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Патент USA US2411141

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Patented Nov. 19, 1946
2,411,141
‘UNITED’ STATES PATENT
OFFICE ‘1
2,411,141
POLYAMINE RESINS AND THE METHOD OF
PREPARING THE SAME
Chester E. Adams, Highland, Ind., assignor to
Standard Oil Company, Chicago, 111., a corpo
ration of Indiana
No Drawing. Application April 30,1943, 5
Serial No. 485,157
16 Claims. (01. 260-2),
1
~
This invention relates to synthetic resins and
more particularly synthetic amine resins and to
the preparation thereof.
An object of the present invention is to provide
an improved synthetic resin of the type contain
ing amine groups. Another object of the inven
2
temperature or higher but below about 480° F.
and preferably at a temperature within the range
of about 140 to about 350‘? F. and under a pres
sure su?lcient to maintain‘ the reactants in a
liquid phase. The reaction time obviously varies
with the reaction temperature and may be a mat
tion is to provide an improved method of pre
paring synthetic amine resins. These as well as
other objects and advantages can be attained by
_ ter of minutes to a matter of~days. When the re
action is ‘conducted within the preferred range;
namely, from about 140° F. to about 350° F., the
preparing resins by reacting certain types of 10 reaction time varies from about'one-half hour to
haloalkyl aromatic compounds with aqueous am
monia.
about thirty hours.
-~
'
l
a The concentration of the aqueous ammonia so
The aromatic component of the reaction is a
lution can be varied depending upon the poly
(haloalkyl) aromatic compounds used and upon
pound having at least two active haloalkyl groups 15 the reaction conditions. However, in any case the
mono-nucleated or poly-nucleated aromatic com
preferably. chloroalkyl and bromoalkyl groups.
aqueous, ammonia solution should be sumciently
concentrated to avoid hydrolysis-of the di(halo
alkyl) aromatic compound. Since sufficient basic
substituted in the aromatic nucleus. The halo
alkyl substituents are preferably halomethyl
' groups and more preferably are halomethyl
material functioning as an acid acceptor should
groups in non-adjacent positions in the ring. In 20 be used in carrying out the reaction, the am- '
addition to the haloalkyl substituents the nucleus
monia may constitute the sole basic material em
may , contain other hydrocarbon
substituent
ployed acting both as a reactant‘and an'acid ac-v
ceptor or other basic compounds may be employed
in conjunction therewith. In the absence of an
other‘ basic material as an acid acceptor, the
groups such as alkyl, cyclo alkyl and other aryl
groups.
,
By the term “active haloalkyl groups" as ‘em
ployed in the above de?nition is meant such halo
alkyl groups'which are capable of precipitating a
_. amount of ammonia used should be in excess of
8 mols of ammonia for each 6 mols of halogen in
the aromatic compound employed. When other
basicmaterials are employed as the acid acceptor,
. silver halide from a silver nitrate solution in the,
cold; for example, an active chloroalkyl group is
one which is capable ot'precipitating- silver chlo 30' the amount of aqueous ammonia employed is cor
ride from a silver nitrate solution in the cold.
Representative of the class of aromatic com
respondingly reduced. Thus, when none of the
aqueous ammonia is utilized asthe acid acceptor,
2 mols of ammonia is used for each 6 atoms of
pounds which is employed .in the preparation of
resins of the present invention are the following:
halogen in the aromatic compound.
While it is preferable to employ aqueous am
35
Dl(chloromethyl) naphthalenes
monia for the synthesis of the polyamine resins '
Di(chloromethyl) benzenes
»
oirthe present invention, aqueous solutions of
Di(bromomethyl)
water
soluble primary amines, preferably alkyl
Di(bromomethyl) benzenes
mono- or polyamines can be used, either alone or
Di (chloromethyl) toluenes ,
40 in combinationwith aqueous ammonia.
Di(bromomethyl) toluenes
In conducting the" reaction suitable inert. or
naphthalenes
‘
_
,
Di(chloromethyl) mesitylene
a,a'-Dichlorodurenes
a,a’-Dichloroisodurenes
a_-a'-Dichloroprehnitenes
Di(chloromethyl) methyl naphthalene
non-reactive diluents can be employed such as,
for example, ether, hexane, dioxane, benzene,
toluene and the like.
The following examples are illustrative of the
methods of. obtaining infusible but moldable poly
amine resins 01' the hereindescribed types.‘
Example I
50
Twenty grams or 2,4-dichlorodurene were re
acted at 170° F. with 200 cc. of a concentrated
Di('chloromethyl) diethylbenzene
Di(bromomethyl) methyl naphthalene
'Tri(c_hloromethyl) naphthalene ,
Di(chloroethyl) naphthalene
' and others.
In accordance with the present invention the
‘
45
aqueous ammonia solution. Although the reac
tion mass solidi?ed in one-half hour, the reaction
ing suitable poly(haloalkyl) ‘aromatic compounds
was continued for two hours. After boiling with
of the above type with aqueous ammoniaat room 55 acetone and water a product yield of 2.5 grams
polyamine synthetic resins are obtained by react
0
2,411,141
.7
3
4
,
'_ dried. A yield of 13.7 grams of an infusible res
was obtained. The washed material was treated
with a hot 5% solution of sodium hydroxide for
two hours and an infusible, but moldable resinous
material obtained.
Example 11
5
inous material was obtained. .
,
.
. Example VIII
Tengrams of 2,4-dichlorodurene and 60 cc. of
28% aqueous ammonia were heated in a sealed 1
Twenty grams of 2,4-dichlorodurene werev re
glass tube for sixteen hours and at 115° F. The
acted with 200 cc. of a concentrated aqueous am
monia solution for four hours at 120° F. An ad- ' ‘ reaction product was broken up and added to
. 300 cc. of acetone and the mixture ?ltered. The
ditional 100 cc. of aqueous NH: were added and
the reaction continued for four more hours. The
reaction mass was ?ltered and extracted-twice
10 solid material was ?nely divided and 'puddled with
with boiling acetone. A yield of 6.5 grams of ‘a ,
moldable resinous material was obtained.
150 cc. of acetone, ?ltered again and dried at
room temperature. The powder was‘reground,
puddled again with acetone and filtered. After
the ?nely divided ‘solid material had dried it was
5 shaken vigorously with 400 cc. of water for ten
to ?fteen minutes and ?ltered. The solid mate
One hundred and forty grams of. 2,4-dichloro
rial was mixed with 500 cc. water and the mixture
durene were reacted with 1000 cc. of a 15% aque
added to 200 cc.- of 2% sodium hydroxide. The
ous solution of ammonia. ‘at 140° F. for eighteen
mixture was re?uxed for one hour, '200 cc. of
hours. The solid reaction material was removed
to a ?lter and washed with cold water and dried 0 water added, and the slurry ‘?ltered. The cake
was washed with 500 co. more of water and the
with alcohol and ether. The washed material
product dried at 110° F. A yield of 4.37 grams of
was then extracted two times with hot benzene, a moldable resinous product was obtained.
?ltered and dried. A yield of 7.0 grams of a mold
.
The polyamine synthetic resins of the present _
able resinous material was obtained.
.25.
invention
are useful for many purposes such as,
Example IV
' for example, in the -molding and preparation of
electrically insulated articles, as acid and alkali
Twenty grams of 2,4-dichlorodurene and 70 cc.
resistant containers and in particular are useful.
of concentrated ammonia were allowed to react
at room temperature for three weeks. The prod
wherever high melting alkali, and acid resistant
uct was ?ltered, washed with water, and extracted 3 as well as electrically insulated ‘plastics and res-)
Example _ III
'twice with boiling hexane to obtaina product
yield of 8.4 grams.
,
inous ‘materials are required.
.
-
,
The material was then re-"
Since many embodiments of this invention may
?uxed with 5% ‘sodium hydroxide solution for
be made without departing from .the spirit and
four hours and ?ltered. A moldable resin was
scope thereof, it is to be understood that the
obtained.
35 invention is not limited to the specific‘ embodi
Example ' V
ments thereof described herein, except as de?ned ,
in the appended claims.
Five grams of . di(chloromethyl) naphthalene
Iclaim:
were reacted with 200 cc. of .a 28% aqueous solu
'
'
1. The method of preparing a polyamine'resin
tion of NH3 in a shaker bomb at 250° F. to 260° F.
for about twenty-one'hours. At the end of this .40 comprising reacting in the liquid phase an aro
matic hydrocarbon’having at least two active
time the temperature increased to 335° F., heating
haloalkyl groups, capable of precipitating a silver '
was stopped and the reaction products shaken v
for another hour, making a total (reaction time
oftwenty-two hours.
-
i
.
.
halide from _a silver nitrate solutionin the cold,
45 substituted in the aromatic-nucleus, with aqueous‘
The bomb was opened and the contents thereof
?ltered.
The solid material was washed with
ammonia su?iciently concentrated to avoid hy
drolysis of said aromatic hydrocarbon, at least two
mols of ammonia being used for each six atoms’ of .
water and dried at 220° F., and a yield of 3.4
halogen in the aromatic hydrocarbon.
grams‘ of solid material obtained. The resinous
material was molded with a platen temperature 50 . 2. The method'of preparing atpolyamine resin comprising‘ reacting a poly(haloalkyl) aromatic.
of 450° F. and-8000 pounds per square inch. A
hydrocarbon having at least‘ two active haloalkyl
molding with a'veryv hard surface vwas obtained. groups, capable of precipitating a silver halide
‘Example VI
» from a silver nitrate solution in the cold, sub
in the aromatic nucleus. with aqueous:
One gram of 1,5-dichloromethyl naphthylene 55 stituted
ammonia at a temperature ranging upward from
and 5 cc. of a 28% aqueous ammonia solution were
heated in an oven in a sealed tube at 172° F. for
forty hours. The contents of the tube were then 'removed to a ?ask and re?uxed with 200 cc. of
water for two hours. The material was then 60
?ltered and dried and a solid material weighing
.85 gram was obtained. The material was insolu
ble in boiling hexane and boiling methyl naphtha
lene.
The resinous material was molded at a
room temperature to below about 480° F. and at a
pressure su?icient to maintain the reaction mix- I
ture in the liquid phase at the reaction tempera
ture, said aqueous ammonia being sufficiently con
centrated to avoid hydrolysis of said aromatic hy- .
drocarbon, at least two mols of ammonia. being
used for each six atoms of halogen in the aro
matic hydrocarbon.
_
3. The method of preparing a synthetic resin as
platen temperature of 425° F. and 8000 pounds 65 described in claim 2 m. which the poly (haloalkyl)
per square inch. The molding obtained was hard
aromatic hydrocarbon is a polyfchloroalkyl) aro
with a high polish.
matic hydrocarbon containing at least two active '
chloroalkyl groups capable to precipitating a silver
halide from a silver nitrate solution in the cold.
Twenty‘ grams of 2,4-dichlorodurene and 80 cc. 70 4. The method of preparing a-synthetic resin as
of 28% aqueous ammonia were heated in a sealed
described in claim 2 in which the poly(haloalkyl)
Example VII
tube at 135° F. for sixteen hours and the tempera
aromatic hydrocarbon is a poly(halomethyl) aro
ture raised to 165 to 170° F. and heating con
‘matic hydrocarbon containing at least two active
tinued for four more‘hours. The reaction product
halomethyl groups capable of precipitating a silver
was ground up, re?uxed in water, ?ltered and 75 halide from a silver nitrate solution in the cold.
5. The method of preparing a synthetic resin as ' \
reaction temperature,_said_ aqueous ammonia be
ing sumciently concentrated to avoid hydrolysis
described in claim 2 in which the poly(haloalkyi)
aromatic hydrocarbon is a di(halo1_nethyl) naph- "
thalene.
‘
of the aromatic hydrocarbon and at least eight
' mols oi.’ ammonia being'used’for each six atoms of
'
6. The method or preparing a synthetic resin as 5 halogen in the aromatic hydrocarbon.
described in claim 2 in which the po1y(haloa1kyl)
' 12. The method 01’ preparing a polyamine resin
aromatic hydrocarbon is a di(chloromethyl).
comprising reacting. amixture of a poly ihaloalkyl)
aromatic hydrocarbon having at least two active
7. The method'of preparing a synthetic resin as
haloalkyl groups, capable of precipitating a silver
described in claim 2; in which the poly(haioalkyl) 10 halide from a silver nitratesolution in the cold,
naphthalene,
'
'
-
V,
-
aromatic hydrocarbon is. a di(chloromethyl)/
methyl naphthalene.
\
I
.
'
v
8. The method of preparing a synthetic resin as
described in claim 2 in which the poly(haloa1ky1)
' substituted in the aromatic nucleus, with a. con
» 'centrated aqueous ammonia solution su?iclently .
‘concentrated to avoid hydrolysis oi’ the IP0ly(halo
alkyl) aromatic hydrocarbon in the presence or a
aromatic hydrocarbon is a poly(halomethyl). 15 basic acid acceptorat a temperature ranging up
mono-nucleated aromatic hydrocarbon contain
ward from room temperature to below about 480° ing at least two active halomethyl groups capable
F. and at a pressure su?lcient to maintain the
of precipitating a silver halide from a silver nitrate
reactants in the liquid phase at the reaction tem-‘
solution in the cold.
7
,
perature, at least two mole of ammonia'being used
‘ 9. The method of preparing a synthetic resin as
for each six atoms or halogen in the aromatic‘ hy
described in claim 2 in which the poly(haloalkyl) 20 drocarbon, extracting the reactionv mass with a
aromatic hydrocarbon is a di(ch1oromethyl)
hot inert solvent and drying the extracted reac
- xylene.
tion mass.
510. The method of preparing a polyamine resin
"
-
a
'_
-
_
V
13. The method of preparing a polyamine resin
comprising reacting a poly(haloalky1) aromatic
as described in claim 12 in which the 'pol?halo
hydrocarbon having at least two active haloalkyl ,25 alkvl) aromatic hydrocarbon is a poiy<halometh~~
groups, capable of precipitating a silver halide
from a silver nitrate solution in the cold, substi
tuted in the aromatic nucleus, with aqueous am
monia at a temperature ranging upward‘ from
room temperature to below about 480° F. and at
a pressure su?lcient to maintain the reaction mix
yl) poly-nucleated aromatic hydrocarbon having
at least two active haiomethyl groups capable of
precipitating a silver halide from a silver nitrate
solution in the cold.
_
‘as described in claim 12 in which the DoLY?ialo
alkyl) aromatic hydrocarbon is a di(chlorometh
ture in the liquid phase at the reaction tempera
ture, said aqueous ammonia being sufficiently con
yl) naphthalene.
centrated to avoid hydrolysis of the aromatic try-m5 ,
drocarbon and at least eight mols of ammonia
being used for each six atoms of halogen in the
aromatic hydrocarbon;
_
g 14'. The method of preparing a, polyamine resin
'
11. The method of preparing a polyamine resin
-
'
_
.
15. The method of preparing a polyamine resin
asrdescribed in claim 12 in which the poly(hal0
alkyl) aromatic hydrocarbon is a pol_y(halometh
yl) mono-nucleated aromatic hydrocarbon having
at least two active halomethyl groupscapable oi’
comprising reacting’ a‘ poly(haloalkyl_) aromatic 40 precipitating a silver halide from a silver nitrate
hydrocarbon having‘ at least two active haloalkyl
solution in the cold.
‘ \ groups, capable of precipitating a silver halide
16. The method of preparing a polyamine resin
from a silver nitrate solutionv in the cold, sub
stituted in the aromatic nucleus, with aqueous
ammonia at a temperature of about 140° F; to
about 350°
and under su?lcient pressure to
maintain the reactants in the liquid phase at a
as described in claim 12 in which the-po1y(halo
alkyl) aromatic hydrocarbon is“ a di(chlorometh
45 yl) xylene.
'
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