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Патент USA US3020261

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United States Patent 0 ”
Patented Feb. 6, 1962
1
2
3,620,251
duced, all of the advantages of the resinous reaction prod
not of a polyamide resin and an alkylbenzene diisocyanate
could be realized with none of the attendant disadvantages.
As used in this speci?cation and appended claim, the
RESEJOUS COMPQSITIONS DERIVED FR?M
PDLY ‘11-!
3,ii20,251
AND ALKYLBENZENE Di
ISOCYANATES
Donald H. Russell, Pennsauken, N.J., assignor to The
Atlantic Re?ning Company, Philadelphia, Pa, a cor
poration of Pennsylvania
No Drawing. Filed Oct. 15, 1959, Ser. No. 846,558
1 Claim. (Cl. 260-18)
term “pot life” and related terms shall mean that interval
of time ‘between which the polyamide resin and the alkyl
benzene diisocyanate exist merely as a physical mixture
and the time at which the mixture becomes a fused resin
ous substance.
10
This invention relates to novel compositions of matter,
‘One of the standard methods for increasing the pot life
of a physical mixture of two reactive components is by
particularly to novel resinous compositions prepared from
the addition of an inert diluent to one or both of the com
a polyarnide resin and a long chain alkylbenzene diiso
ponents. This method has been tried unsuccessfully in
the case of mixtures of polyamide resins and short chain
cyanate to form polymeric thermosetting ?lms or coatings.
As used in this speci?cation and appended claim the 15 alkylbenzene diisocyanates (i.e. benzene diisocyanate,
toluene diisocyanate, ethylbenzene diisocyanate and pro
term “polyamide” and related terms include those mate
rials prepared by condensing a polymeric fatty acid with
plybenzene diisocyanate). In every instance the addition
of an inert diluent such as a saturated hydrocarbon had no
an aliphatic polyamine. These polyamides may be
liquids, tacky gumlike semi-solids or hard brittle resinous
e?’ect on the pot life of the mixture of the polyamide resin
materials. An example of a polyamide which is included 20 and the short chain alkylbenzene diisocyanate. in other
in the scope of the de?nition of this invention is that pre- ‘
words, even though a standard method was tried in an
pared by the condensation of polymerized linoleic acid
with a polyarnine. In general, polyamides ?nding partic
ular utility in the preparation of the novel compositions
attempts were unsuccessful and the pot life remained zero.
It is, therefore, an object of this invention to provide a
attempt to increase the pot life of such mixtures, all such
of this invention are those disclosed and produced accord 25 novel composition of matter.
vIt is another object of this invention to provide a novel
ing to United States Patent No. 2,379,413.
As used in this speci?cation and appended claim the
composition of matter comprising an unreacted physical
term “long chain alkylbenzene diisocyanates” and related
mixture of a polyamide resin and a long chain alkylben
zene diisocyanate.
v '
terms are those alkylbenzene diisocyanates in which the
alkyl group contains 4 or more carbon atoms and which
It is a further object of this invention to provide a novel
alkyl group is either branched or normal in structure.
Also intended to be included within the scope of this
composition, comprising an unreacted physical mixture
of a polyamide resin and a long chain alkylbenzene diiso
de?nition are all of the position isomers of the alkylben
cyanate in which the alkyl radical contains 4 or more car
zene diisocyanates.
bon atoms and which composition is stable for prolonged
-.
These long chain alkylbenzene diisocyanates containing
4 or more carbon atoms in the alkyl radical may be pre
pared by the method disclosed in copending application
Serial No. 713,544, ?led February 6, 1958, now US.
35 periods of time at ambient temperatures and which can
be cured thermally to form a polymeric resinous product.
Other objects of this invention will become apparent
from the following description and appended claim.
Patent No. 2,986,576. In this copending application these
As stated above, the reaction between an alklybenzene
alkylbenzene diisocyanates were prepared from the cor» 40 diisocyanate in which the alkyl group contains from 0 to 3
responding dinitro alkylbenzenes by ?rst reducing the
carbon atoms and a polyamide resin is well-known. This
dinitro compound to the corresponding diamine by either
a catalytic hydrogenation step or in a liquid phase reduc
reaction proceeds instantaneously. Therefore, the physi
cal mixture of an alkylbenzcne diisocyanate in which the
tion reaction. The diamine was then dissolved in a sol
alkyl group contains from 0 to 3 carbon atoms would
vent such as ethyl acetate and reacted with an excess of 45 have a pot life of zero. Since the pot life of benzene diiso
phosgene to convert the carbamyl chlorides to the diiso
cyanates which were further purified by vacuum distilla
tion.
The reaction product of an alkylhenzene diisocyanate
cyanate, toluene diisocyanate, ethylbenzene diisocyanate
and propylbenzene dissocyanate in admixture with a
polyarnide resin is zero in every instance, it would be
expected that the pot life of a mixture of a butylbenzene
in which the alkyl group or radical contains 3 or less car 50 diisocyanate, amylbenzene diisocyanate, heptylbenzene
diisocyanate, octylbenzene diisocyanate, etc. and a poly
bon atoms with a polyamide resin is well-known. Ilt is
amide resin would also be zero.
also well-known that this reaction occurs very rapidly
even at room temperature and, in fact is essentially in
Contrary to the predicted pot life of a physical mixture
stantaneous. The resulting product of this reaction is a
substituted urea.
Since the reaction between a polyamide'resin and an
of along chain alkylbenzene diisocyanate and a polyamide
55 resin, it has been found that the pot ‘life of mixtures of
these long chain alkylbenzene diisocyanate and polyamide
alkylbenzene diisocyanate in which the alkyl group con
resins is of a substantial length of time.
tains from 0 to 3 carbon atoms is essentially instantaneous,
It has been found that a physical mixture of a long
the uses and utility of the resulting products are extremely
chain alkylbenzene diisocyanate and a polyamide resin
limited, for example it would not be possible to prepare a 60 has an extended pot life when the two components are
mixture of the two reactive components and then attempt
admixed in all proportions and also when admixed in
to form a protective coating on a structure by applying
the mixture in any of the standard methods of application,
the presence of an inert diluent. It is preferred, however,
in the practice of this invention for reasons of economy
such as spraying, painting, dipping, etc.
Since the polymeric reaction product of a diisocyanate 65 and ease of handling that the long chain alky-lbenzene
diisocyanate and polyamide resin be admixed in a ratio
and a polyamide has properties which are extremely desir
of from about 1:1 to about 1:3, ‘respectively. These ratios
able in coating and casting systems, it would be a substan
are based on Weight percent.
,
'
tial advance in the art of polymer chemistry if a com
For example, it has been found that av physical mixture
position of matter could be produced comprising merely
a physical mixture of a polyamide'resin and an alkylben 70 of a nonylbenzene diisocyanate and a polyamide resin in
the ratio of 1:2, respectively, will remain a physical mix
zene diisocyanate which would be stable for extended periods of time. If such a composition could be pro
ture for an in?nite period of time, but may be cured, to a
3,020,251
4
3
Example VII
fused resinous material at any time merely by the appli
cation of heat.
To 109 grams of a propylbenzene diisocyanate there
was added 200 grams of a liquid polyamide resin resulting
This invention will be further understood by the fol
lowing examples which are merely intended as illustrative
from the condensation of polymerized linoleic acid with
and should not be construed as limitative.
a polyamine. Immediately upon the addition of the poly‘
amide resin there occurred a spontaneous exothermic re
action between the components that produced a solid
Example I
‘To 1063 grams of a benzene diisocyanate there was
amorphous polymeric material. Thus, it is obvious that
added 200 grams of a liquid polyamide resin resulting
from the condensation or polymerized linoleic acid with
a poly/amine. Immediately upon the addition of the poly
the pot life of such a mixture is zero and it is equally
obvious that there is no longer present a physical admix
ture of the two components.
amide resin there occurred a spontaneous exothermic re
action between the components that produced a solid
, Example VIII
amorphous polymeric material. Thus, it is obvious that
To 100 grams of a propylbenezene diisocyanate dis
‘the pot life of such a mixture is zero and it is equally 15 solved in 900 cc. of toluene there was added 290 grams of
obvious that there is no longer present a physical ad
the same polyamide resin as that described in Example
mixture of the two components.
VII. Upon the addition of the polyamide resin to the
solution of propylbenzene diisocyanate there occurred a
spontaneous exothermic reaction between the components
that producedv a solid amorphous polymeric material.
Thus, it is obvious that the pot life of such a. mixture is
zero and it is equally obvious that there is no longer
present a physical admixture of the two components.
In the above examples it is clearly shown that short
Example 11
To lOO grams of a benzene diisocyanate dissolved in
‘900 cc. of toluene there was added 200 grams of the same
polyamide resin as that described in Example I. Upon
‘the addition of the polyamide resin to the solutionof
ibenzene diisocyanate there occurred a spontaneous exo
thermic reaction between the components that produced 25 chain alkylbenzene diisocyanates (i.e. benzene diisocy
1a ‘solid amorphous polymeric material. Thus, it is obvious
anate, toluene diisocyanate, ethylbenezene diisocyanate
‘that the pot life of such a mixture is zero and it is equally
and propylbenzene diisocyanate) cannot exist as merely
obvious that there is no longer present a physical admix
a physical admixture with a polyamide resin. Examples
ture of the two components.
I, III, V and VII show that the pot life of such a mixture
Example III
30 is zero and Examples II, IV, VI and VIII show that , even
if one or both of the components is diluted with an
To 1G0 grams of a toluene diisocyanate there was added
inert hydrocarbon diluent, the pot life is still zero.
290 grams of a liquid polyamide resin resulting from the
condensation of polymerized linoleic acid with a poly
Example [X
amine. Immediately upon the addition of the polyamide
To 160 grams of a nonlybe’nzene, diis'ocyanate there
resin there occurred a spontaneous exothermic reaction 35
was added 200 vgrains of a liquid polyamide resin result
between the components that produced a solid amorphous
ing ‘from the condensation of polymerized linoleic acid
polymeric material. Thus, it is vobvious that the pot life
with a. polyamine. Upon the addition of the polyamide
of such a mixture is ‘zero and it is equally obvious that
resin
to the nonylbenzene diisocyanate no observable
there is no longer present a physical admixture of the
40 reaction occurred.
‘two components.
Example IV
merely physical as between the two components. This
mixture remained in this condition at ambient tempera
To 100 grams of a toluene diisocyanate dissolved in 900
tures for a period of time in excess of three months.
cc. of toluene there was added 200 grams of the same
polyamide resin as that described in Example III. Upon
the addition of the polyamide resin to the solution of
Example X
To 100 grams of a nonylbenzene diisocyanate dissolved
toluene diisocyanate there occurred a spontaneous exo
in 400 cc. of toluene there was added 200 grams of a
thermic reaction between the components that produced
a solid amorphous polymeric material. Thus, it is obvi
ous that the pot life of such a mixture is zero and it is 50
equally obvious that there is no longer present a physical
admixture of the two components.
There was no measurable evolution
of heat and as far as could be observed the mixture was
liquid polyamide resin resulting from the condensation of
polymerized linoleic acid with a polyamine. Upon the
addition of the polyamide resin to the nonylbenzene di
isocyanate no observable reaction occurred.
There was
no measurable evolution of heat and as far as could be
Example V
observed the mixture was merely physical as between the
To 100 grams of an ethylbenzene diisocyanate there 55 two components. This mixture remained’ in this condi
tion at ambient temperatures for a period of time in excess
was added 200 grams of a liquid polyamide resin resulting
of three months.
'7
from the condensation of polymerized linoleic acid with
Example X!
a polyamine. Immediately upon the addition of the
polyamide resin there occurred a spontaneous exothermic
To 100 grams of a decylbenzene diisocyanate there was
reaction between the components that produced a solid 60 added 200 grams of a liquid polyamide resin resulting
amorphous polymeric material. Thus, it is obvious that
there is no longer present a physical admixture of the two
components.
Example VI
To 100 grams of an ethylbenezene diisocyanate dis
solved in 900 cc. of toluene there was added 200 grams of
the same polyamide resin as that described in Example V.
Upon the addition of the polyamide resin to the solution
of ethylbenzene diisocyanate there occurred a spontane
ous exothermic reaction between the components that
produced a solid amorphous polymeric material. Thus,
it is obvious that the pot life of such a mixture is zero
and it is equally obvious that there is no longer present
a physical admixture of the two components.
from the condensation of polymerized linoleic acid with
a polyamine. Upon the addition of the polyamide resin
to the decylbenzene diisocyanate no observable reaction
occurred. There was no measurable evolution of heat and
65 as far as could be observed the mixture was merely physi
cal as between the two components. This mixture remain
ed in this condition at ambient temperatures for a period
of time in excess of three months.
Example XII
To 100 grams of a decylbenzene diisocyanate dissolved
in 400 cc. of toluene there was added 200‘ grams of a
liquid polyamide resin resulting from the condensation
of polymerized linoleic acid with a polyamine. Upon the
addition of the polyamide resin to the decylbenzene di
3,020,251
6
isocyanate no observable reaction occurred. There was
the two components. This mixture remained in this con
dition at ambient temperatures for a period of time in
no measurable evolution of heat and as far as could be
observed the mixture was merely physical as between
the two components. This mixture remained in this
condition at ambient temperatures for a period of time
excess of three months.
In Examples IX to XIV, inclusive, it is clearly shown
that a long chain alkylbenzene diisocyanate and a poly
amide resin can exist merely as a physical admixture for
prolonged periods of time. This is true whether the mix
ture is composed merely of the alkylbenzene diisocyanate
in excess of three months.
Example XIII
To 100 grams of a dodecylbenzene diisocyanate there
and the polyamide resin or whether one or both of the
was added 200 grams of a liquid polyamide resin result 10 components is diluted with an inert hydrocarbon diluent.
ing from the condensation of polymerized linoleic acid
I claim:
with a polyamine. Upon the addition of the polyamide
resin to the dodecylbenzene diisocyanate no observable
A composition of matter comprising an alkylbenzene
diisocyanate wherein the alkyl radical is selected from the
reaction occurred. There was no measurable evolution of
group consisting of branched and normal chains and con
heat and as far as could be observed the mixture was 15 tains from about 9 to about 18 carbon atoms and a poly
merely physical as between the two components. This
mixture remained in this condition at ambient tempera
meric polyamide in a ratio of from about 1:1 to about
1:3, respectively, based on weight percent, said poly
amide being the reaction product of polymeric fatty acids
tures for a period of time in excess of three months.
containing at least two carboxyl radicals and an aliphatic
Example XIV
To 100 grams of a dodecylbenzene diisocyanate dis
solved in 400 cc. of toluene there was added 200‘ grams
20 polyamine containing reactive radicals selected from the
of a liquid polyamide resin resulting from the condensa
tion of polymerized linoleic acid with a polyamine. Upon
the addition of the polyamide resin to the dodecylbenzene 25
diisocyanate no observable reaction occurred. There
was no measurable evolution of heat and as far as could
be observed the mixture was merely physical as between
group consisting of amine radicals and carboxyl radicals.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,241,321
2,858,296
2,864,780
Schlack _____________ __ May 6,1941
Stilmar ______________ __ Oct. 28, 1958
Katz et a1 ____________ __ Dec. 16, 1958
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