3,642,901 United States Patent Office Patented Feb. 15, 1972 2 converted to oxidation products, which are responsible for 3,642,901 . the eye-irritating, plant-damaging, and reduced visibility BORONTRFLUORDE, ETHERATEAMNE REACTION PRODUCTS characteristics of smog; that the intermediate product is Abraham M. Herbsman, 9721 3rd Ave., believed to break down to form ozone, which in turn may Los Angeles, Calif. 90305 further oxidize certain hydrocarbons, principally olefins; No Drawing. Application Sept. 13, 1968, Ser. No. 759,780, and that some of these intermediate products and the now Patent No. 3,488,169, dated Jan. 6, 1970, which is ozone itself are believed to comprise the high "oxidant' a continuation-in-part of application Ser. No. 283,550, content of the Los Angeles atmosphere. (Chemistry and May 27, 1963. Divided and this application July 31, Physiology of the Los Angeles Smog, Industrial and Engi 1969, Ser. No. 864,241 neering Chemistry 44, pp. 1342-6; 1952 and "Ozone For Int. CI. C07c35/00, 87/00, 87/06 O mation in Photochemical Oxidation of Organic Sub U.S. C. 260-583 A 4 Claims stances,” Industrial and Engineering Chemistry 45, pp. 2086-9; 1953). In a paper, entitled “Relative Reactivity of Various Hydrocarbons in Polluted Atmospheres' by ABSTRACT OF THE DISCLOSURE E. R. Stephens and W. E. Scott, presented May 17, 1962 A composition of matter, which is soluble in gasoline 5 to the American Petroleum Institute's Division of Refin and in liquid aliphatic hydrocarbons, and which consists ing, it is stated that irradiated "dilute mixtures of olefin of the product, produced by reacting boron trifluoride with nitrogen dioxide in air' produced most of the symp ethyl ether complex with an amine reagent, selected from toms of photochemical air pollution with eye irritant prod the group consisting of tertiary nonyl amine, a mixture of ucts, identified as formaldehyde, acrolein and peroxyacyl tertiary-alkyl primary amines, ranging from t-C12H25NH2 20 nitrates; and with plant damaging products, identified as to t-CH3NH2, a mixture of tertiary-alkyl primary ozone and peroxyacyl nitrates. amines, ranging from t-C18H3NH2 to t-C4H49NH2, and It is generally conceded that the major contaminant of primary alkyl aryl amines in which the alkyl radical is the air in Los Angeles is automobile exhaust. For the large enough to impart solubility to the reaction product efficient performance demanded, an automotive engine is in gasoline and liquid aliphatic hydrocarbons. 25 operated under "rich mixture' conditions with insufficient air for complete combustion. Because an internal com -cars... sees actres bustion engine acts as a "cracking' device with regard This application is a division of my prior copending to the fuel introduced therein, the major portion of the application Ser. No. 759,780, filed Sept. 13, 1968, and now exhaust hydrocarbons is unsaturated or olefinic in char U.S. Pat. 3,488,169, which is in turn a continuation-in-part 30 acter and, as such, is easily reacted upon in the atmos of my prior application Ser. No. 283,550, filed May 27, phere to produce Smog conditions. In their study of hy 1963, and now abandoned. drocarbon emission by automobile exhausts to the atmos The present invention relates to new compositions of phere, Magil et al. ("Hydrocarbon Constituents of Auto matter and method for treating internal combustion engine mobile Exhaust Gases,” Proceedings of the Second Na fuel gases, which consists in employing with the fuel or the 35 tional Air Pollution Symposium, Stanford Research In gases formed on combustion of the fuel a catalytic agent, stitute, pp. 71-83; 1952) concluded that the exhaust com capable of promoting polymerization and chemical con position is independent of the type of gasoline burned densation of organic compounds, such as unsaturated and stated, "The fact that the C5 to C olefin concentra hydrocarbons, olefins and aldehydes. This treatment has tion in the exhaust is the same for widely different types been found to inactivate and lessen the smog-inducing 40 of gasoline burned emphasizes that the olefinic material in components of the engine exhausts to a material degree, the gasoline does not contribute, except to a very small principally by decreasing the nitrogen oxides content and extent, to the olefinic material in the exhaust.' The Air increasing the molecular structure of the olefinic and Pollution Field Operations Manual by U.S. Department unsaturated hydrocarbons of the combustion gases. It also of Health, 1962, states that ethylene (present in auto has been found to inclusively improve combustion, effect mobile exhaust) causes severe damage to vegetation (page smoother engine performance and give better mileage, 3) and that the smog-forming potential is also dependent when the catalytic agent, as a catalytic composition, is on the ability of specific hydrocarbons to be oxidized added to automobile fuel. (page 32). According to certain aspects of my invention, the com It appears that the effort to overcome the problem of bustion engine gases are subjected to continuous intimate 50 emission of noxious gases by internal combustion engines gaseous admixture with the catalyst in a practically nas has been mainly confined to treatment of the gases at the cent vapor state. Thus, the most efficient means of cata muffler or tailpipe of the automobile in the design of lytic application is attained. Also of note, is the fact that chambers in which oxidation of the exhaust gas hydro the catalytic effect, herein employed, does not require the carbons might be completed. These adaptations are known injection of supplemental or secondary air into the 55 as an "afterburner' and a "catalytic converter.” Both exhaust, as demanded with the use of “afterburners' and adaptations demand the introduction of additional air to oxidation catalysts; and accordingly obviates the pollution complete the combustion. With the “afterburner, a pilot that results from the additional oxides of nitrogen, pro light or spark ignites the hydrocarbon-air mixture, and duced by such introduction of air. combustion is completed on a hot ceramic surface; while The untreated engine exhaust gases contain unsaturated 60 in a catalytic converter, oxidation is completed catalyti hydrocarbons, including olefins, which, accompanied by cally at a much lower temperature. The afterburner would oxides of nitrogen in the exhaust, readily react in the seem to present a hazard, due to the necessity of having atmosphere in the presence of sunlight to produce Smog high temperature and a flame or spark. The catalytic and irritating conditions. Also, expelled in the exhaust are converter has the drawbacks of back pressure and the aldehydic, ketonic and organic acid type compounds 65 necessary replacement or regeneration of the catalytic ("Nature of Smog' by W. L. Faith in Chemical Engineer pellet or otherwise arranged solid contact material. This ing Progress, 53, 406, August 1957). One of the most is explained by Thomas E. Corrigan in Chemical Engineer smog-afflicted areas is Los Angeles, California. As stated ing, January 1955, page 199; March 1955, page 197, of in Report No. 2 (1954) by the Los Angeles Air Pollution which the following excerpts are of note: “When a gas Foundation, Haagen-Smit shows that exhaust hydrocar 70 phase chemical reaction is promoted by a solid catalyst, bons in the presence of sunlight and nitrogen dioxide, are it has to be accompanied by adsorption. The reactants are 3,642,901 3. 4 adsorbed; the products are formed in an adsorbed con combustion, may also be treated in accordance with the dition and must be desorbed.” . . . "In many reactions present invention. there is a continual deposit upon the surface of the cat If desired, some of the components arising from the alyst which reduced its effectiveness. Even at a constant operation of this invention, can also be trapped and re flow rate the conversion in a flow reactor may continue 5 covered. The trap can be so designed as to take the place to decrease during a run. When the catalyst activity drops of the muffler and provided with a material to aid in the to a certain point it is removed and regenerated.” . . . “A coalescing of the vapor. Such materials may be in the material which vitiates the value of the catalyst is a form of coatings or loose packs or cartridges of water poison. A foreign material in the gas stream may either wettable (lyophillic) materials and hydrocarbon-oil wet combine permanently with the active centers or merely O table (hydrophobic) materials. Examples of lyophillic ma block the pore opening and hinder diffusion.' . . . “A terials include fiber glass, ceramics, pumice and silica gel reaction may be self-poisonous; if the adsorption of the and examples of hydrophobic materials include metallic product is so great that most of the active centers become sulfides, such as iron sulfide, amino or urea resins, and Occupied by product molecules. There would be no room metallic soaps. The incorporation in such a trap of polym for further adsorption of reactant molecules and the reac 5 erization catalysts such as fluorides of aluminum, cobalt, tion would cease.' Zinc and calcium or like metallic fluorides and metallic Of more significant concern, is the resultant increase soaps, such as the resinates or stearates of aluminum, cop of oxides of nitrogen, created by the mandatory use of per, calcium and magnesium, would serve the dual func Secondary air in both the “afterburner' and “oxidation tion of promoting both coalescence and additional polym catalytic converter.” Report No. 2 (1954) by the Los 20 erization capability. The lyophillic and hydrophobic ma Angeles Air Pollution Foundation states: “One of the terials are preferably intimately mixed, as for example: peculiarities of the Los Angeles atmosphere is its high (1) partial silicon-treated pumice, (2) partial silicon oZone content on Smoggy days. Atmospheric ozone meas treated spun glass, (3) a fusion product of pumice, iron urements elsewhere are seldom higher than 10 pphm and sulfide, sodium silicate and borax, (4) incorporation of then only after periods of upper air turbulence. On Smoggy 25 metallic fluorides and metallic soaps in examples (1) or days in Los Angeles, ozone concentrations (strictly speak (2) or (3). Physical aids, including the use of cooling ing, these are oxidant values, determined iodometrically) and sonic effects may also be incorporated as a means range from 30 to 80 pphm and even higher.” for promoting coalescence. The by-product trap recovery As mentioned previously, Haagon-Smit has shown that may be handled in the same manner as crankcase oil the oxidant present in the Los Angeles atmosphere may 30 drainings, either separately or by addition to the crankcase result from the reaction of nitrogen dioxide and certain drainings. The trap must be so constructed as to present hydrocarbons in the presence of sunlight. Experimentally, a large coated contact Surface, as for example a perfo he has duplicated this reaction by reacting 0.4 p.p.m. of rated coated helix or a cartridge containing the lyophyllic nitrogen dioxide with 0.1 to 1.0 p.p.m. of 3-methyl hep and hydrophobic materials. Also to provide cooling and tane in the presence of sunlight reference omitted. A sonic effects, the trap may be jacketed with an arranged similar action results, using olefins. funnel-shaped inlet for on-rushing air or coolant and a Recently haagen-Smit reference omitted reported that complementary outlet at the rear of the jacket. automobile exhausts irradiated with sunlight in the pres Although it is preferable to introduce the catalyst in ence of nitrogen dioxide, both in experienced atmospheric solution with the fuel or gasoline as aforementioned, the concentrations, forms a rubber-cracking oxidant, presum 40 catalyst can also be injected in a liquid state at the car ably ozone. buretor or between the rear of the engine and the muffler, In his book on “Photochemistry of Air Pollution' at which interval catalysis takes place in the vapor state, (Academic Press 1961), Prof. Phillip A. Leighton stresses mainly at a temperature between 700° F. and 300° F. the conversion of nitric oxide to nitric dioxide-a rather The literature and prior art cite many catalysts for toxic Substance, and states that with the expected adoption 45 polymerizing and condensing various organic compounds, of an auto exhaust control device reducing hydrocarbon among which are mentioned unsaturated hydrocarbons, but not nitric oxide emissions, the question arises whether olefins and aldehydes. There is no mention, however, of Such adoption may result in an increase in the nitrogen employing these catalytic principles to inactivate smog dioxide level to make it a real health hazard. forming components of exhausts from internal combus This invention does not necessitate the use of Secondary 50 tion engines. air. and thus, at the outset, lessens the amount of nitrogen For the most desirable means of application, which is oxides that would be formed with the use of an “after dependent on the catalyst being in solution within the burner" or "catalytic converter.” It also does not present fuel, the composition of the catalytic agent was neces the problem of having to contend with back-pressure and sarily so constructed as to enable its effect to take place replacement or regeneration of solid catalysts. continuously in the vapor state, without any appreciable A. principal object of the invention is to provide a cat precipitation of the catalyst in the fuel tank, carburetor alytic composition, which in addition to possessing the and engine. As a supplementary test, such catalytic agent, capabilities of providing catalytic polymerization and con in Solution in a standard grade of gasoline and also with densation, is freely soluble in the fuel or gasoline and a premium leaded gasoline, was subjected to sunlight for readily vaporized therewith to provide a material decrease 60 a period of two months alongside corresponding blanks in the oxides of nitrogen content and the Smog-forming of gasoline. In both grades of gasoline, the catalytically reactivity of the exhaust gases. Such catalyst may be in treated gasoline proved to be clearer with less precipita corporated into the fuel at the refinery, and thus would tion than in the untreated gasolines. This preferred type obviate the disadvantages of installation, inspection and of catalytic composition is herein described for use in enforcement as required with exhaust devices. materially inactivating the smog-forming constituents of A further object of the invention is to conjunctively exhausts from internal combustion engines. treat the engine blowby gases, emitted from crankcase As stated in “The Chemistry of Petroleum Derivatives' breather pipes, by leading and permitting said gaSeS to by Ellis (1934 edition), the introduction of electronega intermingle with the catalyst contained in the catalyzed tive atoms or groups (such as halogen atoms or phenyl engine exhaust. Mechanical appliances have been installed 70 groups) into the olefin hydrocarbon molecule very greatly to draw Slich blowby gases into the carburetor, so as to increases the tendency to polymerization (p. 592). Boron be mixed with the fuel to be combusted. In various cases, fluoride can be substituted for aluminum chloride in it has been reported that such combustion tends to lower Friedel–Crafts synthesis, as well as in other reactions cata engine efficiency; also that the blowby gases tend to foul lyzed by the latter compound, and can be used to effect the carburetor. However, the exhaust, resulting from such 7 Condensation of aromatic hydrocarbons with aliphatic 3,642,901 5 6 chlorides and the addition of hydrogen halides to olefins (C) In reactions such as (p. 596). The conversion of the olefins to high molecular weight oils capable of being utilized as lubricants, by (1) Alkylations of aromatic hydrocarbons and of phenols polymerization under the influence of aluminum chloride with olefins and alcohols. or boron trifluoride, is an interesting development in the 5 (2) Cyclizing of natural and synthetic elastomers.' application of the olefins (p. 613). Since boron fluoride is a gas which readily decomposes with moisture and is By reacting boron trifluoride ethyl ether complex or like difficult to handle because of its corrosive and poisonous ether complex with certain nitrogenous or amino organic nature, double compounds can be substituted for it in compounds, I have obtained a type of derivative that is various reactions. Landolph used the ethereal liquid con 10 soluble in the fuel or gasoline and in liquid aliphatic hy densate of ethylene and boron fluoride (ethylene fluoboric drocarbons, and which is capable of acting as a polym acid) with camphor. A double compound of ether and erization and condensation catalyst. This type of com boron fluoride has been employed to condense Saturated pound, designated herein as "Type A,” in liquid form, compounds with olefins (p. 597). Catalysts, such as anhy was found useful for directly treating the engine exhaust drous metallic halides and aryldiazonium fluoroborates to decrease its deleterious reactivity, and preferably by promote the polymerization of styrene (p. 611). injecting the “Type A” compound between the rear of the Various organic complexes of boron trifluoride, (which engine and the muffler. Although “Type A' compound is may also serve as a source of material for practicing this Soluble in gasoline and aliphatic hydrocarbons, it was invention), have been made commercially available as found that when introduced into solution in the fuel for listed below: 20 indirectly treating the exhaust, a perceptible precipitation occurs on carburetion which will eventually foul the car Boron trifluoride ethyl ether complex buretor. Boron fluoride di-n-butyl-etherate For treating the exhaust indirectly, i.e., where the cat Boron fluoride ethyl Cellosolve (boron fluoride ethylene alyst is used in solution with the fuel, I have employed a glycol monoethyl ether) type of compound which possesses the properties of being Boron trifluoride phenol-polyethylene glycol complex soluble in gasoline and in aliphatic hydrocarbons and has Boron trifluoride, phenol complex the capability of inhibiting precipitous depositary action Boron fluoride p-cresol in the carburetor or the engine. This composition, herein Boron fluoride dihydrate designated as "Type B,' consists of the “Type A' nitrog Boron fluoride monohydrate 30 enous boron fluoride either complex in admixture with Boron fluoride di-acetic-acid an alkyl or aryl compound, bearing an inorganic negative Boron fluoride complexes with nitrogenous compounds to radical. In addition to being capable of maintaining solu include: bility of the end product in the fuel and of inhibiting pre Boron fluoride piperidine cipitous deposition, the alkyl or aryl compound, bearing Boron trifluoride monoethylamine complex an inorganic negative radical, was found to have the ca Boron trifluoride triethanolamine complex pacity of combining with any of the amine that might be Boron fluoride urea present as such in the “Type A' composition. Boron fluoride hexamethylene tetramine. The requirement of complete solubility of the end prod uct catalyst in the fuel and in liquid aliphatic hydrocar Also, made available are publications of numerous 40 bons proved to be a primary means for selecting a suitable abstractive references, relative to organic complexes of alkyl or aryl compound, bearing an inorganic negative boron trifluoride. Yet nowhere in these several hundred radical. For example, although diethyl sulfate is an alkyl references or elsewhere is there any mention of their ap compound, bearing an inorganic negative radical, the plication to inactivating and treating internal combustion product of the admixture of diethyl sulfate with the “Type engine gases, and particularly as herein set forth. A” compound, when added to gasoline, was found to give Of specific significance, as a source of material for per 45 an unstable turbid solution and therefore was inadequate forming this new process, is boron trifluoride ethyl ether for making the “Type B' compound. complex, BF(CH5)2O, to which is ascribed the follow Both 'A' and “B” types, in the methods attributed ing in the General Chemical Division data sheet: thereto, provide for continuous introduction of a vapor “Boron Trifluoride Etherate, with approximately 48% forming catalyst in intimate gaseous admixture with the Boron Trifluoride content, is a liquid at room tempera 50 exhaust gas flow from the engine. In addition to being ture, and represents a convenient way of dispensing or directly added to the fuel, the “Type B' compound can using Boron Trifluoride etherate as a catalyst or as a raw also be used for injection between the rear of the engine material for chemical reactions.” and the muffler, and thus may serve as a general catalyst In general, the uses of Boron Trifluoride Etherate are 55 agent for the purpose of this invention. similar to those of Boron Trifluoride gas; however, in some Although Boron Fluoride Di-n-butyletherate or Boron cases it may perform while the gas would not and vice Fluoride Ethyl “Cellosolve' (Boron Fluoride Ethylene versa. Some uses of the Etherate (from literature, patents Glycol Monoethyl Ether) or Landolph's ethereal liquid and trade reports) are: s condensate of ethylene and boron fluoride with camphor (A) For Polymerization (or Copolymerization), includ 60 or a complex of boron fluoride and an ether amine may ing those of: be used instead of Boron Trifluoride Ethyl Ether Com (1) Olefins and di-olefins. plex in the preparation of the “A” and “B” type com (2) Styrene or derivatives with various unsaturated com pounds, the factors of availability and economy make it pounds. more practical to use of Boron Trifluoride Ethyl Ether (3) Heterocyclic organic unsaturates (indene, coumarone, 65 Complex as the main catalyst source for practicing this etc.) invention. (4) Unsaturated acids and esters. In my investigation of suitable nitrogenous organic (5) Terpenes and homologs. compounds for combination with Boron Trifluoride Ethyl 70 Ether Complex or the like, to give a Type A or a Type (B) In the preparation of: B product, which is soluble in the gasoline and in liquid aliphatic hydrocarbons, I have found that the water solu (1) Esters ble nitrogenous compounds, such as the water soluble (2) Steroids amines, were unsuitable, and that only certain types of (3) Synthetic resins. 75 water-insoluble amines fulfilled such requirement. Suit 3,642,901 7 8 able amines of this nature were found among the aliphatic The following examples are given for producing the and aromatic types, namely the following: composition of matter of this invention, herein referred Tertiary-alkyl primary amines (R3C-NH2), containing to as "Type A' and "Type B' compounds and designated at least nine carbon atoms, such as t-Nonylamine and with the numeral, following the alphabetic letter. 5 those commercially available under the trade names of EXAMPLE A-1 “Primene 81-R' to designate a Parts by volume Boron trifluoride di-ethyl ether complex (approxi composition and “Primene JM-T' to designate a mately 48% boron trifluoride content) ------100 t-C18H3NH2 to C2a HapNH2 composition. O t-C12H25NH2 to t-C15H3NH2 (Primene 81-R) ----- 200 Primary alky1 aryl amines, wherein the alkyl radical com The reaction vessel is preferably fitted with a reflux con position is large enough to render requisite solubility denser and cooling coil. The ether complex is first intro of the end product in gasoline and in liquid aliphatic duced and cooled to a temperature of approximately 50 hydrocarbons, and including Dodecylaniline, which is F. the "Primene 81-R’ is slowly added with stirring and commercially available as a technical grade, termed cooling, so that the temperature of the reaction preferably "Alkylaniline C-21.' does not exceed 80 F. Ethyl ether is evolved and is re The requirement that the organic nitrogenous deriva tained in the reaction vessel as a diluent component of Ex tive of the boron fluoride ether complex give a clear or ample A-1. Stirring is continued for approximately one stable solution in gasoline and in liquid aliphatic hydro hour after completion of the amine addition. carbons, as demanded in adding the catalyst to the fuel, proved to be a marked differentiating factor for deter EXAMPLE A-2 mining the proper organic nitrogenous compounds. This Parts by volume is demonstrated by the large number of nitrogenous Or Boron trifluoride di-ethyl ether complex ------. 100 ganic compounds, which could not meet this test, although t-C18H3NH2 to t-C24H49NH (Primene JM-T) - - - - 280 on the water-insoluble side. The following organic nitro Same procedure as in Example A-1. Ethyl ether is evolved genous compounds showed this inadequacy of not being and retained as a diluent component. able to render a derivative of the boron fluoride ether complex, which would give a clear or stable solution in EXAMPLE A-3 gasoline and aliphatic hydrocarbons: 30 Parts by volume Aniline, diethylaniline, primary t-butyl amines, primary Boron trifluoride di-ethyl ether complex ------100 t-octyl amine, dicyclohexylamine, diamylamine, octyl Tertiary nonylamine ------200 amine, tetradecylamine, decylamine, rosin amine, coco Same procedure as in Example A-1. Ethyl ether is evolved amine, soy amine, octadecylamine, hexadecylamine, 2 and retained as a diluent component. methyl-5-ethyl pyridine, ortho toluidine, 2,4-lutidine (dimethyl pyridine), secondary C16 to C18 fatty amines, EXAMPLE A-4 N-di-secondary-butyl-p-phenylene diamine and triallyl Parts by volume amine. Boron trifluoride di-ethyl ether complex ------100 Dodecylaniline (Alkylaniline C-21) ------as - up - 28O Triamylamine, dodecylamine and tallow amine deriva tives of boron fluoride ether complexes were border line 40 Same procedure as in Example A-1. Ethyl ether is evolved cases, but proved unsuitable because of their inability to and retained as a diluent component. stay in Solution in the fuel. EXAMPLE A-5 Also, the following available boron fluoride nitrogenous Parts by volume compounds could not meet this requirement of Solubility 45 Boron fluoride di-N-butyl ether complex (approxi and did not give a clear or stable solution in gasoline mately 34% boron trifluoride content) ------140 and aliphatic hydrocarbons: t-C12H25NH to t-C15H3NH2 (“Primene 81-R”) --- 200 Boron fluoride piperidine, boron trifluoride monoethyl Same procedure as in Example A-1. Di-N-butyl ether is amine complex, boron trifluoride triethanolamine con evolved and retained as a diluent component. The tem plex, boron fluoride urea, boron fluoride hexamethyl 50 perature is kept approximately the same as in Example ene tetramine. A-1 to prevent excessive fuming, although the boiling Although it is preferable, if injection is to be made at point of di-N-butyl ether is much higher than that of the rear of the engine, to employ the fuel soluble deriva ethyl ether. tives, i.e., “Type A" or “Type B' compounds, the require EXAMPLE A-6 ment of solubility is not so necessary here. The boron Parts by volume trifluoride etherate itself or its reaction products with Boron fluoride di-N-butyl ether complex ------140 other amines such as referred herein as unsuitable for t-C18H3NH2 to t-C2H49NH2 ("Primene JM-T) --- 300 making “TypeA' or “Type B' compounds, can be added directly to the exhaust gases. The resultant compounds, Same procedure as in Example A-5. Di-N-butyl ether is or the above listed boron fluoride nitrogenous compounds 60 evolved and retained as a diluent component. or the other herein listed boron fluoride compounds, could be injected in conjunction with an additive or Solvent, EXAMPLE A-7 when so required. Parts by volume For making “Type B' compounds, suitable alkyl and Boron fluoride di-butyl ether complex ------140 aryl compounds bearing an inorganic radical were found 65 Tertiary nonylamine ------'m as ran a a as - a was 200 to be as follows: Same procedure as in Example A-5. Di-N-butyl ether is Chlorinated hydrocarbons, e.g., perchloroethylene, tri evolved and retained as a diluent component. chlorobenzene, 2 ethyl hexyl chloride, chloroform, tri EXAMPLE A-8 chloropropane, methylene chloride, ethylene dichlo 70 Parts by volume ride, trichloroethylene, butyl chloride, monochloroto Boron fluoride di-N-butyl ether complex ------40 uene, monochlorobenzene and orthodichloro benzol; ethylene chlorhydrin; carbon tetrachloride, dichloro Dodecylaniline ("Alkylaniline C-21") ------300 ethyl ether; nitro benzol; triphenyl phosphite; triethyl Same procedure as in Example A-5. Di-N-butyl ether is phosphate; benzo-trifluoride, and tricresyl phosphate. evolved and retained as a diluent component. 3,642,901 9 10 EXAMPLE A-9 Corresponding products to those obtained in Examples Parts by volume B-1 to B-7 inclusive are obtained by substituting in each Boron fluoride ethylene glycol monoethyl ether com individual case for the "Product of Example A-1,” any plex (termed boron fluoride "Cellosolve' Com of the corresponding end products, shown under Examples plex) (approximately 43% boron trifluoride con A-2 through A-12 respectively. tent.) ------' - a - as as see see or ever as 112 In making “Type A' compounds by the interaction of t-C12H2NH2 to t-C15H3NH2 (“Primene 81-R”) --- 200 a boron fluoride ether complex with a suitable amine, Same procedure as in Example A-5. Ethylene glycol mon an ether is broken loose from the boron fluoride ether oethyl ether is evolved and retained as a diluent com complex and replaced by the amine, which had been ponent. O reacted with said complex, as illustrated by the following EXAMPLE A-10 equations: Parts by volume Boron fluoride ethylene glycol monoethyl ether com- 112 plex ------t-CH3NH2 to t-C2H4NH. ("Primene JM-T") --- 300 5 Same procedure as in Example A-5. Ethylene glycol monoethyl ether is evolved and retained as a diluent In making the "Type B" compound, wherein the product Component. of "Type A" is admixed with an alkyl or aryl compound, EXAMPLE A-11 20 bearing an inorganic radical, any available uncombined Parts by volume amine that might be present of the “Type A com Boron fluoride ethylene glycol monoethyl ether com pound is combined with or taken up by a requisite amount plex ------12 of Said alkyl or aryl compound to leave the balance of Tertiary nonyl amine ------200 inorganic alkyl or aryl compound as a component of the Same procedure as in Example A-5. Ethylene glycol 25 "Type B' compound. monoethyl ether is evolved and retained as a diluent com The proportion of percentage of the additive which may ponent. be used with relation to the fuel will depend upon the type EXAMPLE A-12 of internal combustion engine and the degree of polym Parts by volume erization and condensation capability which is desired. Boron fluoride ethylene glycol monoethyl ether com 30 Although the percentage of additive for automobiles would plex ------112 generally come within the range of 0.1% to 1.0% by Dodecylaniline ------300 Weight of the fuel the catalyst may be used within the Same procedure as in Example A-5. Ethylene glycol broad range of 0.01% to 5% by weight of the fuel to monoethyl ether is evolved and retained as a diluent com cover all types of internal combustion engines and degrees ponent. 35 of catalytic effect. EXAMPLE B-1 One method for determining the increase in molecular Parts by volume Structure, to show inactivation of the exhaust, consisted Product of Example A-1 ------140 in analyzing the exhausts from various engine runs ac Perchlorethylene ------60 cording to the following procedure: 40 The engine was first warmed by running the car for Mixed at ordinary temperatures for a period of about a period of 15 minutes and then turned off. Immediately one hour under reflux condenser. thereafter, a tight fitting attachment was made to the EXAMPLE B-2 end of the exhaust pipe, consisting of a filterable trap, Parts by volume to which Was attached a condenser with ice water as the Product of Example A-1 ------as see - arra 140 45 coolant. Trichlorobenzene ------60 The engine was then started and run at idling speed Procedure as in Example B-1. for 20 minutes. At the end of this interval, the trap was disconnected and the contents thereof washed with water EXAMPLE B-3 to remove and recover adherent sediment and oily mate Parts by volume 50 rial. These Washings were acidified with sulfuric acid and Product of Example A-1------140 titrated with a 0.1% aqueous solution of potassium Ethylene chlorhydrin ------60 permanganate, Procedure as in Example B-1. The condensate from the cooled condenser was also acidified with sulfuric acid and titrated with 0.1% aqueous EXAMPLE B-4 5 potassium permanganate solution. Parts by volume An average of the various runs gave the following Product of Example A-1 ------140 results: Benzotrifluoride ------60 Without addition of catalyst, the Washings from the Procedure as in Example B-1. trap alone required an average of 80 cc. of the perman EXAMPLE B-5 50 ganate Solution, while the corresponding condensate re W Parts by volume quired an average of 46 cc. Product of Example A-1 ------me a gas 200 With addition of catalyst, the washings from the trap Triphenyl phosphite ------60 alone required an average of 115 cc. of the potassium permanganate Solution, while the corresponding conden Procedure as in Example B-1. 65 sate required 11 cc. EXAMPLE B-6 The increased potassium permanganate consumption Parts by volume of the treated trap washings, relative to the untreated Product of Example A-1 ------120 trap washings, demonstrated that an increase in particle Triethyl phosphate ------8O size or molecular structure of the unsaturated or olefinic EXAMPLE B-7 O hydrocarbons had taken place to enable trap retention. Parts by volume By taking the aforesaid figures of 115 cc. plus 11 cc. or Product of Example A-1 ------as ame as an as aw 140 those of 80 cc. plus 46 cc. as the total of 126 to represent 2-ethylhexyl chloride ------60 the available unsaturates in the untreated exhaust, the Procedure as in Example B-1. 75 percentage thereof retained in the trap, because of in 3,642,901 11 12 crease in particle size or molecular structure, would be In the preferred method for practicing this invention equivalent to with the “Type B" compound as an additive to an ali 115X100 phatic hydrocarbon motor fuel, complete solubility of the additive therein to provide a stable solution constitutes 126 5 the primary requirement for the motor fuel to function or 91.3%. properly. I have found that boron trifluoride etherates It may be noted that approximately 80% of the or the other fluoride compounds herein shown, other than reducible substances, recovered from the trap alone, as the “Type A' and “Type B' compounds, in solution with aforestated, is oil soluble or oil extractable. The remaind a solvent, will separate when the solvent solution is added er is somewhat water-soluble or water-miscible. O to gasoline or aliphatic hydrocarbons. To further demonstrate inactivation in the exhaust BF (CH)2O is soluble in isopropyl alcohol and gaso omission, additional tests, with and without the catalytic line is also soluble in isopropyl alcohol. Isopropyl alcohol additive, were made as follows: can, therefore, be termed “a gasoline-soluble solvent.” To insure adequate distribution, the catalyst was added However, when the isopropyl alcohol solution of boron in the proportion of 0.5%, relative to the fuel. trifluoride etherate is mixed with the isopropyl alcohol : The automobile was placed on a Clayton dynamome solution of gasoline, the boron trifluoride etherate sepa ter. Samples were then taken by collecting the automobile rates from the resultant mixture. It would, therefore, be exhaust gases produced in a large plastic bag, as the impractical to add a mixture of gasoline with an isopropyl automobile was driven through the seven modes of opera alcohol solution of boron trifluoride etherate to a storage tion, specified in the California Motor Vehicle Pollution 20 tank. This was demonstrated by comparison tests in which Control Board sampling method, to simulate the inertia isopropyl alcohol solutions of BF3(C2H5)2O were added of the moving car at rates up to 50 miles per hour, so to gasoline and a "Type B' compound was added in gaso as to cover cruising, acceleration, deceleration and idling. line at the same concentrations. The “Type B" compound This produced two integrated samples, with and without used for this comparison is that shown in “Example B-5' the additive, which were then returned to the laboratory as the derivative obtained from the admixture of Tri for analysis. Separate samples were taken for the oxides phenylphosphite with the reaction product of of nitrogen determinations. BF (C2H5) 20 and the t-C12H2NH2 to t-C5H3NH2 Total saturated hydrocarbons were determined with a non-dispersive infrared instrument, in accordance with commercial tertiary primary amine reagent. the California Motor Vehicle Pollution Control Board 30 Both 5% and 50% by weight solutions of MF (C2H5)2O method. in isopropyl alcohol gave clear stable solutions. Similarly, A Perkin-Elmer model 154B gas chromatograph was 5% and 50% by weight solutions of the “Type B' com used to determine the distribution of hydrocarbons from pound in gasoline as the solvent gave clear stable solutions. C and C6 using a dimethylsufolane column at 30° C. When the 5% by weight boron trifluoride etherate The carbon dioxide, oxygen, and carbon monoxide isopropyl alcohol solution was added to gasoline in an concentrations in the exhaust gas were determined by the amount of 0.02% by weight of the gasoline, which is Orsat gas absorption method. equivalent to 0.00001% by weight of BF3(C2H5)2O, a Oxides of nitrogen were determined by the phenoldi turbid dispersion results which on immediate shaking Sulfonic acid colorimetric method of analysis. causes an adherent deposit to form on the side of the 40 bottle. After 24 hours, a film is also deposited on the sides The results are summarized in the following tables: of the bottle. Shaking with additional gasoline does not remove or solubilize the deposit or the film. Without With When the 5% by weight boron trifluoride etherate additive additive isopropyl alcohol solution is added to gasoline in an Carbon dioxide, percent------10.9 12.0 Carbon monoxide, percent- 1. 1.6 amount of 2.5% by weight, which is equivalent to Oxygen, percent------4.4 2.3 45 0.0012.5% by weight of BFs(C2H5)2O, a heavier turbid Oxides of nitrogen, p.p.m.------1,820 1,290 Nondispersive infrared: saturated hydrocar dispersion is formed and immediate shaking causes a bons, p.p.m.------337 437 heavier adherent deposit to form on the bottom of the Gas chromatographic analysis: total C-Co hydrocarbons, p.p.m.------380 325 bottle. On standing for 2 hours, the dispersed The total hydrocarbon emission showed the engine to settles out and after 24 hours, a film is deposited on sides be in excellent running condition and thus makes the of the bottle in addition to the residue and precipitated differentiating factors predominant. etherate. Shaking with additional gasoline does not remove Road tests, wherein the catalyst was added as 0.1% or solubilize the film or the adherent residue or the of the fuel, showed such additive to give better running 5 5 precipitated etherate. performance with an average of 20% increase in mileage When the 5% by weight BF (CH5)2O-isopropyl alco per gallon of gasoline, as compared to road tests without hol solution is added to gasoline in an amount of 50% the additive in the fuel. This result is substantiated by by weight, which is equivalent to 0.0025% by weight of the above analyses for carbon dioxide, carbon monoxide BF (C2H5)2O, a heavy turbid dispersion is formed and and oxygen as demonstrating better combustion with the 60 the dispersed etherate settles out within 2 hours. After catalytic additive. 24 hours, a film is deposited on the sides of the bottle An interpretation of the above tabulated comparative and in addition to the precipitated etherate, an adherent results disclosed that the additive caused a 45% increase residue appears on the bottom of the bottle. Shaking with in carbon monoxide and a 29% decrease in oxides of additional gasoline does not remove or solubilize the film, nitrogen. These two factors indicate that the additive pro the residue or the precipitated etherate. duced a change in the specific gravity of the hydrocarbons When the 50% by weight boron trifluoride etherate to effect a fuel-air ratio change. Also, the additive caused isopropyl alcohol solution is added to gasoline in the pro a 13% increase of the saturated hydrocarbon, as shown portion of 0.02% by weight, which is equivalent to with the nondispersive infrared analyzer, and a 14% re 0.0001% by weight of BF (C2H5)2O, a turbid dispersion duction of the C-C6 hydrocarbons, as measured by gas 70 is formed and some settling takes place. The chromatograph. The latter two results disclose that a change in the hydrocarbon type had taken place and support the findings of the aforestated potassium perman settles out within one hour and after 24 hours, a film is ganate tests to denote increase in molecular structure of deposited on the sides of the bottle and an adherent the unsaturated hydrocarbons with the use of the additive. residue appears with the precipitated etherate on the bot 3,642,901 13 14 tom of the bottle. Shaking with additional gasoline does In blank tests using isopropyl alcohol in gasoline in not remove or solubilize the film, the residue or said the same concentrations employed in the above tests there etherate. was no film, no settling and no residual deposit. When the 50% by weight boron trifluoride etherate Having fully defined my invention in the foregoing isopropyl alcohol solution is added to gasoline in an specification, I desire to be limited only by the lawful amount of 2.5% by weight, which is equivalent to 0.0125% scope of the following claims, as interpreted according to by weight of BF (C2H5)2O, the BF3(C2H5)2O settles to the spirit and purpose of my invention. the bottom and after being shaken, a turbid dispersion I claim: of the etherate takes place and then immediately settles 1. The product produced by reacting a boron trifluoride out. After 24 hours, a film is deposited on the sides of the O etherate selected from the group consisting of a boron bottle and an adherent residue appears with the settled trifluoride-diethyl ether complex, a boron trifluoride-di-N- etherate on the bottom of the bottle. Shaking with addi butyl ether complex, a boron trifluoride-ethylene glycol tional gasoline does not remove or solubilize the film, the monoethyl ether complex or an ethereal liquid condensate residue or said etherate. of ethylene and boron trifluoride with comphor with a When the 50% by weight boron trifluoride etherate 5 tertiary alkyl primary amine containing from 9 to 24 car isopropyl alcohol solution is added to gasoline in an bon atoms or dodecyl aniline, the ether group being dis amount of 5% by weight, which is equivalent to 0.025% placed from said etherate in the formation of said by weight of BFs(C2H5)2O, the BF (C2H5)2O immediately product. settles to the bottom and after being shaken, the etherate 2. The composition of claim 1 wherein said primary again settles out immediately. There was no turbidity or 20 amine is tertiary nonyl amine. adherent residue and after 24 hours, the etherate still 3. The composition of claim 1 wherein said primary remained separated with no turbidity or adherent residue. amine is a mixture of t-C12H25NH2 to t-C15H3NH2. Shaking with additional gasoline causes residual deposits aIeS. on the sides and bottom of the bottle and does not remove 4. The composition of claim 1 wherein said primary or solubilize the etherate. amine is a mixture of t-CH3NH2 to t-CHNH In comparsion, tests using a 5% by weight solution and amines. a 50% by weight solution of the “Type H” compound References Cited in gasoline alone as the solvent, additions of the solutions were made to gasoline in the same concentrations em UNITED STATES PATENTS ployed in the above tests, i.e., 0.02, 2.5, and 50% of the 30 2,751,285 6/1956 Bartleson ------44-76 5% and the 50% solutions in the gasoline. In all of these 3,037,985 6/1962 Lang et al. ------44-72 X tests, the "Type B' compound formed a clear stable solu tion in the gasoline and there was no film formation, no CHARLES B. PARKER, Primary Examiner settling of the "Type B" compound and no residual deposit R. L. RAYMOND, Assistant Examiner was formed. 35 In a blank test using gasoline alone, there was no film, U.S. C. X.R. no settling and no residual deposit. 44-72, 76; 252-182; 260-579