected to the same test procedure of Example VI with the
following re~ults:
Table 5
23 -
8cH-l946
~ .~
L ¦ ~1 o H H H
!~ I m
~q~
o o o o
~,
op
P~
'E~
~n a~
, .
I ~ ~ U~
o I
~ .
r~
U~ ~ bq
,~ ~ o
~ ~ ao
:~ ~ ~ ~:
i
Q)
^
~Q
Q ~ o _
la ~ o ,,
Ul
O
s~
~ -I ~ 0 a
Q ~ N
u~
O 0 N 0 0
O
.
,l ~ ~ o
~ z ~ ~ ~ ~
o Q ..
V U~
- 24 -
. .
8CHi94 6
EXAMPLE IX
This example i5 set forth to demonstrate the ef~ect
of ~he additives of this invention at limits of 0~50 parts
per hundred parts of the polycarbonate.
In preparing the test specimens ~or this Example,
100.00 parts of the polycarbonate of Example I is mixed with
0.50 parts of the additives listed in Table 6 employing
the same procedure. Test specimens are then molded using
the same procedure employed in Example I. The test specimens
are subjected to the same test procedure of Example VI with the
following results:
Table 6
~,~
- 25 ~
8CH~946
,~
~- I
I ~ ~ O H H
!~1 p~ m
s~
0
s~ a)
o o o
o ~
.
h
.~
E~
~ O ~9 ~ U~
O U N
~ Cq
_l
~D O
0
O) O Ct)
m ~ ~ ~ a~
~i
E~
_
1 40
I
I
I ~ ~ I
I ~ ~ a
I o o ,~
I ~ ~ ~
h ~
r~ 3 ~:s
~q ;n _I
a~
I
N N ,~:
~_ 5
¦ , ~ R .Q
. I ~1 ~rl rl
I
o o ~ o
I ~ u~ m u~
2 6
~ 8CH~46
In the practice of this invention, aromat~c carbonate
polymers are renderad flame retardant by the addition of
certain particular additives which are the metal salts of
mon~meric or pol~meric aromatic-sulfonic acids or mi~tures
thereof~ The amount of the additives employed in the practice
of this invention may vary from 0.001 to up to about 10 parts
per hundred parts of aromatic polycarbonate.
As indicated previously, the additive of the
additional aspect of the instant invention comprise~ the alkali
or alkali earth metal salts of t~e monomeric or polymeric
aromatic sulfonic acids and includes mixtures thereof having
a refractive index in the range of 1.54 to 1.65. While a great
number of such salts are set forth in the tables of the
Examples of the instant invention, these are only a representative
~ample of the additives of this invention. The sodium, calcium,
magne~ium, potassium, strontium, lithium~ barium, rubidium and
cesium salts of other aromatic sulfonic aci~s can be empl~yed
- in place of those of the Examples with the same effective
ome
~ ~ ~lame retardancy being achieved. ~k~s~ other aromatic
sulfonates are:
meta-benzenedisulfonic acid, disodium salt
para-benzenedisulfonic acid, dipotassium salt
1,3,5-benzenetrisulfonic acid, trisodium salt
biphenyl-4-sulfonic acid, calcium salt
naphthalene-l-sul~onic acid, barium salt
xylene sulfonate, sodium salt
naphthalene-2-sulfonic acid, strontium salt
naphthalene-2,7-disulfonic acid, disodium salt
naphthalene-1,4,7-trisulfonic acid, trisodium salt
anthracene-2,6-disulfonic acid, sodium-potassium salt
phenanthrene-l-sulfonic acid, magnesium salt
pyrene~l,3,6,8-tetrasulfonic acid, tetrasodium salt
diphenylmethane-4-sulfonic acid, calcium salt
.~
- 27 -
8CHi946
~g~
1,1-diphenylethane-4,4'-disul~onic acid, disodium salt
2,2-dichloro-1,1-diphenylethylene-4',4"-disulfonic acid,
disodium salt
triphenylmethane-4,4'~4"-trisulfonic acidi tr;~odium
salt
1,1,2,2-tetraphenylethane-4,4',4",4"'~tetrasulfonic
acid, tetrapotassium ~alt
fluorenedisulfonic acid, dilithium salt
9,10-dihydroant~race~e-2,7-disulfonic acid, disodium
salt
sulfonated polybenzyl, polysodium salt
sulfonated polystyrene, polysodium salt
sulfonated polystyrene ~crosslinked with divi~ylbenzene),
polysodium salt
sulfonated polybiphenyl, polysodium-potassium salt
sulfonated poly[l,l-di(biphenyl)ethane~, polysodium ~alt
In the practice of this invention, any of the aromatic
polycarbonates can be employed herein having a re~ractiva index
in the range of 1.54 to 1.65. These are homopolymers and
copolymers and mixtures thereof that are prepared by reacting
a dihydric phenol with a carbonate precursor.
It is, of course, possible to employ two or more
dif~erent dihydric phenols or a copolymer of a dihydric p~enol
with a glycol or with hydroxy or acid terminated polye~ter, or
with a dibasic acid in the event a carbonate copolymer or
interpolymer rather tha~ a homopolymer is desired for u9e in
~he preparation of the aromatic carbonate polymers of ~his
invention. Also employed in the practice of this invention may
be blends of any of the above materials to provide the
aromatic carbonate polymer.
The carbonate precursor may be either a carbonyl
halide, a carbonate ester or a haloformate. The carbollyl
28 -
~ CH~46
halides which can be employed herein are carbonyl
bromide, carbonyl chloride and mixtures thereof~ Typical o~
the carbonate esters which may be employed herein are diphenyl
carbonata, di-(halophenyl) carbQnates such as di-(chloro-
phenyl) carbonate, di-(bromophenyl) carbonate, di-(trichloro-
phenyl) carbonate, di-~tribromophenyl) carbonate, etc., di-
(alkylphenyl~ carbonate such as di(tolyl) carbonate, etc., di-
(naphthyl) carbonate, di-~chl~ronaphthyl) carbonate, phenyl tolyl
carbonate, chlorophenyl chloronaphthyl carbonate, etc~, or
mLxtures thereof. m e halo~ormates ~uitable for use herein
include bis-haloformates of dihydric phenols (bischloroformates
of hydroquinone, etc.) or glycols (bishaloformates of ethylene
glycol, neopentyl glycol, polyethylene glycol, etc.). While
other carbonate precursors will occur to those skilled in the
art, carbonyl chloride also known as phosgene is preferred.
Also included are the polymeric derivatives of a
dihydric phenol, a dicarboxylic aci~ and carbonic acid.
The aromatic carbonate polymers of this invention
may be prepared by employing a molecular weight regulator; an
acid acceptor and a catalyst. The molesular weight regulators
which can be employed in carrying out the process of this
invention include monohydric phenols such as phenol, chroman-I,
paratertiary-butylphenol, parabromophenol, primary and secondary
amines, etc. Preferably, phenol is employed a~ the molecular
weight regulator~
A suitable acid acceptor may be either an organic or
an inorganic acid acceptor. A suitable organic acid acceptor.
A suitable organic acid acceptor is a tertiary amine and
includes such material3 as pyridine, triethylamineO climethyl-
aniline, tributylamine, etc. The inorganic acid acceptor may
be one which can be either a hydroxide, a carbonate, a
bicarbonate, or a phosphate of an alkali or alkaline earth metal.
The catalyst~ which are employed herein can be any of
. .
_ ~9 _
~c~9~
the suitable catalysts that aid the polymerization of bisphenol-
A with phosgene. Suitable catalysts include tertiary amines
such as for example, triethylamine, triprlopylamine, N,N-dimethyl-
aniline, quaternary ammonium compounds such as for example
tetraethylammonium bromide, cetyl triathyl ammonium bromide,
tetra-n-hyptylammonium iodide, tetra-n-propyl ammonium bromide,
tetramethylammonium chloride, tetramethyl ammonium hydroxide,
tetra-n-butyl-ammonium iodide, benzyltrimethylammonium chloride
and quaternary phosphonium compounds such as for example,
n-butyltriphenyl phosphonium bromide and methyltriphenyl
phosphoniu~ bromide.
Also, included herein are branched polycarbonates
wherein a polyfunctional aromatic compound is reacted with the
dihydric phenol and carbonate precursor to provide a thermo-
plastic randomly branched polycarbonate.
These polyfunctional aromatic compounds contain at
least three functional groups which are carboxyl, carbioxylic
anhydride, haloformyl or mixtures thereof. Examples of these
polyfunctional aromatic compounds which may be employed in the
practice of this invention include: trimellitic anhydride,
trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic
anhydride, pyromellitic acid, pyromellitic dianhydride,
mellitic acid, mellitic anhydride, trimesic acid, benzophenone-
tetracarboxylic acid, benzophenonetetracarboxylic anhydride and
the like. The preferred po~yfunctional aromatic compounds are
trimellitic anhydride or trimellitic acid, or their haloformyl
derivatives.
Also, included herein are blends of a linear poly
carbonate and a branched polycarbonate.
As indicated previously, the additive employed herein
can consist of mixture of the metal salts~ These mixtures can
be mixtures of the various metal salts of the monomeric
- 30 -
~ 8CHi946
aromatic sulfonic acid or mixtures o~ the various metal ~alts
o~ the polymeric ar~matic sulfonic acids or mixtures of the
metal salts o the monomeric and the polymeric aromatic sulfonic
acids. The mixtures have provided certain advantages ~uch as V-O
rating of 5 test bars and es~entially ~ero number of drips
per test bar.
It will thus be sean that the objects set ~orth
above amvng those made apparent from ths preceaing description
are efficiently attained and since certain changes may be
made in carrying out the above process and in the composition
set forth w~thout departing from the scope of this invention,
it is intended that all matters contained in the above
description shall be interpreted as illustrative and not in a
limiting sense.
- 31 -
