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Патент USA US3028378

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3,028,308
United ?tates §atent
1
2
3,023,368
bon atoms and said substituents selected from the class
PQLYMERIC ORGANO-BGRON CQMPOUNDS AND _
_
Patented Apr. 3, 1962
THEIR PREPARATION
William David English, Garden Grove, Allen L. Mc
Closkey, Grange, and Howard Steinberg, Fullerton,
consisting of alkyl and alkoxy radicals having one carbon
atom, when R’ is derived from a diisocyanate Z is hydro
gen and when R’ is derived from a triisocyanate Z is the
ureido radical
Calif” assignors to United States Barax & Chemical
Corporation, Los Angeles, Calif., a corporation of
OR
Nevada
N0 Drawing. Filed Aug. 10, 1959, Ser. No. 832,430
12 Claims. (Cl. 260-775)
The present invention is a continuation-in-part of our
previously ?led application bearing Serial Number 746,
10 and wherein the boron atoms in said polymer are bonded
only to nitrogen atoms.
The present polymeric tris(dialkylureido)boranes are
obtained by addition reaction of a tris(alkylamino)borane
325 and dated July 3, 1958, now abandoned.
with a di- or triisocyanate. These poly[tris(dialkyl
This invention relates as indicated to polymeric organo
boron compounds and has more particular reference to 15 ureido)boranes] will be found to be substantially insoluble
in all of the common organic solvents and thus their
polymeric tris( a1kylureido)boranes and methods for pre
exact molecular weights cannot be determined. How
paring the same.
ever, other methods of determining molecular weights
Various types of organo-boron compounds are well
such as end group analyses and light scattering tech
known and described in the literature. Of the known
polymeric organo-boron compounds those having boron 20 niques have shown that the present polymers have a
molecular weight of at least about 10,000.
bonded to a nitrogen atom are of special interest; how
So that the present invention is more clearly under
ever, prior methods of preparing these materials are not
completely satisfactory.
stood, the following examples are given for illustrative
purposes:
It is an object of this invention to provide new poly
I
mers containing boron, nitrogen and carbon in the poly 25
mer chain, the boron being bonded to nitrogen atoms.
Hexamethylene diisocyanate (8.4 grams; 0.05 mole)
Other objects will appear as the description proceeds.
was added dropwise in one hour to a stirred re?uxing solu
To the accomplishment of the foregoing and related
tion of 9.25 ‘grams (0.05 mole) of tris(isopropylamino)
ends, said invention then comprises the features herein
after fully described and particularly pointed out in the 30 borane in 46 ml. of dry benzene. A white precipitate
claims, the following description setting forth in detail
certain illustrative embodiments of the invention, these
being indicative, however, of but a few of the various
ways in which the principle of the invention may be
employed.
Broadly stated, the present invention comprises poly
[tris(dialkylureido)boranes] having a molecular Weight
of at least about 10,000 and having as the recurring struc
formed almost immediately. After the addition was com
plete, re?ux was continued for about one hour. The
mixture was then cooled and ?ltered under nitrogen. The
resulting polymeric tris(dialkylureido)~borane weighed
35 10.4 grams when dry.
When heated in a capillary it
shrinks at 206° C. and partially melts at 208-211’ C.
This polymer is insoluble in benzene, dioxane, di-n-butyl
ether and acetone, and reacts rapidly in methanol. Anal
ysis indicates the material contains 1.57% boron and
17.1% nitrogen.
11
A solution of 10.1 grams (0.06 mole) of hexamethylene
diisoeyanate in 125 ml. of di-n-butyl ether was added
dropwise to a stirred re?uxing solution of 11.0 grams
wherein R is a material selected from the class consisting
(0.06 mole) of tris(isopropylamino)borane in 200 ml. of
of the alkyl and aryl radicals derived from tris(alkyl
di-n-butyl ether in about 1.5 hours. After the addition
amino)boranes said alkyl group having from 1-12 carbon
was complete the mixture was heated at re?ux for about
atoms, and tris(arylamino) boranes said aryl group
an additional 1.5 hours. As in Example I a White pre
selected from the class consisting of phenyl and sub 50 cipitate formed during the addition. The mixture was ?l
stituted phenyl radicals and said substituents selected
tered hot and yielded 13.6 grams of a white solid. Anal
from the class consisting of alkyl and alkoxy radicals
ysis indicates the polymer contains 2.13% boron and
having one carbon atom, R’ is a material selected from
18.00% nitrogen.
the class consisting of the alkylene radicals derived from
III
alkylene diisocyanates having from 1-12 carbon atoms,
the arylene radicals derived from unsubstituted arylene
A solution of 4.7 grams (0.027 mole) of toluene 2,4
diisocyanates having from 6~12 carbon atoms, the arylene
diisocyanate in 100 ml. of xylene was added in about
1.5 hours to a stirred heated solution of 10.0 grams
radicals derived from substituted arylene diisocyanates
(0.054 mole) of tris(isopropylamino)borane in 250 ml.
having from 6—28 carbon atoms and said substituents
selected from the class consisting of alkyl and alkoxy radi 60 of xylene. After the addition was complete the mixture
cals having one carbon atom, the arylene radicals derived
was stirred at re?ux for about another 12 hours, after
from unsubstituted arylene triisocyanates having from
which it was cooled'and ?ltered. The resultant solid
6-12 carbon atoms and the arylene radicals derived from
polymer was insoluble in toluene, xylene and partially
soluble in acetone.
'
substituted arylene triisocyanates having from 6-28 car
8,028,368
4
3
The following list is illustrative of the isocyanates ap
plicable to the present invention:
iv
A solution consisting of 3.0 ‘grams (0.012 mole) of
diphenylmethane p,p’-diisocyanate and 4.44 ‘grams (0.012
Hexamethylene diisocyanate
mole) of tris(isopropyla1nino)borane in 300 m1. of ben
Toluene 2,4-diisocyanate
zene reacted to form a white precipitate after about 30
Diphenylmethane p,p'-diisocyanate
Triphenylme-thane p,p’p”-triisocyanate
minutes re?uxing.
V
A solution consisting of 3.0 grams (0.012 mole) di
phenylmethane p,p’-diisocyanate and 5.46 grams (0.024
mole) of tris(t-butylamino)borane in 300 ml. of benzene
was stirred for about 12 hours at room temperature and
then at re?ux .‘for about two hours. The mixture was
then stripped of benzene at reduced pressure and room
temperature and then heated. At about 200° C. a sudden
reaction took place to yield 5 .2 grams of a white resin.
Dianisidine diisocyanate
The proportions of the tri(alkylamino)borane or tris
(arylamino)borane and the foregoing isocyanates are not
critical. An excess of either reactant can be used if
desired.
The poly[tris(dialkyluredio)boranes] of this invention
2
15 can be used in the preparation of ?lms, shaped objects
and ?bers. While these polymers are substantially in
soluble in the known organic solvents, they can be han
10
dled as other substantially insoluble polymers, i.e., nylon,
by extrusion or other well-known manufacturing tech
A solution of tour grams of tris(isopropylarnino)borane 20 niques. At temperatures of from about 180—215° C.
in 10 ml. of methylene chloride was added dropwise to
these materials can be molded under pressure in dies,
a solution of eight grams of triphenylmethane p,p’,p"-tri
extruded in the form of ?lms, ?bers, tubes, rods, etc.
isocyanate in 200 ml. of methylene chloride. The mix
The molded or extruded material when cooled can then
be machined, cut, sawed, drilled, etc., ‘by the usual tech
ture was stirred at room temperature for about four
hours, then allowed to stand for about 64 hours. The 25 niques.
Other modes of applying the principle of the inven~
precipitate formed was ?ltered, washed and ‘dried. The
tion may be employed, change being made as regards
yield was 15.9 grams of a grey powder.
the .details described, provided the features stated in any
VII
of the following claims or the equivalent of such be em
1 A solution of 15 grams (0.052 mole) tris(anilino)bo
30
rane in 20 ml. of dioxane was added to a solution of 16
grams (0.054 mole) of dianisidine diisocyanate in 200
ml. of dioxane.
The mixture was heated to re?ux tem
perature and held at that temperature with stirring for
about 48 hours. It was then cooled, ?ltered under ni
trogen, and the solid washed with fresh dioxane. Solvent
was removed from the product in a vacuum oven. The
yield was ‘22.3 grams of a pale brown solid which had
a boron content of about 1.17%.
While the foregoing examples disclose tris(isopropyl 40
amino) or tris(t-butylamino)borane and tris(anilino)
borane as one of the reactants necessary to produce the
present polymers, it is to ‘be understood that any tris
(alkylamino)borane wherein the alkyl group has from
1-12 carbons and any tris(arylarninor)borane where the
aryl groups are phenyl or substituted phenyl and the
substituents comprise alkyl and alkoxy groups having
ployed.
We, therefore, particularly point out and distinctly claim
as our invention:
1 1. A poly[tris(dialkylureido)borane] having a molecu
lar weight of at least about 10,000 and having as the re
curring structural unit
L
l
where said polymer consists essentially of said recurring
structural units bonded together only through boron to
nitrogen bonds and where R is selected from the group
consisting of the alkyl and aryl radicals of tris(alkyl
amino)boranes and tris(arylamino)boranes said alkyl
radicals having from 1 to 12 carbon atoms and said
aryl radicals selected from the group consisting of phenyl
and substituted ,phenyl said substituents selected from
amino)boranes are typical examples of ingredients which 50 the group consisting of alkyl and alkoxy radicals having
one carbon atom, and R’ is selected from the group con
can be used to produce the present polymers:
sisting of the alkylene radicals of alkylene diisocyanates
said alkylene radicals having from 1 to 12 carbon atoms,
Tris (methylamino ) borane
the arylene radicals of unsubstitued arylenetdiisocyanates
Tris ( ethylarnino ) borane
said arylene radicals having from 6 to 12 carbon atoms,
Tris (.n-propylamino )borane
the arylene radicals of substituted arylene diisocyanates
Tris.(isopropylamino ) borane
said arylene radicals having from .6 to 28 carbon atoms
Tris (n-butylamino) borane
and said substituents selected from the group‘ consisting
Tris ( sec-butylalnino) borane
of alkyl and alkoxy radicals having one carbon atom, the
Tris (tert-butylamino ) borane
60 arylene radicals of unsubstituted arylene triisocyanates said
Tris (isobutylamino) borlane
arylene radicals having from 6 ‘to 12 carbon atoms and
Tris ( amylamino) borane
the arylene radicals of substituted arylene triisocyanates
Tris.( sec-. ar'nylamino )borane
Tris ( tert-amylamino) borane
said arylene radicals having from 6 to 28 carbon atoms
Tris (hexy1amino)borane
and said substituents selected from the group consisting
65 of alkyl and alkoxy groups having one carbon atom,
Tris ( sec-hexylamino ) borane
Tris (tert-hexylamino) borane
when R’ is selected from the group consisting of alkylene
Tris (heptylamino) borane
and arylene radicals of diisocyanates Z is hydrogen and
Tris (octylamino) borane
when R’ is selected from the group of arylene radicals
Tris ( nonylamino ) borane
of triisocyanates Z is the ureido radical
Tris ( decylarnino) borane
Tris (dodecylamino ) borane
OH
Tris ( anilino ) borane
Tris (.xylidino ) borane
Tris (toluidino) borane
2. A poly[tris(dialkylureido)borane] having a molecu
Tris ( anisidino ) borane
75
one carbon atom are applicable to the invention.
' The following tris(all<ylamino)boranes and tris(aryl
3,028,368’
5
recurring structural unit
6
6. A poly[tris(dialkylureido)borane] having a mo
lar weight of at least about 10,000 and having as the
lecular weight of at least about 10,000 and having as,
the recurring structural unit
'
0 R
II
/
I
/
L
where said polymer consists essentially of said recurring
unit bonded together only through boron to nitrogen
where said polymer consists essentially of said recurring
bonds and where R is an alkyl radical of a tris(alkyl 10, units bonded together only through boron to nitrogen
bonds and where R is an alkyl radical of a tris(alkyl
amino)‘oorane said alkyl radical having from 1 to 12 car
amino)borane said alkyl radical having from 1 to 12
bon atoms, R’ is an alkylene radical of an alkylene di
carbon atoms, R’ is an arylene radical of an arylene
isocyanate said alkylene radical having from 1 to 12 car—
triisocyanate said arylene radical selected from the group
bon atoms and Z is hydrogen.
15 consisting of unsubstituted arylene radicals having from
3. A poly[tris(dialkylureido)-borane] having a molecu
6 to 12 carbon atoms and substituted arylene radical
lar weight of at least about 10,000 and having as the re
having from 6 to 28 carbon atoms said substituents se
curring structural unit ,
lected from the group consisting of alkyl and alkoxy
I“? r
t
t 1r 2L
20
v
radicals having one carbon atom and Z is the ureido
radical
-——1 T—C) —NH R’——NH C —N—-B
'
\
OR
\
where said polymer consists essentially of said recurring
units bonded together only through boron to nitrogen
7. A poly tris(dialkylureido)borane] having a mo-‘
lecular weight of at least 10,000 and having as the re
bonds and Where R is an aryl radical of a tris(arylarnino)
borane said aryl radical selected from the group consist
curring structural unit
ing of phenyl and substituted phenyl said substituents se
lected from the group consisting of alkyl and alkoxy radi
clas having one carbon atom, R’ is an alkylene radical 30
from 1 to 12 carbon atoms and Z is hydrogen.
35
2
III
OR
I
III/
/
where said polymer consists essentially of said recurring
units bonded together only through boron to nitrogen
bonds and where R is an aryl radical of a tris(aryl
amino)borane said aryl radical selected from the group
—N—c—NHit'~NHc-N-B/3/
L
E
no
z
L
of an alkylene diisocyanate said alkylene radical having
4. A poly[tris(dialkylureido)borane] having a molecu
lar weight of at least about 10,000 and having as the re
curring structural unit
*
on
consisting of phenyl and substituted phenyl, said sub
III
stituents selected from the group consisting of alkyl and
alkoxy radicals having one carbon atom, R’ is an arylene
\
40
radical of an arylene triisocyanate, said arylene radical ,
selected from the group consisting of unsubstituted
where said polymer consists essentially of said recurring
units bonded together only through boron to nitrogen
arylene radicals having from 6 to 12 carbon atoms and
bonds and where R is an alkyl radical of a tris(alkyl
substituted arylene radicals having from 6 to 28 carbon
atoms, said substituents selected from the group con
amino)borane said alkyl radical having from 1 to 12
carbon atoms, R’ is an arylene radical of an arylene 45 sisting of alkyl and alkoxy radicals having one carbon
diisocyanate said arylene radical selected from the group
atom, and Z is the ureido radical
consisting of unsubstituted arylene radicals having from
OR
6 to 12 carbon atoms and substituted arylene radicals
having from 6 to 28 carbon atoms said substituents se
lected from the group consisting of alkyl and alkoxy 50
8. A poly tris(dialkylureido)borane] having a mo
radicals having one carbon atom and Z is hydrogen.
lecular weight of at least about 10,000 and having as
5. A poly[tris(dialkylureido)borane] having a mo
the recurring structural unit
lecular weight of at least about 10,000 and having as the
recurring structural unit
55
R oI
zI
0II R|
—l/
/
where said polymer consists essentially of said recurring
units bonded together only through boron to nitrogen
L
where said polymer consists essentially of said recurring
60 unit bonded together only through boron to nitrogen
bonds.
9. A poly[tris(dialkylureido)borane] having a mo
lecular Weight of at least about 10,000 and having as the
bonds and where R is an aryl radical of a tris(arylamino)
borane said aryl radical selected from the group con
recurring structural unit
sisting of phenyl and substituted phenyl said substituents 65
selected from the group consisting of alkyl and alkoxyl
PriOH
IT III
radicals having one carbon atom, R’ is an arylene radical
~—1\ ——C—N
of an arylene diisocyanate said arylene radical selected
from the group consisting of unsubstituted arylene radi 70
I
cals having from 6 to 12 carbon atoms and substituted
arylene radicals having from 6 to 28 carbon atoms said
substituents selected from the group consisting of alkyl
and alkoxy radicals having one carbon atom and Z is
hydrogen.
/
HOP!‘i
I II I /
N-C ——N—B
ii
where said polymer consists essentially of said recurring
unit bonded together only through boron to nitrogen
75
bonds.
10. A poly[tris(dialkylureido)borane] having a mo
3,028,368
I
8
lecular Weight of at least about 10,000 and having as
the recurring structural unit
lecular weight of at least about 10,000 and having as
the recurring structural unit
.7
i
where said polymer consists essentially of said recurring 10
structural units bonded together only through boron to
nitrogen bonds.
11. A poly[tris(dialkylureido)borane] having a mo
lecular Weight‘ of at least about 10,000 and having as
the recurring structural unit
But 3 1?;
'
where said polymer consists essentially of said recurring
structural units bonded together only through boron to
nitrogen bonds.
H 0 But
20
nitrogen bonds.
12. A poly[tris(dialkylureido)borane] having a mo
N—Pr1
l_.—l
15
Where said polymer consists essentially of said recurring
structural units bonded together only through boron to
AILH
i=0
25
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,424,883
2,517,945
2,729,618
Habgood _____________ __ July 29, 1947
Upson ______________ __ Aug. 8, 1950
Huller et al ____________ __ Jan. 3, .1956
2,864,780
Katz _______________ .._ Dec. 16, 1958
2,945,841
Aries _______________ __ July 19,v 1960
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