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Патент USA US3094466

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June 18, 1963
F. s.l BLACK
3,094,456
coNcENTRATEn INsEcTIcInAL coMPosITroNs
Filed Jan. 1'?, 1961
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INVEN TOR.
BY
June 18, 1963
F. s. BLACK
3,094,456
CONCENTRATED INSECTICIDAL COMPOSITIONS
Filed Jan. 17, 1961
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June 18, 1963
F. s, BLACK
3,094,456
CONCENTRATED INSECTICIDAL COMPOSITIONS
Filed Jan. 17, 1961
3 Sheets-Sheet 3
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Uníted States Patent O ” ICC
1
2
the solvent. It will ‘be noted from this curve that the
maximum amount of aldrin which remains in solution at
20° F. is less than about 42%; if more than 42% aldrin
is present at 20°. F. crystals of aldrin form.
FIGURE 2 is a curve showing the temperature
percentage content relation for a commercial grade of
3,094,456
CÜNCENTRATED INSECTICIDAL COMPOSITIONS
Frank Shumway Black, Westwood Manor, Wilmington,
Del., assigner to FMC Corporation, a corporation of
Delaware
Filed Jan. 17, 1961, Ser. No. 83,291
9 Claims. (Cl. 167-30)
heptachlor (67% active material) in methylene chloride.
It will be noted from this curve that the maximum amount
of heptachlor which remains in solution at 20° F. is
This invention relates to novel insecticidal solutions.
‘In this speciiication, all percentages and parts are by
about 38%; more heptachlor, if present, will crystallize.
weight.
FIGURE 3 is a curve showing the temperature
percentage content relation for a commercial grade of
The impregnation of solid fertilizers with solutions
containing chlorinated hydrocarbon insecticides is well
known.
Patented June 18, 1963
aldrin (91% active material) in xylene. It will be noted
Solutions `containing 1,2,3,4,l0-hexachloro-l,4,
from this curve that the maximum amount of aldrin
4a,5,8,8a - hexhydro - 1,4-endo,exo-5,8~dimethanonaphtha- 15
which remains in solution at 20° F. is approximately
lene (hereinafter called ald-rin) or 1,4,5,6,7,8,8-hepta-
50%; more aldrin, if present, will crystallize.
chlor-3a,4,7,7a-tetrahydro-4,7-methanoindene (hereinafter
called heptachlor) have been used for this purpose.
«FIGURE 4 is a curve showing the temperature
percentage content relation for a commercial grade of
In
the impregnation of dry fertilizers with chlorinated hydro
carbon insecticides, such as aldrin or heptachlor, a solu
heptachlor (67% active material) in xylene. It will be
20 noted from this curve that the maximum amount of hepta
tion having a high concentration of the active ingredient
chlor which remains in solution at 20° F. is about 38%;
is desirable so that the required amount of insecticide
more heptachlor, if present, will crystallize.
may be applied to the fertilizer without making it too
I"FIGURE 5 is a curve showing the temperature
wet or sticky. Moreover, in the storage- and shipment
percentage content relation for Ia commercial grade of
of solutions of aldrin or of heptachlor for use in impreg 25 aldrin (91% active material) in methylated naphthalene,
nating fertilizers and for other insecticidal uses, it is
desirable to employ relatively concentrated solutions. By
the specification for which is given above. ‘It will be
noted from this curve that the maximum amount of
so doing, waste of solvent is minimized. Also an im
aldrin which remains in solution at 20° F. is about 46%;
portant economy is eifected in transportation costs in that
more aldrin, if present, will crystallize.
less solvent and more active material is shipped per unit 30
4FIGURE 6 is ya curve showing the temperature
weight.
percentage content relation for a commercial grade of
It is important that the amount of solvent used is
heptachlor (67% active material) in the same methylated
enough to give a stable solution, one from which aldrin
naphthalene. It will be noted from this curve that the
or heptachlor, as the case may be, crystals will not for-m
maximum amount of heptachlor which remains in solu
at the temperature conditions encountered in storage or 35 tion at 20° F. is about 38%; more heptachlor, if present,
shipment. `As a practical matter, such solutions should
will crystallize.
be stable, i.e., discrete crystals should not form at tem
It is among the objects of the present invention to
peratures as low as 20° F., which temperatures are fre
provide a solution of aldrin and heptachlor containing at
quently encountered »in the storage of such solutions under
least about 53% of these active ingredients, `which solu
winter conditions in the colder climates. It is not unusual 40 tion remains stable at temperatures as low as 20° F.
to store and handle these solutions in unheated buildings
It is a further object of this invention to provide an
where the temperature may fall to 20° F.
insecticidal solution containing both aldrin and hepta
The accompanying drawings depict a series of curves
chlor, which solution is stable at temperatures as low
showing the temperature-percentage content relation for
as 20° F . and contains these active insecticidal materials
aldrin and heptachlor, respectively, in the solvents methyl 45 in a concentration markedly greater than the solubility of
ene chloride, xylene and methylated naphthalenes. The
either of t-he active materials in the same solvent at
particular methylated naphthalene used as the solvent is
temperatures of about 20° F.
the heavy aromatic naphthta household grade sold by
These and other objects of the invention will be appar
Standard Oil of New Jersey having the following
speciñcations :
50
Specitic gravity, 60/60° F __________________ __ 0.9224
Gravity, °API, 60° F ____________________ __
21.9
Lbs/gallon, 60° __________________________ __
Viscosity, cs. at 25° ______________________ __
Color, Saybolt ____________________________ __
7.68
1.627
16
Refractive index, 20° F ____________________ __ 1.5059
Distillation range, ° F.:
IBP
____ __
___
5% _
320
343
50%
_______________________________ __
406
90%
_______________________________ __
488
95%
_______________________________ __
509
-Dry point ____________________________ __
532
Flash point, ° F. (tag closed cup) __________ __
141
Percent aromatics ______________________ __ 83% min.
ent from the following description.
In accordance with the present invention, a single phase
insecticidal solution is provided, which solution will not
crystallize at temperatures as low as 20° F. and contains
at least about 53% of active ingredients consisting essen
tially of a mixture-of aldrin and heptachlor in a ratio of
55 3 to 1 parts of heptachlor to l to 3 parts of aldrin, prefer
ably about 1 to 1 of heptachlor to aldrin, in a liquid sol
vent, namely, xylene, methylene chloride, methylated
naphthalenes, or a mixture of these solvents. Preferably
the insecticidal solution contains from 60% to 90% of a
60 mixture of aldrin and heptachlor in the relative propor
tions indicated and from 10% to 40% of the solvent
above mentioned. The solution may, of course, contain
small amounts of other common additives, such as emul
sifying agents including anionic, nonionic and mixtures of
65 anionic and nonionic emulsitiers.
Non-volatile content, g./ 100 ml _____________ __
0.189
Surprisingly I have found that a mixture of aldrin and
Kauriabutanol value _______________________ __
95.0
heptachlor in the ratio of 3 to 1 parts of heptachlor to
1 to 3 parts of aldrin is more soluble in the solvents men
FIGURE 1 is a curve showing the temperature 70 tioned at low temperatures, Le., as low as 20° F., than
either aldrin alone or heptachlor alone. While the rea
percentage content relation for a commercial grade of
sons for this phenomenon are not fully known or under
aldrin (90% active material) in methylene chloride as
In the drawings,
3,094,456
4
Example VI
stood, it is believed that the aldrin and heptachlor in the
indicated proportions form eutectic mixtures which have
better solubility characteristics in the enumerated solvents
Percent
Aldrin _____________________________________ __
36
than does aldrin alone or heptachlor alone. It will be
appreciated that this invention is not to be limited to the
above explanation which is advanced to facilitate a bet
ter understanding of the invention.
In addition to the use of the single phase insecticidal
solutions of this invention as a ready-made formulation
for application to dry fertilizers, such solutions with or 10
without an emulsifying agent may be used for insecticidal
Heptachlor
purposes to control insects such as southern army worms
Methylene chloride __________________________ __ l0
(Prodenz'a eridanz‘a). Dispersing and emulsifying agents
Xylene
which can be employed include polyoxyethylene alkyl
phenols, polyoxyethylene fatty esters, polyoxyethylene
Heptachlor _________________________________ __ 44
Methylene chloride __________________________ __ 20
This solution was stable at 20° F.
Example VII
Percent
Aldrin _____________________________________ __ 36
_________________________________ __ 44
____________________________________ __ 10
This solution was stable at 20° F.
15
sorbitan fatty esters blended with oil-soluble sulfonates,
Examples
for example, a mixture of the calcium salt of an oil
soluble sulfonate (Emcol H-300X) and polyoxyethylene
glycol ether (Emcol H-500X).
VIII
The following examples are given for illustrative pur 20
poses. -It will be understood the invention is not limited
to these examples. In these examples the aldrin and
heptachlor were commercial grades. The heptachlor in
Aldrin, percent ____________ __
Heptachlor, percent _______ -_
Xylene, percent ___________ __
45
45
10
IX
47
43
10
X
43
47
10
XI
49
41
l0
XII
41
49
10
These solutions did not crystallize at 32° F. after five
all examples contained 72% active material, the aldrin
from 91% to 93% active material. In all cases the con 25 days at this temperature. At 10° F., after standing for
ñve days, the entire mass solidified but without crystal
stituents mentioned in the proportions indicated were
formation. Upon permitting the mass to stand at about
mixed at room temperature.
40° F., the solidified mass again became a substantially
Example 1
Percent
Aldrin ____________________________________ __
32
Heptachlor ________________________________ __
42
Xylene
___________________________________ __
21
Emcol H-300X _____________________________ __
3.75
EmcolH-SOOX _____________________________ __
1.25
homogeneous solution.
30
The above examples demonstrate the surprising increase
in solubility of the mixture of aldrin and heptachlor in
the ratio of -3 to 1 parts of heptachlor to 1 to 3 parts
of aldrin in the enumerated solvents as compared with
»aldrin alone or heptachlor 4alone in the same solvent.
35 Compare, for instance, Example I, which ycontains 32%
The solution deposits no crystals at 20° F.
aldrin and 42% heptachlor (la total «of 74% aldrin and
heptachlor) in 21% xylene solvent ywith FIGURES 3
Example II
and 4 which show the solubility curves for :aldrin and
Percent
heptachlor in Xylene. It will be noted from FIGURE
Aldrin __________________________________ __ 23.05
40 4 that the maximum solubility of heptachlor in xylene
Heptachlor _______________________________ __ 30.89
at 20° F. is about 38%. Example I `contains »approxi
Xylene __________________________________ __ 46.06
mately 4% more heptachlor than the maximum solubility
The solution on standing for eleven days at _19° F.
of heptachlor in Xylene `at 20° F. `In addition, 'Example
deposited no crystals. Aíter this ll-day period, it was
I contains :about 32% aldrin, and yet the composition is
seeded with both heptachlor and aldrin and remained at 45 stable at temperatures as low as 20° F. This is indeed
-19° lF. for an additional eight days, at the end of which
surprising -and unexpected. Equally surprising ‘and un
time it still remained free of crystals.
expected is the stability of the solution of Example II
at 20° F. taking into account the fact that as shown in
Example III
Percent 50 FIGURE 4 heptachlor is less soluble in xylene than aldrin,
yet this example contains 30.89% heptachlor and 23.05%
Aldrin _____________________________________ __ 24
aldrin, -appreciably more total active material than the
Heptachlor _________________________________ __ 31
Xylene
maximum amount of the more soluble aldrin which will
____________________________________ __ 45
remain in the xylene solvent without crystallization at
This solution was stable at 20° F.
20° F.
55
Percent
It will be noted that the present invention provides
a single phase insecticidal solution containing at least
___________________________________ __ 31.1
about 53% of active ingredients consisting essentially
Example IV
Aldrin
Heptachlor ________________________________ __ 39.3
Xylene ___________________________________ __ 29.6
60
This solution was tested at temperatures between 0°
to 10° F. and showed practically no solid formation after
two weeks at these temperatures. This solution showed
only a negligible amount of solid formation at 0° F. after
three months storage at 0° F.
65
Example V
Percent
Aldrin ____ ________________________________ __
'Heptachlor
Emulsifier
__» ______________________________ __
27
4
This solution Was stable at temperatures above 0° F.
Only a negligible amount of solid or crystal formation
was observed after one week of storage at 0° F.
this invention provides such solutions containing ap
preciably more of a mixture of these active ingredients
as compared with the maximum solubility of either aldrin
or heptachlor in these solvents at relatively low tempera
tures of the order of about 20° F.
The percentage solubility values given above for aldrin
and heptachlor refer to the solubility of commercial grades
of these materials which contain small amounts of isomers
and other related materials.
30.5
_______________________________ __ 38.5
Xylene ___________________________________ __
of a mixture of aldrin `and heptachlor, which solution
is stable at temperatures :as low as 20° F. Moreover,
70
It is to ‘be understood that this invention is not re
stricted to t-he present disclosure otherwise than as de
ñned by the `appended claims.
This application is a continuation-in-part of applica~
tion Serial No. 623,783, filed November 23, 1956, now
abandoned.
3,094,456
5
What is claimed is:
1. A single phase insecticidal solution which Will not
crystallize at temperatures as low `as 20° F. containing
at least `about 53% by Weight of active ingredients con
sisting essentially of a mixture of aldrin and heptachlor
in the ratio of 3 to 1 parts by weight of heptachlor to
1 to 3 parts by Weight of aldrin in not more than about
47% by weight of a liquid solvent from the group con
sisting of Xyiene, methylene chloride, methylated naphtha
lene and mixtures 01"' at least two of said solvents.
2. A single phase insecticidal solution which will not
crystallize -at `temperatures as low `as 20D F. containing
`at least about 53% by Weight 0f active ingredients con
sisting essentially of a mixture or” aldrin tand heptachlor
in the ratio of 3 to 1 lparts by Weight of heptachlor to l
to 3 parts by Weight of aldrin in not more than about
47% by Weight of Xylene.
5. An insecticidal solution which will not crystalline
at temperatures as -low as 20° F. containing from about
60% to 90% by Weight of active ingredients consisting
essentially of a mixture of `aldrin and heptachlor in ap
proximately equal parts in `from 10% to 40% by Weight
of a liquid solvent `from the group consisting of Xylene,
methylene chloride, methylated naphtbalene and mixtures
of at least two of said solvents.
6. An insecticidal solution which will not crystallize
10 at temperatures `as loW as 20° F. containing about 32%
by Weight vof aldrin, »about 42% by Weight of heptachlor
and about 21% by weight of xylene.
7. An insecticidal solution which will not crystallize
at tempera-tures as low :as 20° F. containing about 23%
by `Weight of aldrin, about 31% by Weight of heptachlor
and about 46% by Weight of Xylene.
8. An insectieidal solution Which will not crystallize
3. An insecticidal solution which will not crystallize
»at temperatures las low as `20° F. containing about 24%
‘at temperatures as low as 20° F. containing »at least about
by weight of aldrin, `about 31% by weight of heptachlor
53% by -Weight of active ingredients consisting essen 20 and about 45% by Weight of Xylene.
tially of :a mixture of aldrin and heptachlor in the ratio
of 3 to 1 parte by Weight of heptachlor to 1 to 3 parts
by weight of aldrin in not more than about 47% by
Weight of methylene chloride.
9. An insecticidal solution which fwill not crystallize at
temperatures as low as 20° F. containing .about 30.5%
by Weight of aldrin, about >38.5% by weight of heptachlor,
about 27% by Weight of Xylene and labout 4% by weight
4. An insecticidal solution which will not crystallize 25 of :an emulsifying agent.
at temperatures as low as 20° F. containing at least about
References Cited in the ñle of this patent
53% by Weight of active ingredients consisting essen
tially of a mixture of taldrin and heptachlor in the ratio
Handbook of Aldrin, Dieldrin >and -Endrin Formula
of 3 to 1 parts by Weight of heptachlor to 1 to 3 parts
tions-«Shell Chemical Corporation, December 1954, pages
by Weight of ialdrin in not more than `about 47% by 30 6, 7, 9, l0 and l1. (Copy in Patent Oiiioe Scientific
Weight of methylated naphthalene solvent.
Library.)
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