CA1077504A - Brominated biphenols and derivatives thereof - Google Patents

Abstract

Abstract of the Disclosure Monomeric and polymeric halogenated organic compounds derived from 2,2',6,6'-tetrabromo-3,3' 5,5'-tetraalkyl-4,4'-biphenols are described. The deriva-tives are useful in their monomeric and polymeric form as flame retardant additives and/or concentrates for normally flammable resinous materials. The thermal stability at elevated temperatures of the brominated biphenol and derivatives thereof advantageously benefits polymeric compositions containing the brominated biphenols and its derivatives especially when the polymeric compositions are molded into three dimensional articles, or formed into films, sheeting or shaped into fibers, laminated or rein-forced plastics by conventional techniques.

Description

~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 . ~ .. . . . .. .

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~)~

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 ~ ~

( 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 -.~ ,, .

~ 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-`

'.
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 :; ~

:

~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~ :~

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~

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.

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

: ~' i - ~
-, ~1~9775~

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 ' :

~3 ;i04 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 ~.

'''~

756119~

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.

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 ''~

'.~, ) ;~
.. .. . .

:`"
~775a~4 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 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~

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 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 -:~L~S~4 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 - ' .

, ,, ..

~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, ~,~.., ~ ':

i~77S~
RD~4998 n ~ W ~ -~
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t~ ~
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o ~D ~ ~ ~ ~ ~ ~ ~ .
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F ~ ~ ~1 $ ~:
~D P `r~ rt O t~
~ a ~
O ~ ~ 3 o JI o i~ o n o o ~ I-J p ~ ~ ,. ..

a ~ n ~

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g l_ l~o C 3 ~ 1~ -P- O O O Q o o o o o tt 1~ C~ P
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~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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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 .. ..

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.

.
'' !

~ .

, ~ , .

~L~'775~

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 '~

~775q~

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 ~ 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.

~' , .

l.~,"i

Claims (18)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A brominated diphenol selected from monomeric and polymeric halogenated organo compounds of the formula (I) wherein each R independently is selected from primary alkyl groups, each R1 is independently selected from hydrogen and organic groups, at least one R1 being an organic group.

2. A brominated biphenol in accordance with claim 1, wherein each R1 independently is selected from the group consisting of (a) (b) (c) (d) (e) wherein R2 is selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and mixtures thereof, and cyano, R2O then defining a cyanato group; R3 is selected from the group consisting of alkylene, cycloalkylene, arylene and mixtures thereof, R4 is selected from the group consisting of hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and mixtures thereof, x is a positive integer of at least 1, y is a positive integer of at least 1, and z is a positive integer of at least 0.

3. A brominated biphenol in accordance with claim 2 of the formula

4. A brominated biphenol in accordance with claim 2 of the formula

5. A brominated biphenol in accordance with claim 2 of the formula

6. A brominated biphenol in accordance with claim 2 of the formula

7. A brominated biphenol in accordance with claim 2 of the formula

8. A brominated biphenol in accordance with claim 2 of the formula

9. A brominated biphenol in accordance with claim 2 of the formula

10. A brominated biphenol in accordance with claim 2 of the formula

11. A brominated biphenol in accordance with claim 1 of the formula and n being a positive integer of at least 1.

12. A brominated biphenol in accordance with claim 1 of the formula and a, b, and n are each positive integers of at least 1.

13. A brominated biphenol in accordance with claim 1 comprising repeating units of the formula wherein R has the formula

14. A brominated bisphenol in accordance with claim 1 having at least one unit of the formula where n is a positive integer of at least 1.

15. A brominated bisphenol in accordance with claim 1 having at least one unit of the formula wherein a has a value of up to about 1, a + 2b has a value of 3, and c has a value of 0 or 1.

16. A brominated bisphenol comprising the free radical reaction product of methyl methacrylate and 4,4'-bis-(acryloyloxy)-2,2',6,6'-tetrabromo-3,3',5,5'-tetramethyl bisphenyl.

17. A fire retardant composition comprising a normally flammable resin and as fire retardant additive therefor a brominated bisphenol as defined in claim 1, 2 or 3.

18. A fire retardant composition comprising a normally flammable resin and as a fire retardant additive therefor a brominated bisphenol derivative as defined in claim 10, 11 or 12.