Патент USA US2405775код для вставки
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 '