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Патент USA US3040004

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3,039,994
United States Patent 0
1
Patented June 19, 1962‘
V
2
obtained by polymerizing hydroxy benzoic acid'at an
3,939,994
elevated temperature in the presence of an organic sol
POLYESTERS OF HYDROXYBENZOIC ACIDS '
William K. T. Gleim, Island Lake, 111., assignor to Uni
versal Oil Products Company, Des Plainea?i, a corpo
ration of Delaware
‘
N0 Drawing. .Filed May 11, 1960, Ser. No. 28,234
‘
13 Ciairns.
(Cl. 260-47)
This application relates to a method for the production
of polymeric products, and more particularly to a method
for the polymerization of hydroxy benzoic acid and sub-}
stituted hydroxy benzoic acids.
It has now been discovered that" polymeric products
possessing unusually high melting points may be prepared
u
vent which acts simultaneously as a polymerization cata
lyst. The starting material for this process will comprise
the acetylated ester of hydroxy benzoic acids such as
p-hydroxy benzoic acid, m-hydroxy benzoic acid, or 0
hydroxy benzoic acid. The desired hydroxy benzoic acid
is then converted to the desired material for polymeriza
tion by any means known in ‘the art depending upon the
particular ester which is used. vFor example, p-hydroxy
benzoic acid is acetylated to form p-acetoxy benzoic acid.
Foilowing this the latter product may then be converted
to the methyl ester thereof by any means well known in
the art and thereafter polymerized by heating to an ele
by polymerizing hydroxy benzoic acid and substituted 15 vated temperature in a solvent which acts simultaneously
as a polymerization catalyst. In the example hereinabove
hydroxy benzoic acids. The polymers thus prepared
set forth which is the polymerization of the methyl ester
which, as hereinbefore set forth, possess relatively high
of acetoxy benzoic acid, methyl acetate is formed, Which is
melting points are useful for a wide variety of purposes.
subsequently distilled off during the polymerization re-'
For example, they may be used for preparing products
action and may be recovered and reused. This recovery
which may be called upon to withstand relatively high
of a portion of the starting material may also be used
temperatures. The products obtained by the polymeriza
with other esters of the hydroxy benzoic acid.
tion process of the present invention, that is, by poly
Examples of esters of acetoxy benzoic acids which may
merizing hydroxy benzoic acid and substituted hydroxy
be used in the process of this invention include
benzoic acids will have melting points of above 400° C.
and, in addition, said products will be insoluble in many 25 the methyl ester of p-acetoxy benzoic acid,
organic solvents such as dirnethylsulfoxide, guaiacol, di
the methyl ester of o-acetoxy benzoic acid,
butyl phthalate, dimethylformamide, etc. '
the methyl ester of m-acetoxy benzoic acid,
it is therefore an object of this invention to provide
the ethyl ester of p-acetoXy benzoic acid,
a process for the production of high melting point poly
the ethyl ester of o~acetoxy benzoic acid,
30 the ethyl ester of m-acetoxy benzoic acid,
meric products.
>
A further object of this invention is to provide a process
the propyl ester of p-acetoxy benzoic acid,
for the polymerization of hydroxy benzoic acid and sub
the propyl ester of o-acetoxy benzoic acid,
stituted hydroxy benzoic acids to prepare polymeric
the propyl ester of m-acetoxy benzoic acid,
products.
.
the butyl ester of p-acetoxy benzoic acid,
One embodiment of this invention is found in a process 35 the butyl ester of o-acetoxy benzoic acid,
for the production of a polymeric product which com
the butyl ester of m-acetoxy benzoic acid,
prises polymerizing an organic acid selected from the
the methyl esters of
group consisting of hydroxy benzoic acid and substituted
Z-chloro-p-acetoxy benzoic acid,
hydroxy benzoic acids in an organic compound which
3-chloro-p-acetoxy benzoic acid,
acts simultaneously as a polymerization catalyst and a
solvent at polymerization conditions to form the desired
polymeric product.
A further embodiment of this invention resides in a
process for the production of a polymeric product which
comprises polymerizing an organic acid selected ?om
the group consisting of hydroxy benzoic acid and substi
tuted hydroxy benzoic acids in a tertiary amine having a
boiling point greater than 150° C. which acts simul
taneously as a polymerization catalyst and a solvent at
polymerization conditions to form the desired polymeric
product.
‘
Yet another embodiment of the invention resides in
a process for the production of a polymeric product which
comprises polymerizing the methyl ester of p-acetoxy
benzoic acid in the presence of a tertiary amine having 55
a boiling point greater than 150° C., said amine acting
simultaneously as a polymerization catalyst and a solvent
at a temperature in the range of from about 150° to
2,3-dichloro-p-acetoxy benzoic acid,
2,5-dichloro-p-acetoxy benzoic acid,
2,6-dichloro-p-acetoxy benzoic acid,
2,3,5-trichloro~p-acetoXy benzoic acid,
2,3,5 ,6-tetrachloro-p-acetoxy benzoic acid (tetrachloro-p
acetoxy methylbenzoate) ,
Z-?uoro-p-acetoxy benzoic acid,
3-?uoro-p-acetoxy benzoic acid,
2,3-di?uoro-p-acetoxy benzoic acid,
2,5-di?uoro-p-acetoxy benzoic acid,
2,6-di?uoro-p-acetoxy benzoic acid,
2,3,5 .-tri?uoro-p-acetoxy benzoic acid,
2,3,5 ,é-tetra?uoro-p-acetoxy benzoic acid (tetr-a?uoro-p
acetoXy methylbenzoate) ,
Z-chloro-m-acetoxy benzoic acid,
2,4-dichloro-m-acetoxy benzoic acid,
2,5-dichloro-m-acetoxy benzoic acid,
2,6-dichloro-m-acetoxy benzoic acid,
2,4,5-trichloro-m-acetoxy benzoic acid,
2,4,5,6-tetrachloro-m-acetoxy benzoic acid,
'Z-?uord-m-acetoxy benzoic acid,
2,4-difluoro-m-acetoxy benzoic acid,
2,5-di?uoro-m-acetoxy benzoic acid,
2,5 -di?uoro-m-acetoxy benzoic acid,
2,4,5-tri?uoro-m-acetoxy benzoic acid,
2,4,5 ,6-tetra?uoro-m-acetoxy benzoic acid, etc.,
about 300° C. to form the desired polymeric product.
A speci?c embodiment of the invention resides in 60
a process for the production of a polymeric product which
comprises polymerizing the methyl ester of p-acetoXy
benzoic acid in tii-N-butylamine at a temperature in
the range of from about 200° to about 225° C. to form
the desired polymeric product.
Other objects and embodiments referring to alternative
3~chloro-o-acetoxy benzoic acid,
substituted hydroXy benzoic acid, solvents which ‘act
4-chloro-o-acetoxy benzoic acid,
simultaneously as polymerization catalysts and organic
'5-chloro-o-acetoxy benzoic acid,
6-chloro-o-acetoxy benzoic acid,
70 3,4-dichloro-o-acetoxy benzoic acid,
detailed description of the invention.
As hereinbefore set forth it has now been discovered
3,5-dichloro-o-acetoxy benzoic acid,
that unusually high melting polymeric products may be
3,6-dichloro-o-acetoxy benzoic acid,
diluents or solvents will be found in the following further
’
3,039,994
l
4
3
through a separate line, or if so desired, it may be ad
mixed with the starting material and charged to the re
3,4,5-trich1oro-o—acetoxy benzoic acid,
3,4,6-trichloro-o-acetoxy benzoic acid,
4,5,6-trichloro-o-acetoxy benzoic acid,
3;4,5,6-tetrachloro-o-acetoxy benzoic acid,
3-?uoro-o-acetoxy benzoic acid,
actor in a single stream. The reactor may comprise an
unpacked vessel or coil or may be lined with an adsorbent
packing material such as alumina, ?re brick, dehydrated
bauxite, or the like. At the end of the required resi—
dence time the solution is continuously Withdrawn, cooled,
the reaction product ?ltered and the ?ltrate recycled
.
4-?uoro-o-acetoxy benzoic acid,
5-?uoro-o-acetoxy benzoic acid,
6-?uoro-o-acetoxy benzoic acid,
3,4-di?uoro-o-acetoxy benzoic acid,
3,5-di?uoro-o-acetoxy benzoic acid,
3,6-di?uoro-o-acetoxy benzoic acid,
3,4,5-tri?uoro-o-acetoxy benzoic acid,
3,4,6-tri?uoro-o-acetoxy benzoic acid,
4,5,6~trichloro-o-acetoxy benzoic acid,
10
3,4,5,6-tetra?uoro-o-acetoxy benzoic acid, etc.
15
to form a portion of the feed stock.
The following examples are given to illustrate the
process of the present invention which,»however, are not
intended to limit the generally broad scope of the present
invention in strict accordance therewith.
Example I
A mixture of 30 g. of the methyl ester of p-acetoxy ,
It is to be understood that the aforementioned substituted
benzoicpacid dissolved in 100 g. ‘of tri-N-butyl-arnine
hydroxy benzoic acids are only‘ representatives of the
was refluxed at a temperature of about 208° C. for a
class of compounds which may be used ‘and that the pres~
period of about 16 hours. During this time methyl
ent invention is not necessarily limited thereto.
acetate was distilled o?. Upon completion of the resi
The polymerization of the above mentioned esters of 20 dence time the reaction mixture was cooled and the poly
’ benzoic acids or substituted hydroxy benzoic acids is
eifected in a solvent which acts simultaneously as a poly
mer was ?ltered. The tri~N-butylamine ?ltrate when evap
orated in vacuum will yield additional product. The
merization catalyst, said catalyst being basic in nature.
polymer was washed with ether, acetone, benzene and
Examples of simultaneously acting polymerization cata
carbon tetrachloride. The desired polymeric product
lysts‘ and solvents which may be used include tertiary 25 comprised a White powder which was insoluble in dimethyl
amines with a boiling point of at least 150° C., and pref
sulfoxide, guaiacol, dibutylphthalate and dimethylform
erably greater than 150° C., for instance tertiary ali
amide. A melting point determination of the powder
phatic amines such as tri-N-propyl amine, tri-N-butyl,
disclosed a melting point of approximately 450° C.
amine, tri-N-pentyl amine, etc., tertiary aryl amines such 30
Example 11
as N,N-dimethyl aniline, N,N-diethyl aniline, N,N-di
propyl aniline, N,N-dimethyl-o-toluidine, N,N-dimethyl
m-toluidine, N,N-dimethyl-p-toluidine, N,N-diethyl-o
toluidine, N,N-diethyl-m-toluidine, N,N-diethyl-p-tolu—
idine, N,N-dipropyl-o-toluidine, N,N-dipropyl-m-toluidine,
N,N-dipropyl-p-toluidine, N,N-dimethyl-o-xylidine, N,N
dimethyl-m-xylidine, N,N-dimethyl-p-xylidine, N,N-di
ethyl-o-xylidine, N,N-dimethylnaphthylamine, N,N-di
ethylnaphthylamine, etc. As in the case, of the hydroxy
benzoic acids or substituted hydroxy benzoic acids the
In this example a solution of 30 g. of tetrachlorop
acetoxy methylbenzoate dissolved‘in 100 g. of N,N-di
methyl naphthylamine is re?uxed at a temperature of
At the
end of this time the reaction mixture is cooled, the prod
35 about 270° C. for a period of about 16 hours.
uct ?ltered and the tri-N-butylamine is evaporated in
vacuum. The desired polymeric product comprising a
powder is recovered and subjected to melting point deter
the powder having a melting point above
minations,
aforementioned tertiary amines having a boiling point 40 450° C.
greater than 150° C. and which act simultaneously as
both a polymerization catalyst and a solvent, said com
pounds being basic in nature, are only representatives of
the class of compounds which may be used and the present
, invention is not necessarily limited thereto.
Example III
In this example 30 g. of tetra?uoro-p-acetoxy methyl
benzoate dissolved in 100 g. of N,N-dipropyl aniline is
treated in a manner similar to that set forth in the above
examples, that is, by re?uxing at a temperature of about
245° C. for 16 hours. The desired polymeric product,
after cooling, is separated and recovered.
temperature will, of necessity, be dependent upon the,
particular reactant and the organic compound hereinbe
Example IV
fore set forth which acts simultaneously as a polymeriza 50
In this experiment 30 g. of the ethyl ester of p-acetoxy
tion catalyst and a solvent. When tri-N-butyl amine is
benzoic acid is dissolved in 100 g. of N,(N-diethy1 aniline
utilized as the catalytic agent ‘and the solvent the reaction
The reaction is effected “at, an elevated temperature in
the range of from about 150° to about 300° C.
The
and re?uxed at a temperature of about 210° C. for a pe
will be e?ected at a temperature of about 210° C.
riod of 16 hours. At the end of this time the polymeric
The reaction may be effected in any suitable manner
and may .comprise either‘a batch or a continuous type 55 product comprising a white powder is separated by con
operation.
V
ventional' means and recovered. '
'
For example, if a batch type operation is
I claim as my invention:
used a quantity of the desired material along with the
1. A process for the production of a polymeric prod
desired catalytic agent which acts simultaneously as the
uct which comprises polymerizing an organic acid selected
diluent or solvent, is placed in an appropriate apparatus.
The apparatus and contents thereof are then heated to 60 from the group consisting of hydroxy benzoic acid and
alkyl esters of acetoxy benzoic acids in the presence of
the desired reaction temperature and maintained thereat
a tertiary amine having a boiling point greater than 150°
for a predetermined period of time. During the re
C. in su?icient amount to act simultaneously as a-poly
action rtime any ef?uent which may distill ,over may be
merization catalyst and a solvent.
recovered and reused. At the end of this time the ap
2. A process for the production of a polymeric prod
paratus an contents thereof are allowed to cool to room
uct which comprises polymerizing an organic acid select
temperature, and the polymeric product is recovered by
ed from the group consisting of hydroxy benzoic acid
?ltration.
and alkyl esters of acetoxy benzoic acids in the presence
The reaction of the. present invention may also be
of tri-N-butylamine in sui?cient amount to act simul
effected inv a continuous type operation. When this type
is used the ester of the'acetoxy benzoic acid or substi 70 taneously as a polymerization catalyst and a solvent at a
temperature in the range of from about 150° to about
tuted hydroxy benzoic acid is continuously charged to
300° C. to form the desired polymeric product.
a reactor which may be maintained at the proper operat
3. A process for the production of a polymeric prod
ing conditions of temperature and pressure. The organic
uct which comprises polymerizing an organic acid select
compound which acts simultaneously as the catalytic agent
and the solvent is also continuously charged to the reactor 75 ed from the group consisting of hydroxy benzoic acid
-
3,039,994
5
6
and alkyl esters of acetoxy benzoic acids in the presence
of N,N-dimethyl aniline in sufficient amount to act si
about 150° to about 300° C. to form‘ the desired poly
meric product.
multaneously as a polymerization catalyst and a solvent
at a temperature in the range of about 150° to about 300°
which comprises polymerizing tetra?uoro-p-acetoxy meth
C. to form the desired polymeric product.
4. A process for the production of a polymeric prod
uct which comprises polymerizing an organic acid select
ed from the group consisting of hydroxy benzoic acid
and alkyl esters of acetoxy benzoic acids in the presence
of N;N-dimethyl naphthylamine in su?icient amount to
9. A process for the production of a polymeric product
' ylbenzoate in a tertiary amine having a boiling point
greater than 15 0° C., said amine being in su?icient amount
to act simultaneously as a polymerization catalyst and a
act simultaneously as a polymerization catalyst and a sol
solvent, at a temperature in the range of from about 150°
to about 300° C. to form the desired polymeric product.
“'10. A process for the production of a polymeric prod
uct which comprises polymerizing the methyl ester of
vent at a temperature in the range of from about 150° to .
p-acetoxy benzoic-acid in a sufficient amount of tri-n
butylamine to act simultaneously as a polymerization cat
about 300° C. to form the desired polymeric product.
alyst and a solvent at a temperature in the range of from
5. A process for the production of a polymeric prod
uct which comprises polymerizing an organic acid select 15 about 200° to about 225° C. to form the desired poly
meric product.
ed from the group consisting of hydroxy benzoic acid and
11. A process for the production of a polymeric prod
alkyl esters of acetoxy benzoic acids in the presence of
uct which comprises polymerizing the ethyl ester of p
N,N-dipropyl aniline in su?icient amount to act simulta
acetoxy benzoic acid in a sui?cient amount of N,N-diethyl
neously as a polymerization catalyst and a solvent at a
temperature in the range of from about 150° to about ,'
aniline to act simultaneously as a polymerization catalyst
and a solvent at a temperature in the range of from about
300° C. to form the desired polymeric product.
210° to about 225° C. to form the desired polymeric
6. Aprocess for the production of a polymeric prod
product.
7
uct which comprises polymerizing the methyl ester of
12. A process for the production of a polymeric prod
p-acetoxy benzoic acid in a tertiary amine having a boil—
ing point greater than 150° C., said amine being in su?‘i 25 uct which comprises polymerizing tetrachloro-p-acetoxy
methylbenzoate in the presence of su?icient N,N-dimeth
cient amount to act simultaneously as a polymerization
yl naphthyl amine to act simultaneously as a polymeriza
catalyst and a solvent, at a temperature in the range of
from about 150° to about 300° C. to form the desired
polymeric product.
p
7. A process for the production of a polymeric product
which comprises polymerizing the ethyl ester of p-acet
tion catalyst and a solvent at a temperature in the range
of from about 270° to about 290° C. to form the desired
polymeric product.
13. A process for the production of a polymeric prod
oxy benzoic acid in a tertiary amine having a boiling
uct which comprises polymerizing tetra?uoro-p-acetoxy
point greater than 15 0° C., said amine being in su?icient
methylbenzoate in the presence of su??cient N,N-dipro_
pylaniline to act simultaneously as a polymerization cat~
amount to act simultaneously as a polymerization catalyst
and a solvent, at a temperature in the range of from about 35 alyst and a solvent at a temperature in the range of from
150° to about 300° C. to form the desired polymeric
product.
about 240° to about 250° C. to form the desired poly
meric product.
'
8. A process for the production of a polymeric prod~
uct which comprises polymerizing tetrachloro-p-acetoxy
References Cited in the ?le of this patent
methylbenzoate in a tertiary amine having a boiling point 40
greater than 150° C., said amine being in sufficient
amount to act simultaneously as a polymerization cat
alyst and a solvent, at a temperature in the range of from
UNITED STATES PATENTS
2,471,023
2,600,376
Cook et a1. __________ __ May 24, 1949
Caldwell ____________ __ June 17, 1952
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