A method of refining 2,2-isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol is described which is characterized by recrystallization of 2,2-isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol using one or more aromatic hydrocarbons such as benzene, xylene, toluene, ethylbenzene or pseudocumene

Hiratsuka, K.

Kobayashi, T.

Nawata, K.

English

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NASA TECHNICAL MEWRANDU4
	
NASA TM-77458
c	 ^
METHOD OF REFINING 2,2-ISOPROPYLIDENEBIS-3,5-DIBROMOPHENYLENE-4-
OXYDIETHANOL
Takayuki Kobayashi, Kiyoshi Nawata, Kyuo Hiratsuka
it -<<
Translation of Japanese Patent No. 51-63161 (1976) to
Takayuki Kobayashi; Applicant Teijin K.K.; IPC C C 07 C
43/20; Date of Application, November 26, 1974; Date of
Disclosure, June 1, 1976; Japanese Title: 2,2-
isopuropiridenbis-3,5-jiburomofueniren-4-okishijietanoru no
seiseiho
(NASA-TM-77458)	 jjE ,."iiGD uF i EFINING
2,2-1S0PRUPYLIDLNEDiS-3 , 5-
DIBRO:lUi?H7NYLENE-4-OXYDIEIHA6CL (National
Aeronautics and Space Administration`SC7 07D G3/25
HC A02/MF A01
N84-19492
Unclas
12471
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, DC 20546
	 JULY 1982
OF PC,
Z * S 5 , *ft
NASW-77458
METHOD OF REFINING 2,2-ISO-
iPROPYLIDENEBIS-3,5-DIBROMOPHENYLENE-4- 	 July 1982
OXYDIETHANOL
T. Kobayashi, K. Nawata and
K. Hiratsuka
Leo Kanner Associates
	
NASW-3541
Redwood City California 94063
translation
..	
......	
..	 .
National Aeronautics and Space Adminis-
tration, Washington DC 20546
ITranslation of "2,2-isopuropiridenbis-3,5-jiburomofueniren-
i.4-okishijietanoru no seiseiho," Japanese Patent No. 51-63161,
I date of application November 26, 1974; date of disclosure
i June 1, 1976.
A method of refining 2,2-isopropylidenebis-3,5-dibromo-
phenylene-4-oxydiethanol is described which is characterized
! by recrystallization of 2,2-isopropyl 4-denebis-3,5-dibromo-
lphenylene-4-oxydiethanol using one or more aromatic hydrocarbons
:such as 1-junzene, xylene, toluene, ethylbenzene or pseudo-
A
Unclassilied - Unlimited
Unclassified	 Unclassified
•,
_J^
^i
METHOD OF REFINING 2,2-ISOPROPYLIDENEBIS -3,5-DIBROMOPHENYLENE-4-
OXYDIETHANOL
Takayuki Kobayashi, Kiyoshi Nawata, Kyuo Hiratsuka
1. Title of Invention	 /431*
Method of refining 2,2-isopropylidenebis-3,5-dibromophenylene-4-
oxydiethanol.
2. Scope of Patent Claim
A method of refining 2,2-isopropylidenebis-3,5-dibromophenylene-
4-oxydiethanol characterized by recrystallization of 2,2-
isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol using one or
more aromatic hydrocarbons such as benzene, xylene, toluene,
ethylbenzene or pseudocumene.
3. Detailed Description of the Invention
This invention relates to a method of producing 2,2-
isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol (below
abbreviated Br compound, specifically to a method of refining Br
compounds illustrated by the following structural formula
insert formula
which is capable of imparting a high degree of incombustibility to
linear or unsaturated polyester.
Incombustible polyesters can be produced through additive
copolymerization of Br compounds during linear polymerization of
linear polyester, for example, as is well known. There is a
pronounced tendency for coloration due to slight amounts of
impurities contained in said Br compounds since said incombustible
polyester has a history of extreme heating in the course of
production.
"Numbers in the margin indicate pagination of the foreign text."
1
r-7, LV
Consequently, a very high degree of refining of Br compounds is
required to produce very incombustible polyester with high
commercial value using said Br compounds.
The inventors have conducted thorough research into methods of
refining the aforementioned Br compounds with very high purity, the
result of which was the discovery that said conditions could be
satisfied by recrystallization refining of Br compounds using a
specific aromatic compound as the recrystallization solvent, thereby
completing this invention.	 /432
Specifically, this invention provides a method of refining
2,2-isopropylidenebis-3,5-dibromophenylene-4-oxydiethanol
characterized by recrystallization of 2,2-isopropylidenebis-3,5-
dibromophenylen(!- 4-oxydiethan,)l using one or more aromatic
hydrocarbons such as benzene, xylene, toluene, ethylbenzene or
pseudocumene.
be that which is
produced througr
igh nuclear
or it may be
and ethylene
The Br compound used in this invention may
produced by any method. For example, it may be
reaction of tetrabromobisphenol A produced thro
bromination of bisphenol A with ethylene oxide,
produced through reacting tetrabromobisphenol A
chlorohydrin in the presence of alkali.
Among the aforementioned aromatic hydrocarbons used in
recrystallization, benzene and toluene are interesting in terms
of their solubility and the purity of the refined product. The
recrystallization solvent is restricted tc specific aromatic
hydrocarbons, and the raw materials present in slight quantities
in the Br compounds as well as tetrabromobisphenol A and its
monohydroxyethyl ether etc. which are intermediate products can
be effectively removed through suitable selection of the solvent.
Aliphatic hydrocarbons and alcohols, which are general
2
iW
'^ a
recrystallization solvents in addition to these aromatic
hydrocarbons, du not completely remove the impurities even when
used as recrystallization solvents of Br compounds, and they
cannot be used in the recrystallization methods of this
invention.
The amounts of the aforementioned aromatic hydrocarbons used
vary with the type, but usually 0.5 to 10-fold parts (weight
parts), preferably 1 to 5-fold parts (weight parts) in relation
to the coarse Br compounds to be recrystallized would be used.
Recrystallization using the aforementioned aromatic
hydrocarbons is conducted at normal temperature. Specifically,
coarse Br compounds are heated and dissolved in the
aforementioned aromatic hydrocarbons, and the insoluble materials
are heated and removed. Refined Br compounds are crystallized
and precipitated by then cooling the mother liquor. At this
time, the dissolution temperature would vary with the type of
solvent, and the optimum dissolution temperatures would be 60 to
80°C for benzene, 90 to 110°C for xylene, 80 to 100°C for
toluene, 90 to 1.10°C for ethyl benzene and 100 to 120°C for
I
pseudocumene. In ad ,iition, the cooling temperature as well
varies with the type of solvent used, and the optimum cooling
temperatures are 20 to 30 0
 for benzene, 25 to 35°C for xylene, 15
to 35°C for toluene, 30 to 40°C for ethyl benzene and 30 to 40°C
for pseudocumene.
1
Effective results would be realized with no obstacles
through the use of adsorbents such as active carbon, silica gel,
alumina etc. in the implemention of this invention to raise the
purification effects.	 ^I
This invention is detailed below through actual examples,
but the invention is not restricted to - ,--he following actual
3
1	 v	 ,
examples. In the example, "parts" always refers to weight parts
while "n" always refers to the ultimate viscosity determined from
measurement in orthochlorphenol at 35°C. The softening point was
determined by the penetration method using a softening point
measurement device. The b value indicating the color of the
polyester produced is the measurement using the Hunter type
optical densitometer. This b value indicates that the yellow
color exhibited was intense, and a value above 10 is
unacceptable.
Actual Examples 1-5 and Comparative Examples 1,2
(a) 544 parts of tetrabromobisphenol A, 242 parts of ethylene
i
chlorohydrin and 120 parts of caustic soda were reacted to
produce 63.2 parts of 2,2-isopropylidenebis-3,5-dibromophenol-4-
oxydiethanol which was added to the solvents mentioned in table
1, heated and dissolved under the conditions illustrated in the
table. Subsequently, slight amounts of undissolved substances
remaining were removed by heating and filtration. The filtrate
was cooled to the temperatures mentioned in the table, and the
f
	
	 precipitated crystals were filtered off, `ollowed by
decompression drying at 20 mmHg, 60°C. The color, melting point
and the results of observation of the resulting crystals under a
polarized light microscope are as illustrated in table 1.
i
(b) 14.5 parts of the 2,2-isopropylidenebis-3,5- 	 ► 	 ,
dibromophenylene-4-oxydiethanol obtained in this fashion, 97
parts of dimethylterephthalate, 67 parts of ethylene glycol and 	 i
0.088 parts of calcium acetate as a catalyst were introduced into
a reaction vessel fitted with an agitator, refining tower and
precipitation condenser, followed by heating from 140°C to 225°C
	 '	 !
and reaction while distilling off the methanol produced as a
result of the ester exchange reaction. 32 parts of methanol were
distilled off approximately 3 hours after the start of the 	 j
reaction. The reaction was terminated at this point, and the
4
o
tt.. '. may.
CF pnn.r	 1
reaction blend was transferred to a condensation polymerization
reaction vessel fitted with an agitator and glycol distillation
condenser. The normal pressure reaction was conducted for 30
minutes at 260°C, for 30 minutes at a slight vacuum of 20 mmHg
and for 10 minutes under pressure reduction from 20 mmHg to 3
mmHg. The condensation polymerization reaction was then
implemented under high vacuum of 0.3 mm Hg at 275°C for 60
minutes. Table 1 illustrates the limiting viscosity, the
softening point and the color of the resulting polyester. The
resulting polymers were then recrystalllized for three hours at
140 0 , and the b values measured using a Hunter type optical
densitometer are also illustrated in table 1. Furthermore, these
polymers were all self-extinguishing.
Table 1
n 	 I	 R
1
11
n M 5 ia
IDEAPI
btu	 ^e lu 8	 wOA110tr	
U) ^`^^^1
I
1,
_ 
la
q
^Yi
14	 !omm , 'ZJII	 .	 150
11
7IS	 20	 N _ r 110-1 12 	 112t rraQ L .	 u&sit^to fla	 ,Itl
i	 ^: ► 	 .	 1$0 loo	 ss 110-,/r	 .^5	 ua^t^io . / j	 .os
I
	 llR	 tuo ss	 ^ is ;041 110 -112	 0,64	 2465 •	 ^	 ass^
a t.'(` 	2:J In	 is	 ; I so -112	 I	 ass	 24.21 I	 l,.l
s	 >,,i ^ri	 t o 1Jn	 ss
'
110-112	 n. ♦ 	 :.so
W
.s01
I"A s	 //	 ?^	 ,01 S	 '^` 1s	 I	 soI
0,_„0	 slot rE1	 v	 s	 06s 2s asfYB.,bn6 20 is*	 IissI	
2	 '.f1.-.,till 1so s0	 i	 10	
.
I u	
12 at r913, ►t8/os_1	
.an6ni.	 as  f.q;
	 .	
11.60
1 solvent 2 type
3 amount (parts) 4 dissolution temperature
5 cooling temperature 6 refined material
7 color 8 melting point
9 results of observation using polarized light microscope
10 polyester product 11 softening point
12 color 13 macroscopic
14 actual example 15 comparative example
16 benzene 17 toluene
18 blended xylene 19 ethyl benzene
20 pseudocumene 21 methanol
22 cyclohexanone 23 colorless
24 pale yellow 25 no crystallization at 112°C
26 slight amounts of crystallization evident at 120°C
27 pale yellow
1
1
1
15i


Method of refining 2,2-isopropylidenebis-3,5- dibromophenylene-4-oxydiethanol

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