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Патент USA US2405775

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Patented Aug. 13, 1
2,405,775
r
UNI‘TE s'mre s
PATENT OFFICE _
2,405,775
msuc'rrcma sun momma
William E. Bradley, Los Ane'eles, Calif,
to Union Oil Company of Californla,
geles, CaliL, a corporation of California
No Drawing. Application June 8. 1942,
Serial 100.448.273
' '1 Claims.
,' (or. raw-as)
This invention relates to the production of im
proved fungicides and insecticides containing syn- '
tic.
thetic light oils.
isoparailinic products boiling in the range 350°
.
In the past it has been common practice to em
'
treatment with acid. clay. suliur dioxide or caus
ploy naturally occurring petroleum fractions, es-‘
pecially those fractions boiling in the range of
350° F. to 800° F. in the preparation of insecticides
and fungicides. These oils have been used alone
or commingled with auxiliary additives designed
to produce speci?c toxic, spreading. or emulsify
ing qualities. For example, typical ?y sprays have
comprised highly re?ned kerosene fractions, spe
ci?c toxic ingredients such as pyrethrum extract,
and perfumes. Typical spray oils or fungicide
oils have comprised simply highly re?ned petro
leum fractions boilingin the light lubricating oil '
According to this invention, substantially pure
F. to 800° F. are prepared by any process involving
principally almlation of p
with mono
ole?ns. The product is then subjected to frac
tionation and ?nishing treatment. in either order,
and compounded with the desired additives, such
as toxic, spreading. or emulsifying agents, anti
oxidants, etc. The fractionation is preferably
carried out continuously, in a vacuum, or using
steam. Generally the insecticide base oils such as
tly spray base, are fractionally distilled so as to
boil within the range ofabout 350° F. to 550° F.,
while the spray oils such as those used in fungi
cides, are fractionated so as to boil in the range
of ‘about 450° F. to 800° F. The ?nishing treat
ment may involve treatment with concentrated or
range. “Soluble oil” sprays commonly comprised
petroleum fractions, soaps, alcohols and water.
In ‘all such preparations it is obviously desirable
fuming sulfuric acid in the proportions of about
Y that the product shall have a, controlling effect 20 one pound H2504 per gallon, or in smaller pro
on the insect pest or undesirable fungus and yet
portions, followed by water washing, caustic
be as harmless as possible to human beings, do
washing and/or distillation. Other conventional
mestic animals, plants and to equipment used in 1 ?nishing treatments may also be used, such as
the application. For indoor operation, such as
clay treatment, with or without a. preceding sul
?y spray, it is further desirable that the oil base 25 furic acid treatment: orvapor phase treatment
have an odor which is very bland or rather pleas
ing. It is known that many of the insecticidal
and fungicidal oils now in use are somewhat toxic
with fuller’s earth, clay. ‘partly hydrated zinc
to human beings, domestic animals and plants.
30 para?inie ?y spray base was prepared, using as
a starting material a sample of “heavy alkylate”
obtained as a bottoms fraction from distillation
Furthermore they have a serious destructive ac
tion on equipment due to their tendency to dis;
solve or swell rubber parts used in the equip
ment: Finally the odors of some sulfur- and
‘nitrogen-containing bodies frequently associated
with petroleum fractions. and even the odors of
some of the hydrocarbons themselves, are objec
' tionable.
Many
petroleum fractions which have
chloride, etc.
‘
As a speci?c example of my invention, an iso
of the alkylated product from a commercial al
kylation plant. "ihe latter was-a conventional
plant for continuously reacting isobutane. with
_ butenes and pentenes, employing H1804 as a cataq
lyst, and was similar to that described in the Re;
?ner, vol. 20, 1941,, page 3'39. The reaction mix-‘'
been used in fungicides or insecticides have been
ture in this instance comprised about 45 volumes
heavily treated with strong sulfuric acid or liquid 40 of isobutane and about 100 volumes of approxi
mately 92% sulfuric acid to each volume of ole;
isulfur dioxide for example, in order to remedy to
?ns. The debutanized alkylated product from
some extent the above undesirable properties.
this plant was distilled to obtain a light alkylate
It is the object of this invention to provide in
for use in aviation gasoline and a heavy
Isecticides and fungicides compounded from syn
- suitable
thetic oils having insecticidal and fungicidal 45 alkylate bottoms fraction which, in this case, had
properties equivalent to those of the petroleum
products now in use. but having other properties
in marked contrast to those of the petroleum
products, namely, (1) a less pronounced and more
a boiling range of approxlmatehr 350 to 600° F.
and consisted of substantially ‘pure isoparamns.
A portion of this material was steam distiliedto
obtain a fraction having a boiling range of ap
pleasing odor, (2) relatively low swelling action 50 proximately 380 to 480° F. This fraction was agi
tated one minute with 98% E180; in the ratio of
on natural or synthetic rubbers, (3) relatively low
10 pounds acid per barrel of oil and settled for
tom‘city to human beings, animals, and plants,
one hour. The oil was then decanted from the
(4) relative freedom from sulfur- and nitrogen
acid sludge, washed successively with an equal
containing impurities, and (5) su?lcient purity
and stability as to require only moderate ?nishing 55 volume of water and 10% by volume of 2% caustic
2,405,776
3
soda solution, and steam distilled, taking about
the acid sludge phase was drawn off
95% overhead. This overhead fraction, which
tested over 95% isopara?‘ins, was washed with 5%
by volume of 2% caustic soda solution, and com
pared with a typical high quality kerosene type
?y spray base made in the following manner:
A kerosene fraction of 380 to 480° F. boiling
range distilled from crude oil was subjected to
extraction with an equal volume of liquid sulfur
dioxide at a temperature of about 15’ F. .The 10
“ra?inate" fraction, which contained smaller pro
was agitated one-half hour with a
of 50 pounds of Death Valley clay
per barrel. After one hour of settling the bulk of
the clay was drawn of! and the ?nished oil was
decanted from the remainder. Results of com
parative tests of the two spray oils follow:
Synthetic
lsopara
portions of aromatic type hydrocarbons, sulfur
and nitrogen-containing materials than either the
Speci?c gravity at 60° F./60° F ______ -.
Englei- dist'n, °F.:
“extract” fraction or the feed stock, was freed of
10
sulfur dioxide and treated with 10 pounds of 98%
15
90
o _________________________ ..'....
H2804 per barrel followed by washing with an
Sulfur, per cent by wt ____ __
.
S. U. viscosity at 100° F., se
equal volume of water and 10% of 2% caustic
Pour
int, "F ____ ..
soda solution successively, as described above.
‘The characteristics of the two products follow:
Lgynthetic
paroiiinic
Lack of phiwtocidal e?ects--_ _______ .- 20 Insecticide
value ___________ ..
eroserg
Fungicidal value___; ____ __- __________ _
ra?ina
traction
.- Of particular interest are
r
. - 404
_-
388.
420________ __
452
417.
454.
Approx. viscosity, 8. U.>a't'~l00° F., sec. . 80......... _- 30.
Pour
int, °F_; ......... .»..’~.-.-_--.’-._ Below -90-. About
EquaPgol. aniline point, °F..
‘ 198 ________ __
Insecticidal value ........ ..
Good ...... __
160.
Good.
considered to be a measure of the quality of the
spray oil as being non-injurious to plants. The
two spray‘oils described above were emulsi?ed
with water after addition of 0.5% of tetraethylene
—45.
.30 glycol monolaurate and it ‘was found that the
product containing the isopara?lnic material, in
Lack of phytocidal sheets"... ______ _.- Excellent__._
Do.
Swelling action on rubber, per cent... 1 0 _______ __ 50% to 100%.
Odor
-' -
Excellent
the above values for
25 percent unsulfonated residue which ‘is generally
gulf?!‘
(GI-Eights
per cent by
wt- .__-._-. 0.00:. ..... ._ 0.15.
nger
n, F;
'
...... ._
_
.881.
Equa \vol. an. pt., ° ........... _:...
Spec. gravity at (50°/60° F.'.__._--.___... .787--..;.~_.-__ .806.
102'
.835 ....... .
spray oil
Swelling action on rubber, per cent._._
Unsulfonated residue, de Ong, per cent. 57
Acid treated
'
50 P. ______________ _; ____
00¢.
__
a
Typical
c
spite of its low de Ong value was relatively non
Good.
.
iniurious to plantsv and foliage. Low speci?c
gravity, low sulfur content, low pour point and
Finished insecticide sprays were prepared from 35 high aniline point also distinguish the synthetic
isopara?inic oils of both this table and the earlier .
the above two materials by adding to each 0.2%
table from the typical. petroleum products.
of pyrethrins as a lethal ingredient and a small
amount oi’ perfume. The two products were
equally effective insecticides.
The relative toxicity to animals of the above
‘
‘ described synthetic isopara?‘lnic oils, compared to
The yield of heavy alkylate in the process de 40 the petroleum fractions may be deduced from
scribed above may be improved by (1-) operating
data included in Report No. 80 of the Medical
' at relatively low ratios of isobutane to ole?n in
Research Council of the British Industrial Health
the feed stock and recycle stream, (2) alkylating'
Research .Board, published as a book entitled
"Toxicity of Industrial Organic Solvents" by His
at relatively high temperatures, particularly above
Majesty's StationeryO?ice, London in 1937. In
50° F., and (3) using H2804 of rather low strength,
in the neighborhood of 90% or below.
An isoparai?nic spray oil was prepared as fol
lows: Five volumes of “heavy alkylate," as de- '
scribed above, and ?ve
the course of a discussion of the relative toxicities
of various types of hydrocarbon mixtures it is
volumes ‘of 98% , H2504
were introduced ‘into a vessel equipped with an 50
agitating device. While agitating this mixture at
a temperature of about 60° F. One volume of crude
stated that for mixtures containing principally
cyclopara?ins and acyclic para?ins, the toxicity
increases with increasing cycloparai?n concentra
tion, and alsowith increasing speci?c gravity.
On this basis the isopara?lnic oils described above
di-isobutylene was added in small proportions
over a period of one-half hour.
After an addi
tional three hours of agitation the mixture was
allowed to settle and the hydrocarbon phase was
decanted from the acid phases The hydrocarbon
phase was washed with 101% '~ by volume of 2%
caustic soda solution and steam distilled to re
move that fraction boiling below 480° F. The 60
high boiling residue was treated with 10 pounds
of 98% H2304 per barrel followed by water and
in which naturally occurring antioxidants have
been removed in the re?ning process.
caustic, as described above, and steam distilled to
obtaina distillate having a ?nal boiling point of
about 620° F. -,'I'his product was compared with 65
a typical high quality spray oil made from a petro
leum fraction as follows:
A'fraction from crude oil distillation having a
boiling range of about 480 to 620° F. was treated
with 125%‘ by volume of liquid sulfur dioxide in
four counter-current stages at a temperature of
about 50° F. The rai?nate fraction after removal
of; all sulfur dioxide was agitated one-half hour
with sulfuric acid in the ratio of 50 pounds of
103% H2804 perbarrel of all. 7 After two hPurs'
._Y
I
7
..
- 8,405,776
5
While the character-of certain materials has
been described in detail in order to clarify the
signi?cance of the invention, it is not intended
to impose limitations thereby. ‘For example the
alkylation process may involve other catalysts,
such as I-IF' or AlCla, etc., other oleilns such as A
those produced from cracking, chlorination and
dehydrochlorination, oxidation and dehydration,
ed with insects, which comprises spraying said
areas with a material comprising a substantially
pure isopc oil boiling in the range of about
350° F. to about 550° F.
.
3. A process for the treatment of areas infest
ed with fungus, which comprises spraying said
areas with a material comprising a substantially
the range of about
450° F. to about 800° F‘.
- pure lsoparamnic oil boiling‘in
eta, other isoparaiiinic i’eed stocks, and other
et- An insecticide consisting essentially of small
apparatus or operating conditions. The‘emulsi 10 amounts of pyrethrins, dissolved in a substan
tying agents used with the isoic spray oils
tially pure isoparc base oil boiling within
to: emulsions, suspensions, or soluble oils may
include not only tetraethylene glycol mono
laul'ate' but other esters, soaps, alcohols, etc.. such
as calcium caseinate, saponin. soaps of whale oil,
their oil. cottonseed oil,‘v oocoanut oil. etc.. and their
fatty acids. fatty acids themselves, phenol homo
iogs, Bordeaux mixture, and resin. Some or these
may‘also have other effects such as spreading,
stlckinz. or toxic/silicate. Other auxiliary toxic
agents may include nicotine suli'ate. rotenone.‘
etc, It will lie/apparent to those skilled in the
art that numerous other modi?cations may be
made without departing trom the scope of the
iollowing claims. I claim:
-
the range‘350°-F. to 550° F.
-
5. An insecticidal and fungicidal spray emul
sion consisting essentially of a substantially pure
mop'arc base oil boiling in the range 350° F.
to 800° E, an emulsifying agent. and water.
6. An 'insecticideconsisting essentially of small
amounts of pyrethrins and a perfume, dissolved
in a substantially pure isoparafnnic oil boiling in
20 the range of approximately 350° F. to 550° F.
and prepared by a process involving alkylation
of an ole?n andvan isoparamn'.
7. An insecticidal and fungicidal spray emulsion consisting essentially of an emulsifying
25 agent. water, ‘and a substantially pure isopar
ai?nic oil boiling in the range 01' approximately
1. A process for the treatment of areas infest
450° F. to 800° F. and prepared by a. process in
ed .with tunsus and insects. which comprises - volvins alkylation 0! an ole?n and an isopara?in,
spraying said areas with a material comprising
said oil having a speci?c gravity of about 0.835
a substantially pure isoparamnic oil boiling in 30 and a do On: unsullonated residue of about 57%.
, p
E. BRADLEY
‘ the ranle of about 350° 1''. to about 800° 1'',
2. A process for the treatment of areas infest
'
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