Note: Descriptions are shown in the official language in which they were submitted.
RD-4998
~77~04
This invention relates to monomeric and poly-
meric halogenated organic compounds of the formula:
. ~
R Br Br R
Rl ----O ~(~ ~ ~ ~o_Rl
R Br Br R
wherein each R independently is selected from primary ~.
alkyl groups, each Rl is independently selected from
hydrogen, and organic groups, at least one Rl being an ~.
organic group.
In our Canadian application, Serial No. 149,429 :
filed August 15, 1971, and assigned to the same assignee as
the present invention, we disclosed the preparation of
2,2',6,6'-tetrabromo-3,3',5,5'-tetraalkyl-4,4'-biphenol
(hereinafter sometimes referred to as TATB) by reacting .
a 3,3',-5,5'-tetraalkyl substituted diphenoquinone with
bromine and the subsequent conversion of the monomeric
. ~ .. . . . .. .
RD-4998
derivatives into reactive monomeric materials suit@d to
the preparation of polyesters, polycarbonates, epoxy resins,
polyethers, etc. These materials are useful as fire-
retardant additives for polymeric compositions, and are
useful in the preparation of flame-retardant polymeric
compositions having bromine constituents integrated within ~-
the skeletal backbone of the polymer structure.
Although other halogenated biphenols, including
monomeric and polymeric derivatives thereof, such as bis-
phenol-A and those derived from bisphenol-A are well-known
to the art, the tetraalkyltetrabromo-biphenol derivatives
of our invention are advantageously employed in the prepara-
tion of fire-retardant polymeric compositions because of the
unexpected ~hermal stability associated with the molecular
arrangement found within the 2,2',6,6'-tetraprimaryalkyl-
3,3'-5,5'-tetrabromo~4,4'-biphenyldioxy molecular structure.
Quite unexpectedly, it has been found that the polymeric
entity associated with the halogenated biphenols and biphenol
derivatives described herein are more thermally stable at
elevated temperatures than other well-known halogenated
biphenols, such as bisphenol-A, and derivatives thereof.
Although we do not wish to be bound by our theory,
we believe that the symmetrical oxygen-alkyl-bromine bi-
phenyl spatial relationship associated with the TATB of
formula ~I.) is such a spatial relationship that compositions
_ _ ,
,~,; ',~ ~'
.. .. .. .. ..
~'775~)~
RD-4998
containing such molecular arrangement are especially stable
against thermal degradation at elevated te~peratures.
This resistance to thermal degradation, as evidenced by
the lack of discoloration of polymeric compositions con-
taining such molecular configurationsg is noticeable when
the discoloration of similar polymeric compositions
containing other halogenated biphenols are mixed expecially
at temperatures comparative within the range of from
about 200C. to as high as 550C., or even higher.
For illustrative purposes, the difference in
thermal stability of 2,2',6,6'-tetramethyl-3,3',5,5'-
tetrabromo-4,4'-biphenol (hereinafter sometimes referred
to as TTB) and 2,2'-bis(3,5-dibromo-4-hydroxypheny~ propane
(hereina~ter sometimes referred to as tetrabrominated
bisphenol-A ~BBPA) are illustrated by the percentage weight
losses associated with the aforementioned halogenated
biphenols when each is separately heated at 10C. per
minute under TGA test conditions in (a) the presence of
air and (b) in the presence of nitrogen set out hereafter.
,
'.
.~ ,,~ ;' .
3L0775~4 ~ ~
RD-4998
( 1 ) TGA DATA- TTB
(a~ AIR (10C. /min.) ~`
Weight Loss 1% 5% 10% 25% 50~/O 75% 95%
Temp. C. 260 295 312 370 448 493 527
(b) N2(10/min.)
Weight Loss 1% 5% l~/o 25% 5~% 75% 95%
Temp. C. 240 270 280 298 312 325 510
(2) TGA DATA-TBBPA
(a) AIR (10 C. /min.)
Weight Loss 1% 5% 10% 25% 50% 75% 95%
Temp. C. 245 275 280 310 315 340 510
(b) N2(10 C./min.)
Weight Loss 1% 5~/O 10% 25~/o 5~/O 75% 95%
Temp. C. 245 275 280 320 330 370 770
, '
From the above TGA thermal decomposition data, TTB
is more stable than TBBPA at temperatures within the range
of from about 240 to about 530, temperatures well within
the range at which many resins and plastic materials are
substantially thermally dedompo~ed to monomeric materials,
, , .
e.g. polyacrylonitrile, (250C.); polymethylmethacrylate
(350C.); polystyrene (350C.); polyalphamethylstyrene ~ ;
(350C.); polyisoprene (370C.); poly-n-methylstyrene
(390C.); polyisobutylene (400C.); polyvinylacetate
(280C! under vacuum), polyacrylonitrile (350C. in the
presence of nitrogen); polypropylene (410C. under vacuum);
polyvinylchloride (440C. in the presence of nitrogen);
polyvinylidene chloride (440C. in the presence of nitrogen);
polybutadiene (420QC under vacuum), and polyethylene
. ~
'
'''J~' ~
,, ,"., .. , . ,. , .,.. , . . .. .. . .-. ..
5~ ~ RD-4998
~'
(475C. under vacuum), etc.
In accordance wi-th this invQntion, we have found
that novel monomeric and polymeric halogenated organic .
compounds of the formula: ;
. ~
' ,
R Br Br R
S Rl _ O _ ~ O - R
R Br Br R .
wherein each R independently is selected from primary alkyl
groups, each R iS independently selected from hydrogen ~:
and organic groups, at least one Rl is an organic
group.
Representative of monomeric halogenated organic
compounds included within the scope of the above formula are
2,2',6,6'-tetrabromo-3,3',5,5'-tetraalkyl-4,4'-biphenol
derivatives wherein each R1 independently is selected from
the radicals consisting of~
(i) organic radicals, such as
(a) R2
(b) R ~ O - R~
,,'. y
(a) R4 ~ C - ~oR3
.
; - 5 -
.~ ,, .
RD-4998
~ A
~d~ R4 ~ 52 ~ (oR3~ ~
O ~ :
(e) R - - CH CH(R )x t
~ / :
wherein R2 is selected from the group consisting of hydrogen,
cyano, alkyl, alkenyl, cycloalkyl, cycloalkenyl,
aryl and mixtures thereof, such as alkylaryl, alkylcyclo- ;
alkyl, arylalkyl, alkenylaryl, alkenylcycloalkyl, arylcyclo-
alkenyl, arylalkenyl, etc., R3 is selected from the group ~ ;~
consisting of alkylene, cycloalkylene, arylene and
mixtures thereof, such as alkylcycloalkylene,
alkylarylene, etc., R4 is selected from the group
consisting of hydrogen, alkyl, alkenyl, cycloalkyl,
cycloalkenyl, aryl and mixtures thereof, such as alkylaryl,
alkylcycloalkyl, arylalkyl, alkenylaryl, alkenylcycloalkyl,
arylcycloalkenyl, arylalkenyl, etc., x is a positive
integer of at least l, y is a positive integer of at least
1, and z is a positive integer of at least 0. Preferably,
the organic hydrocarbyl radicals represented by R2, R3
and R4 contain from about 1 to about 10 carbon atoms, and
more preferably contain from about l to about 5 carbon
atoms. Among the derivatives includes within th~ above
organic groups are such compounds as 4,4'-bis(20hydroxy-
~ ethoxy)-2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl
., :
:.1
;-
; - 6 - ~
: /
"
: , , ... . . . , .. ., " ,~ . ,.,.. , .. I - .
~5~4 RD-4998
(for purposes of brevity sometimes hereafter the phrase :
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl will
be referred to as TTBP); 4-hydroxy-4'(2-hydroxyethoxy~~
TTBP; 4-(2-hydroxyethoxy)-4l[2-(2-hydroxyethoxy)-ethoxy~-
TTBP; 4,4'-diacetoxy-TTBP phenyl; 4,4'-dihydroxy-TTBP-
diglycidylether; 4,4i,diallyloxy-TTBP, 4,4'dicyanato-TTBP;
4,4'-diaryloyloxy-TTBP; 4,4'-bis(2-hydroxypropoxy-TTBP;
4,4'-bis(4-hydroxycyclohexoxy)-TTBP; 4,4l-bis(4-hydroxy-
phenoxy~-TTBP; 4,4'-bis(4-hydroxydecylox~ TTBP;4,4'-bis~7-hy-
droxynaphthoxy)-TTBP; 4-hydroxy-4'-(2-hydroxyethoxy)-TTBP;
4-hydroxy-4'-(4-cyclohexyloxy~-TTBP, 4-hydroxy-4 t _ ~ '
(hydroxyphenoxy)-TTBP, 4-hydroxy-4'-~4-hydroxydecyloxy)-TTBP,
4-hydroxy-4'-{hydroxynaphthoxy)-TTBP, etc. :
As disclosed in our Canadian application Serial . ;
No.149,429 filed Augustl5, 1972, referred to hereinbefore :~
TTB derivatives such as 4,4'-bis(2-hydroxyethoxy)-2,2',
6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl can be
converted readily to esters of monocarboxylic acids, can
be reacted with ethyleneox^ide to form 4,4'-bis(2-hydroxy- .~?
. 20 e~hoxy)-2,2',6,6'~tetrabromo-3,3',-5,5'-tetramethylbiphenyl
~ which in turn can be incorporated into either polyesters
or polycarbonates or made into plasticizers, can be .
reacted with epichlorohydrin to form 4,4'-dihydroxy-2,2',-
6,6l-tetrabromo-3,3',~,5'-tetramethylbipheny diglycidyl-
`
RD-4998
'.
ether which is useful in making epoxy resins, can be
reacted with a mixture of acetic acid and acetic anhydride
to prepare the diacetate ester, i.e., 4,4'-diace~oxy-
2 9 2',6,6'-tetrabromo---3,3',5,5'-te~ramethylbiphenyl, can
be reacted with allyl chloride to prepare 4,4'-diallyloxy-
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl, can
be reacted with cyanogen bromide to replace both hydroxy
groups with a -CN groups in the preparation of 4,4'-
dicyanato-2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbi-
phenyl, etc.
As previously pointed out in our Canadian
application, Serial No. 149,429 referred to hereinbeforeg
the monomeric reactan~ 4,4'-diallyloxy TTBP and a 4,4'-
dicyanato-TTBP can be polymerized when heated with or
without a polymerization catalyst, either alone or with
other polymerizable monomers into useful polymers.
4,4'-diglycidyloxy-TTBP can readily be conver~ed to epoxy
resins, either alone or with other epoxides, by reaction
with monomeric or polymeric diols in the presence of
- 20 polyamine or anhydride catalysts. The 4,4'-bis(2-hydroxy-
:.,
; ethoxy)-TTBP can be reacted to form polyesters with dicar-
boxylic aci~ esters by ester interchange with low molecular
weight glycols, e.g., 1,4-butanediol, etc., polyesters of
terephthalic acid in the presence of a transesterification
-8
:; ~
:
RD-4998
~L0~5~4
.
catalyst to produce homopolymers as well as copolyesters.
These polyesters like other polymers described hereinbefore
have fire-resistant properties, per se, or can be blended
with other polymers to impart flame resistant properties
to the blend. ;
The following examples illustrate the preparation
of the 2,2',6,6'-tetrabromo-3,3 t ~ 5,5'-tetraalkyl-4,4'-
biphenol derivatives which are within the scope of this
invention. They are not to be construed, however, to limit
the scope of our invention in any manner whatsoever.
~ '
EXAMPLE 1 Preparation of 4,4'-bis(2-hydroxyethoxy)-2,2', -
6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl.
...
CH ~ r Br CH3
~o(CI2)2~ o(C~2)2~
C~13 Br Br CH3
A solution of 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbi-
,~. .
.:
'
_ g _
:
~,~
., .,. :;,.
,. . ..
~,7,~Q,9~ :~
RD-4998
phenol ~400 g., 0.718 mole) and sodium hydroxide (65.2 g.,
1 63 mole, 2.27 molar equivalents) in 600 ml. of deaera~ed
50% acqueous ethanol was heated at reflux under nitrogen
for 30 minutes. Deaerated distilled ethylene chlorohydrin ~;
(237 g., 2~94 mole) was added slowly to this hot solution
and the resulting mixture was hea~ed for one hour. About ;
30 minutes into this reflux period, an additional 200 ml.
of deaerated 95% ethanol was added to partially redissolve `
a solid which had ~ormed (some sodium chloride remains
precipitated). After the one hour reflux period, an
additional 65.2 g. (1.63 mole) of sodium hydroxide and 50
ml. of deaerated water were added and the mixture refluxed
for 30 minutes. Ethylene chlorohydrin (237 g., 2.94 mole)
was added slowly and this mixture heated for 75 minutesO
Sodium hydroxide (100 g., 2.5 mole), deaerated water (200
ml.) and deaerated 95% ethanol (450 ml.) were added, and
this mixture refluxed for 45 minutes. A final portion of
-, ethylene chlorohydrin (474 g., 5.88 mole) was added and this
mixture refluxed for 75 minutes. Deaerated water (3 liters)
;1 20 was then added to the vigorously stirred mixture and, while
still stirring, the mixture was allowed to cool. After
standing overnight, the crystals were filtered and dried
in vacuo for 4 hrs./100Co The product was reerystallized
from 500 ml. of methanol giving, after vacuum drying,
: 10
,, , ,. . , - . , j . .. . .
0~
RD-4998
322.0 g, of the diol 4,4l-bis(2,hydroxyethoxy)-TTBP, m.p.
170-172C. Additional product was obtained from the original
reaction mixture totaling 137.7 g. The total yield of
product was 99.3%.
EXAMPLE II - Preparation of 4,4l-bi~(2-hydroxyethoxy)-
2~2'~6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl
.. :
CH Br Br CH
HO(CH2)20~0(CH2)20H
C 3 Br Br H3
, , , ~,
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbi-
phenol (2.00 g., 3.59 mole) and triethylamine (34 mg,, 0.34
mole) in 3 ml. of diethyl carbitol (CH3CH20CH2CH2)2p) were ;i
heated to 175. Ethylene oxide was then bubbled through the
~ solution. Solvent was added as necessary to maintain the
'~ volume and an additional 34 mg. of triethylamine was added
, after the first 34 hours. The progress of the reaction was
monitored by TLC and at the end of the 53 hours, the reac-
tion product consisted essentially of 4,4~-bis(2-hydroxy-
ethoxy)-TTBP with only traces of the monohydroxyethylated
material 4 hydroxy-4'-(2-hydroxyethoxy)-TTBP and the
product of further reaction, 4 (2-hydroxyethoxy-4'[2-
(hydroxyethoxy)ethoxy]-TTBP.
11-
j, .
~775~4 ::
RD-4~98
EXAMPLE III - Preparation of 4-hydroxy.~4'-(2-hydroxyethoxy)-
2~2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl _
CH~Br Br CH
H0 ~O ~ - ~ ~o_~(CH2)20
C 3 Br Br ~H3
A mixture of 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl-
biphenol (9.9 g., 0.0177 mole), sodium hydroxide (0.8 g.,
0.02 mole), 10 ml. water and 10 ml. 95% ethanol was
refluxed for 30 minutes. Ethylene chlorohydrin (10 ml., ;
11.8 g., 0.147 mole) was added and the mixture refluxed
for 90 minutes. Crystals formed from the hot solution
were filtered to give 7.8 g~ of a product. This solid
was recrystallized several times from benzene affording,
after drying, 3;5 of 4-hydroxy-4'-(2-hydroxyethoxy)-TTBP,
m.p. 235-41. TLC analysis of this purified product
indicated a small amount of 4,4'-bis(2-hydroxyethoxy)-
TTBP as an impurity. A second crop bf crystals, 1.6 g.
m.p. 234-239, provided a total yield of product of 51%.
~XAMPLE IV - Preparation of 4-(2-hydroxyethoxy-4'[2-(2
hydroxyethoxy)ethoxy]-2,2',6,6'-tetrabromo-3,3l,5,5'-
tetramethylbi~henyl
CH Br Br CH
~ ~ 3
HO(~H2)2O- ~O(~CH2CH20)2H
CH3 3
-12-
: ~'
i - ~
-
,
~1~9775~
RD-4998
In a procedure similar to that described above for the
preparation of 4,4'-bis(2-hydroxyethoxy)-TTBP in Ex;lmple I,
200 g. of 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenol
was treated a total of four times with sodium hydroxide
and ethylene chlorohydrin. The resul~ant material (227 g )
was recrystallized from benzene (400 ml.), affording a
mother liquor rich in 4-(2-hydroxyethoxy)-4'-[2-(2-hydroxy~
ethoxy,~-TTBP and crystals rich in 4,4'-bis(2-hydroxyethoxy)-
TTBP. The crystals were recrystallized from benzene (350 ml.)
to afford 157 g. (68%) of 4,4'-bis(2-hydroxyethoxy)-TTBP
m.p. 16905-171.5C. The mother liquor rich in 4,(2-hydroxy-
ethoxy)-4'- 2-(2-hydroxyethoxy)-TTBP was evaporated to a
! solid which after recrystallization (3 times) from methanol
(40 ml., -28C.) gave 34 g. of solid This product was
predominantly 4-(2-hydroxyethoxy)-4~- 2-(2-hydroxyethoxy)-TTBP.
Several further recrystallizations from methanol (-28C)
afforded 4~3 g. of 4-(2-hydroxyethoxy)-4'-[2-(2-hydroxy
ethoxy)-TTBP m~p. 121-126C.
' .
EXAMPLE V - PREPARATION of 4,4'-Diacetoxy-2,2',6,6'~tetra-
bromo-3,3'25~5'-tetramethylbiphenyl.
, .:
O CH3 Br Br ~H3 0
CH3CO~OCCH3
CH3 3
-13-
' :
~3
;i04
RD-4998
A solution of 2.0 g. ~0.00358 mole) of 2,2',6,6'-tetrabromo-
3,3',5,5'-tetramethylbiphenol (TTB) in 1 ml. of acetic
anhydride and 25 ml. of acetic acîd was refluxed for 2
hours. The mixture was poured into 100 ml of water and
extracted with carbon tetrachloride. The extract was dried
~MgSO4), filtered and evaporated to a solid which was
recrystallized from methanol to give the diacetate 4,4'
diacetoxy-TTBP, 1.7 g. (75%), m.p. 1~3 185C.
EXAMPLE VI - Preparation of 4,4'-dihydroxy-2,2',6,6'-
tetrabromo-3,3',5 5'-tetramethylbiphenyl dig~cidylether
/ \CH2-~ CH2
C 3 Br B CH3
A solution of 0.83 gO (0.036 mole) of sodium in 30 ml.
of methanol was prepared and 7.9 g. (0.014 mole) of TTB
was added. The resulting solution was heated and the
methanol was distilled off and gradually replaced by 20 ml.
of benzene. The reaction mixture was finally brought to
dryness by distilling off all of the benzene. A total
of 11.8 g. ~0.127 mole~ of epichlorohydrin was added to
the solid and the resulting mixture was refluxed for 1
~0 hour. The reaction mixture was cooled and diluted with
-14-
~.
'''~
756119~
RD-4998
a 1:1 mixture of CC14 and water. The CC'14 layer was
separated, dried (MgS04) and evaporated to dryness. The ~
residue was diluted with methanol, filtered free of some ;
insoluble solid and heated to boiling. Water was added to
the hot methancl solution until turbid and cooled to give
crystals of 4~41-dihydroxy-TTBp-diglycidyether~ 4.6 g.
(50%), m.p. 146-147C. -;;
EXAMPLE VII - Preparation of 4,4'-Diallyloxy-2,2',6,6'-tetrabromo-
3,3 2 5,5 -tetramethylbiphenyl. ;s~
CH3 Br Br CH3
CH2 =CH-CH2 ~ O-CH2 -CH-CH2 ,
CH3 Br Br CH3
A mixture of 11.59 g (0.02 mole) of TTB, 4.0 g. (0.052
mole) of allyl chloride and 700 gO (00052 mole) of
potassium carbonate in 50 mlO of dry acetone was refluxed
for 10 hoursO The reaction mixture was diluted with 100
}5 ml. of water and extracted with three 50 mlO portions of
ether. The ether extracts were combined and dried (MgS04),
iltered and evaporated to a solidO This solid was
recrystallized from methanol to give needles of 4,4'-dially-
loxy-TTBP~ 5.0 g. (4 ~/0), m.p. 120-123C.
RD-4998
EXAMPLE VIII-Preparation of 4,4'-Dicyanato-2,2',6,6'-
tetrabromo-3 2 3',5,5'-tetramethylbiphenyl.
....... _ _
G ~ r B ~ CH3
NCO ~ ~ OCN
C~3 r B CH3
A mixture of 1 g. (0 0017 mole~ of TTB and 0.4 g. (0.0037
, 5 mole) of cyanogen bromide in 50 ml. of acetone was cooled
in an ice-water bath and stirred at this temperature for
30 minutes. A solution of 0.5 g. (0.005 mole) of tri~
ethylamine in 4 ml. of acetone was then added to the
1 reaction mixture. Upon addition of the amine solution,
i3l 10 a solid precipitated. The entire mixture was stirred at
ice-water temperature for an additional 2 hours. The
reaction mixture was filtered and the filtrate evaporated ~:
to a solid which was recrystallized from 95% ethanol to
give crystals of 4,4'-dicyanato-TTBP, 0.67 gO ~65%), mO
226-228 C.
.
~! EXAMPLE IX-Preparation of 4,4'-Bis(acryloyloxy) 2,2',~
6 2 6'-tetrabromo-3 2 3'~5 ? 5'tetramethylbiphenyl. _
, .
O C~3 Br Br CH3 0
CH2-CHC-O ~ ~ - O-C-CH~CH~
CH3 Br Br ~H3
-16-
''~
'.~, ) ;~
.. .. . .
:`"
~775a~4
RD-4998
Under nitrogen, 558 g. of TTB (lo 00 mole) was suspended
in 2 1. of deaerated benzene (ACS grade) in a 5 1. flask
equipped with a dropping fulmel, a mechanical stirrer and
a cooling bath~ Deaerated triethyl amine (350 ml., East-
man white label) was added, causing the temperature to
jump from 23 to 35. Freshly distilled deaerated acryloyl
chloride (217 g., 2.40 moles~ was then added over 30 minutes
while cooling so as to maintain a temperature of 45-50.
The suspension was then stirred at 42 for an add:Ltional
~0 minutes, cooled to room temperature, and filtered
through scintered glass to remove the hydrchloride. The
filter cake was washed with benæene, and the wash added
to the rest. The analysis showed only a single spot
(silica gel, 1 elution CHC13, bisacrylate Rf=0.70, TTB
reference Rf = 0.36; 1 elution CH2C12, bisacrylate Rf =
0.553. The solvent was removed on a rotary evaporator,
affording a crystalline massO The material was taken up
in 3.1 of dichloromethane and filtered through 2 kg. of
silica gel slurry packed in dichloromethane The last of
the material was washed off the column with an additional
3 1. of dichloromethane The solvent was removed on a
rotary evaporator and the product recrystallized from 400
ml. of dichloromethane at 3. The crystals were filtered,
washed with a small amount of cold 2:1 dichloromethane/
, ~
-17~
. ~ . ,, -, ~ ,- . . . .
i~7~7504
RD-4998
hexane, and dried in a vacuum oven at 100 to constant
weight, affording a first crop of 547 g., 82% yield, of
2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl bis-
acrylate, also appropriately described as 4,4'-bis(acryl-
oyloxy)-TTBP, m.p. 200-201~.
.
EXAMPL~ X - Incorporation of 4,4'-bis(acryloyloxy)-TTBP
into a Polvmethvl MethacrYlate
'l 4,4'-Bis(acryloyloxy)-TTBP (4.0 g.) was
dissolved in 28 g. of a 35% solids solution of poly(methyl
methacrylate) in methyl methacrylate which is stable
i indefinitely at 40F. The material contains a sensitizer
-~l which kicks off a radical initiator at room temperature~
An initiator is added just before the polymerization ;
reaction is desired. The initiator was added and the
material poured into a mold. After 1.5 hours, the material
(which still smelled slightly of monomer) was placed in
:,
an oven at 60 for an additional 2 hours to afford the
final crosslinked polymer. The crosslinked nature of the `
material was illustrated by its insolubility on stirring
at room temperature in chloroform for 5 days to contrast
to the behavior of a comparison piece of uncrosslinked
material.
'' ~
.. . . . . ..
~6~'775~
RD-4998
The copolymer of 4,4l--bis(acryLoyloxy)-TTBP/
methylmethacrylate was evaluated to determine ~s fire-
retardant polymeric property, in accordance with the
oxygen index test described by ASTM tesit method D-28639 .
and exhibited an oxygen index value of 18 3 whereas the
homopolymer of methylmethacrylate had an oxygen index of
` 17.4. ~lthough an increase of oxygen index was relatively
small, the increase in the value of the oxygen index to
18.3 versus the 17.4 value for non-brominated poly-
' 10 acrylate polymer substantiates the conclusion that the
flammability characteristics of the brominated poly-
acrylate had been reduced to some measureable degree by
the inclusion of the bromine containing TTB derivatives
in the polymer skeletal structures.
EXAMPLE XI~Preparation of TTBlBis~henol~A Polycarbonates
CU3
C 3 r r H3 CH3
A polycarbonate was prepared from 2,2',6,6'-
tetramethyl-3,3',5,5'-tetrabromo-4,4'-biphenol was inter
facial polymerization with bisphenol-A bischloroformate
according to the foll~wing procedure: 2.79 gm. of TTBg
100 ml. of 0,2 N aqeuous sodium hydroxide, 0.2 gm. of
-19-
-
:~L~S~4
RD-4998
benzyltriphenylphosphonium chloride, 0.1 g. sodium hydro-
sulfite and 5 ml. o methylene chloride were vigorously
agitated in a blender, and one equivalent of bisphenol-A
bischloroformate in 50 ml. of me~hylene chloride added
The resultant polymer was precipitated in methanol and
dried. The material having an I~V. (CHC13) of 0.84 dl/g. `
was cast into a clear thin film.
The resulting resin, on molding, discolored at ~ ~
740F., which is the temperature at which the base resin ~ ~`
discolors and decomposes. By way o contrast, te~rabromo-
bisphenol-A/bisphenol-A polycarbonates streaks (discolors)
at a temperature be~ween 650 and 700F~ The lack of ~-
discoloration at 740F. of polycarbonates containing the
TTBP molecular unit in contrast to the discoloration at
, .
temperatures of 650-750F. for polycarbonates containing
the tetrabromobisphenol-A molecular unit exemplifies the ;`
distinct thermal and color stability of the polymeric
derivatives of TTB in contrast with the thermal and color
stability of other polymeric materials derived from other ;~
well-known halogenated biphenol monomer reactants.
EXAMPLE XII - Terephthalate polyesters of bu~anediol and
4,4'-bis(2-hydroxyethoxy) 2,2',6,6'-tetrabromo-3,3 t ~ 5,5._
tetramethvlbinhenvl
- '
.
,
-20
,,
..
~377s~
_ RD-~998
~2~2 ~ (CH2)2~
3 Br Br CH~
~c~co(CH2)40~
Bix(hydroxye~hoxy)tetrabromotetramethylbiphenol ~ :
was prepared in accordance with ~he process described in
S Example I, A series of polyesters derived from (1) a
poly(butyleneterephthalate) prepolymer having an intrinsic
viscosity of 0.1~ dl/g and (2) bis(hydroxyethoxy)-TTBP
were copolymeriæed by melt polymerization in a small screw ~:
(~ reactor at ~emperatures within the range of from 200-240C.
in the presence of a titanate-ester catalystO The tere- ~
phthalate acid esters were prepared with varying diol ~:
content in order to vary the bromine content o the result-
ing pol~ner as well as to determine the efect from the :~
polymer's molecular intrinsic viscosity, glass transi~ion
temperature in relationship to the TTB diol content andtor
: the butanediol content of the polyester. Tab~ I set out ::
hereafter shows the composition, reaction conditions and
some of the properties of the series of polyester polymers
~ ranging from poly(butyleneterephthalate) homopolymer to the
: 20 copolymer derived from terephthalate acid and bis(hydroxy-
ethoxy)te~ramethyl~etrabro~nobiphenyl,
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~,~..,
~ ':
i~77S~
RD~4998
n ~ W ~ -~
,.
t~ ~
O (D . ' .
O CD ~ CO O O O ~ O ~ " ~ .
æ ~
o ~D ~ ~ ~ ~ ~ ~ ~ .
~1 U 11 U ~ ~ a~ ~ I~ U~ ~ ~ 11 U~ ~ : .
F ~ ~ ~1 $ ~:
~D P `r~ rt
O t~
~ a ~
O ~ ~ 3 o JI o i~ o n o o ~ I-J p ~ ~ ,. ..
a ~ n ~
~ H ~ , ~
g l_ l~o
C 3 ~ 1~ -
P- O O O Q o o o o o tt 1~ C~ P
O ~ i" ~ fD It ~ . .
~n ~n o ~ o o o ~n o w~ ~ ~ . '
o o o o ~
C 1-3 .'
O O ~D ~0 W ~ ~ '~: ,
0 ~o t O Oo o Cl~ I W ~ ~2 ~
o O O ~ ~ ~o~" :~
~22
,~r ~
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RD-4998
An advantage in the employment of the TTB ~;
derivatives in the preparation of the terephthalate esters
set out hereandbefore is associated with the fact that
polymerization process can be carried out at temperatures
of 240-280C.
EXAMPLE XIII-Preparation of a cyanurate from a bis-cyanate
ester of tetrabromotetramethylbi~henolO _ _
:~
R--
i - R R -
c~r Br CH
R=~O ~ O~
CH3 Br r 3
4,4' Dicyanato 2,2~,6,6~-tetrabromo-3,3',5~5'-
tetramethylbiphenyl prepared in accordance with procedures ~ .
set out in Example VIII9 hereandbefore, was slowly heated :
to room temperature to about 300C. over a period of one
hour to form the cyanurate of the formula set out here-
after. The cyanurate polymer when cooled formed a powder
which was insoluble in acetone, alcohol or chloroformO
EXAMPLE XIV - Preparation of a polyurethane from bis(hydroxy- ~`
ethoxy)-tetrabromotetramethylbiphenyl and toluene
diisocvante
A solution containing an 80/20 mixture of 294- and
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2,6-toluenediisocyanates (1.74 gm, 10 mmole) and 4,4'-bis-
(2-hydroxyethoxy~ 2,2,6,6'-tetrabromo-3,3~,5,5~-tetra-
methylbiphenyl (6.46 gm, 10 mmole) in 25 ml of N-methyl-
pyrolidone was prepared. DABC0, (80 mg.) was added, and the
`! 5 solution stirred at room temperature for 90 minutes. The
I resulting polymer was precipitated in methanol, filtered,
redissolved in 100 ml. of chloroform and reprecipitated
in methanol. Filtering and drying the material afforded
4.3 gm, 53% yield, of the polyurethane of the formula set
out hereafter
`";
CH ~ Br B ~ H3 0, ~ ~
C~3 ~r ~- ~ H )n
having an intrinsic viscosity ~NMP + 0.1 N LiBr) of 0.13
dl/g and exhibits a glass tranllition or 156 C.
.
'' !
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~ .
, ~ , .
~L~'775~
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EXAMPLE XV ~ Preparation of Phosphorous Containing Halo-
~g ~ h~ y~ls and ~ _Derivatives of TTB.
19s~38 gm. o~ bis(hydrogyethoxy)tetrabromotetra-
methylbiphenyl and. 4,67 ml~ of triethylphosphite (0,9 molar
S equivalents) were heated under nitrogen at 160 Eor 45
minutes distilling ethanolJ Vacuum (0~3 mm) was then applied
for 90 minutes,. Cooling a~forded a glassy material which
was easily broken into a free-flowing powder~ The highly
branched material exhibited a glass transition at 78 C~ The
resulting material was identi~ied.by nmr and carbon, hydrogen,
oxygen,bromine and phosphorus analysis which established
that a polymer having the folLowing recurring units in the
following proportions resulted from the foregoing reaction. .:
~ (C~ ~ O(CH~)2 ~ p ~ ~ ~
C r Br CH3
In a similar manner, in accordance with the
procedure set out hereinbe~ore, triphenylphosphite and tri- :
phenylphosphate were reacted with bis(hydroxyethoxy)tetrabromo-
tetramethylbiphenyl and nmr and elemental analysis of the
resulting polymers established that the follvwing polymeric
recurring units ~ormed the skeletal backbone o~ the polymers
~rom the phosphite and phospha~e reactant monomer species,
respectively 9 '~
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~775q~
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CH Br Br CH
OEI3 Br Br C
CH3 Br Br CH3~
~0~).8 ~ `
- Y~-'
CH3 Br Br CH3 1 -
In addition to the above TTB phosphorus contain-
ing polymeric materials, other polymeric organic compounds
containing TTB and TTB derivatives which contain poly-
phosphites and polyphosphates wi~hin the skeletal backbone
of polymeric materials can also be prepared~ Further~
organic TTB phosphorus polymeric materials can be prepared
by the reaction of suitable phosphorus compounds such as `~
dichlorophenoxyphosphine with bis(hydroxyethoxy)tetrabromo-
tetrame~hylbiphenyl under suitable reac~ion conditions.
The above examples illustrate wide variety of
polymer systems into which TTB and its derivatives can be
incorporated. The resulting polymer systems exhibit the
excellent thermal and chemical stability characteristics
associated with the parent TTB biphenolr The characteristic
thermal and chemical stability associated with ~he molecular
; structure o~ the TTB is especially appreciated in high
performance thermal and fire-retardan~ resin applicationsg
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~ 75~ :
and is more particularly appreciated in those applications
requiring a flame-retardant halogen containing material to
be chemically joined with the polymeric skeletal structure
during preparation of a normally flammable resin structure.
The monomeric and polymeric halogenated organic
compounds of our invention can be employed as flame
retardant additives for normally flammable resin compositions
or can be employed in the preparation of polyesters,
polycarbonates, epoxy resins, polyethers, cyanurate polymers,
halogenated phosphorous organic polymers, and the like. :~
Obviously, other modifications and variations of
the present invention are possible in light of the above ..
teachings.
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~'
, .
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