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United States Patent Office Patented Jan 3,017,356 United States Patent Office Patented Jan. 16, 1962 1. 2 rated aliphatic radical, a cycloaliphatic radical, an aryl 3,017,356 radical, an aralkyl radical, an alkaryl radical, an alkoxy WillianPROCESS B. Hughes, OF andINHIBITING Verner L. Stronberg,CORROSION Webster alkyl radical, an aryloxyalkyl radical, and the like; and Groves, Mo., assignor's to Petroite Corporation, Wii A is an alkylene group; for example, ethylene and propyl mington, Del, a corporation of Delaware ene radicals, such as No Drawing. Original application Mar. 3, 1958, Ser. No. 718,391 Divided and this application Nov. 23, 1959, Ser. No. 854,553 -CH2CH2CH 15 Claims. (C. 252-8.55) CH-CH2 O B This application is a division of Serial No. 718,391, CHs filed March 3, 1958. This invention relates to esters of cyclic amidines of -CH-CH-CH,- the formula gh, CHis O 15 -bH-bH In general, the amidine esters are prepared by reacts o-o-c- ing a hydroxyaliphatic cyclic amidine ()-ROH with less where (A) and (B) are cyclic amidine-containing radicals, than a stoichiometric amount of a polycarboxylic acid to for example, imidazoline and tetrahydropyrimidine radi form a half ester cals (hereafter referred to as “amidine esters'). More 20 particularly, this invention relates to esters wherein. A contains one type of cyclic amidine ring and B contains (a)-R-O C-Z-COH the same or another type not selected in A. This inven which is subsequently reacted with an amidine forming tion also relates to a process of preparing these com polyamine to form the amidine ester pounds which comprises reacting a hydroxy-containing 25 O cyclic amidine with less than a stoichiometric amount of a polycarboxylic acid to form a partial ester and then re Q-R-O-)-2- acting this partial ester with a polyamine capable of form More specifically, the corrosion inhibiting aspect of this ing a second amidine ring of the same or different type. invention relates to a method for inhibiting corrosion of This invention also relates to using these compounds as 30 ferrous metals by hydrocarbon fluids containing water corrosion inhibitors in preventing the corrosion of metals, and corrosive materials such as H2S, CO2, inorganic acids, most particularly steel and ferrous metals. organic acids, etc., combinations of these materials with Heretofore, a wide variety of cyclic amidine com each other, combinations of each of said corrosive ma pounds have been employed to inhibit the corrosion of terials with oxygen, and combinations of said materials oil well equipment. Although we had expected that hy 35 with each other and oxygen, which comprises adding to droxyaliphatic cyclic amidines would also be effective in said fluids at least 5 parts per million of the above inhibiting oil field corrosion, we found that these com amidine esters, said compounds being sufficiently soluble pounds had very poor corrosion inhibiting properties. in the hydrocarbon fluid to inhibit corrosion. However, we have now unexpectedly discovered that THE HYDROXY CYCLIC AMIDINE the derivatives of these hydroxyaliphatic cyclic amidines, 40 The expression "cyclic amidines” is employed in its particularly the amidine esters thereof, are very effec usual sense to indicate ring compounds in which there are tive corrosion inhibitors, in many cases 10 or more times present either 5 members or 6 members, and having 2 as effective as the corresponding hydroxyaliphatic cyclic nitrogen atoms separated by a single carbon atom sup amidine. - 45 plemented by either two additional carbon atoms or three More specifically, in the above formula A and B con additional carbon atoms completing the ring. All the tain either imidazoles or tetrahydropyrimidine radicals, carbon atoms may be substituted. In the present in for example, the following radicals stance, the nitrogen atom of the ring involving two mono (1) valent linkages is substituted with a hydroxy-containing 50 grOllp. These cyclic amidines are further characterized as be ing substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally (2) bonded to a hydrocarbon radical or comparable radical 55 derived from an acid, such as a low molal fatty acid, a high molal fatty acid, or comparable acids, polycarboxy acids, and the like. For details of the preparation of imidazolines substi tuted in the 2-position from amines, see the following 60 U.S. patents, U.S. No. 1,999,989, dated April 30, 1935, Max Bockmuhl et al.; U.S. No. 2,155,877, dated April 25, 1939, Edmund Waldmann et al.; and U.S. No. 2,155,878, dated April 25, 1939, Edmund Waldmann et in which al. Also see Chem. Rev. 32, 47 (43), and Chem. Rev. 65 54,593 (54). Equally suitable for use in preparing compounds of and =C-R-C-F are the residual radicals derived from our invention and for the preparation of tetrahydro the carboxylic acids; pyrimidines substituted in the 2-position are the poly amines containing at least one primary amino group and O g R-C-OH R=(C-OH)2 70 at least one secondary amino group, or another primary where R comprises, for example, a saturated or unsatu amino group separated from the first primary amino group by three carbon atoms instead of being separated 8,017,356 3 4. by only 2 carbons as with imidazolines. This reaction, acids, the hydroxy stearic acids, the hydroxyoctadecenoic as in the case of the imidazolines, is generally carried acids, for example, ricinoleic acid, ricinelardic acid, hy out by heating the reactants to a temperature at which 2 droxyoctadecynoic acids, for example, ricinstearolic acid, moles of water are evolved and ring closure is effected. the hydroxyeicosanoic acids, for example, hydroxy For details of the preparation of tetrahydropyrimidines, arachidic acid, the hydroxydocosanoic acids, for example, see German Patent No. 700,371, dated December 18, hydroxybehenic acid, and the like. 1940, to Edmund Waldmann and August Chwala; Ger Examples of acetylated hydroxyacids comprise ricin man Patent No. 701,322, dated January 14, 1941, to Kark oley lactic acid, acetyl ricinoleic acid, chloroacetyl Kiescher, Ernst Urech and Willi Klarer, and U.S. Patent ricinoleic acid, and the like. No. 2,194,419, dated March 19, 1940, to August Chwala. 0. Examples of the cyclic aliphatic carboxylic acids com Substituted imidazolines and tetrahydropyrimidines are prise those found in petroleum called naphthenic acids, obtained from a variety of acids beginning with the one hydrocarpic and chaulmoogric acids, cyclopentane car carbon acid (formic) through and including higher fatty boxylic acids, cyclohexanecarboxylic acid, campholic acid, acids or the equivalent having as many as 32 carbon fencholic acids, and the like. atoms. Modified fatty acids also can be employed as, for 5 Examples of aromatic monocarboxylic acids comprise example, phenyl stearic acid or the like. Cyclic acids may benzoic acid, substituted benzoic acids, for example, the be employed, including naphthenic acids. A variety of toluic acids, the xyleneic acids, alkoxybenzoic acid, phenyl other acids including benzoic acid, substituted benzoic benzoic acid, naphthalene carboxylic acid, and the like. acid, salicyclic acid, and the like, have been employed to Mixed higher fatty acids derived from animal or vege 20 table sources, for example, lard, cocoanut oil, rapeseed oil, furnish the residue sesame oil, palm kernel oil, palm oil, olive oil, corn oil, RC cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish from the acid RCOOH in which the C of the residue oils, teaseed oil, partially or completely hydrogenated ani 25 mal and vegetable oils are advantageously employed. Ré Fatty and similar acids include those derived from various is part of the ring. The fatty acids employed, for example, waxes, such as beeswax, spermaceti, montan wax, Japan may be saturated or unsaturated. They may be hydroxyl wax, coccerin and carnauba wax. Such acids include ated or nonhydroxylated. Branched long chain fatty acids carnaubic acid, cerotic acid, lacceric acid, montanic acid, may be employed. See J. Am. Chem. Soc. 74, 2523 30 psyllastearic acid, etc. One may also employ higher mo (1952). This applies also to the lower molecular weight lecular weight carboxylic acids derived by oxidation and acids as well. other methods, such as from paraffin wax, petroleum and Among sources of such acids may be mentioned straight similar hydrocarbons; resinic and hydroaromatic acids, chain and branched chain, saturated and unsaturated, such as hexahydrobenzoic acid, hydrogenated naphthoic, aliphatic, cycloaliphatic, aromatic, hydroaromatic, aralkyl 35 hydrogenated carboxy diphenyl, naphthenic, and abietic acids, etc. acid, aralkyl and aromatic acids, such as Twitchell fatty Examples of saturated aliphatic monocarboxylic acids acids, naphthoic acid, carboxydiphenylpyridine carboxylic comprise: acetic, propionic, butyric, valeric, caproic, acid, blown oils, blown oil fatty acids and the like. heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, Other suitable acids include phenylstearic acid, ben tridecanoic, myriatic, pentadecanoic, palmitic, hepta 40 Zoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, decanoic, Stearic, nonadecanoic, eicosanoic, heneicon chlorostearic acid, etc. sanoic, docosanoic, tricosanoic, tetracosanoic, pentaco Examples of the polycarboxylic acids comprises those sanoic, cerotic, heptacosanoic, montanic, nonacosanoic, of the aliphatic series, for example, oxalic, malonic, suc melissic and the like. cinic, glutaric, adipic, pimelic,
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