United States Patent Office Patented June 6, 1961

2,987,515 United States Patent Office Patented June 6, 1961

2,987,515 (4) URETHANES Verner L. Stromberg, Shrewsbury, and William B. Hughes, Webster Groves, Mo., assignors to Petrolite Corporation, Wilmington, Del, a corporation of Dela Ware No Drawing. Filed Feb. 3, 1958, Ser. No. 712,662 W 17 Claims. (C. 260-256.4) 2 NCA. This invention relates to urethanes of hydroxy-ali 0 phatic cyclic amidines and more particularly to the di (The dotted lines indicate the undetermined structure, urethanes of imidazolines and tetrahydropyrimides. This probably polymeric) in which invention also relates to a process of preparing these com pounds which comprises reacting a hydroxyaliphatic cyclic amidine, for example, a hydroxyaliphatic imadazoline or 5 are the residual radicals derived from the carboxylic tetrahydropyrimidine with an organic isocyanate, but acids preferably an organic diisocyanate. This invention also relates to a process of using these urethanes as corrosive inhibitors in preventing the corrosion of metals, most R-COH or R=(COH) particularly iron, steel and ferrous alloys. 20 where R comprises, for example, a saturated or unsatu Heretofore, a wide variety of cyclic amidine com rated aliphatic radical, a cycloaliphatic radical, an aryl pounds have been employed to inhibit the corrosion of radical, an aralkyl radical, an alkaryl radical, an alkoxy oil well equipment. Although we had expected that alkyl radical, an aryloxyalkyl radical, and the like, and hydroxyaliphatic cyclic amidines would also be very ef A is an alkylene group, for example, ethylene and propyl fective in inhibiting oil field corrosion, we found that 25 ene radicals, or substituted derivatives thereof, such as these compounds had very poor corrosion inhibiting prop -CH-CH- CHCHCH- CFI-CH erties. However, we have now unexpectedly discovered that Hs the derivatives of these hydroxyaliphatic cyclic amidines, (H, CH (H, particularly the diurethane derivatives thereof, are very 30 -CH-CH-CH- -bH-CH effective corrosion inhibitors, in many cases from 10-15 and R is the urethane product of the reaction of a hy or more times as effective as the corresponding hydroxy droxy-containing alkylene, polyoxyalkylene, etc., groups aliphatic cyclic amidine. with an isocyanate. The corrosion inhibitors disclosed herein are particu More specifically, the corrosion inhibiting aspect of larly useful in preventing the corrosion of oil equipment, 35 this invention relates to a method for inhibiting corrosion for example, in producing wells, pipe lines, refineries, of ferrous metals by hydrocarbon fluids containing water tank storage, etc., which are in contact with corrosive oil and corrosive materials such as H2S, CO2, inorganic containing medium, for example, in oil wells producing acids, organic acids, etc., combinations of these materials corrosive oil or oil-brine mixtures in refineries, and the with each other, combinations of each of said corrosive like. These compositions possess properties which impart 40 materials with oxygen, and combinations of said ma to metals resistance to attack by a wide variety of corro terials with each other and oxygen, which comprises sive agents, among which may be mentioned brines, or treating ferrous metals such as by adding to said fluids ganic and inorganic acids, CO2, H2O, Oa, etc. and com at least 5 parts per million of the above urethane com binations thereof. pounds, said compounds being sufficiently soluble in the More specifically, the above-described cyclic amidine 45 hydrocarbon fluid to inhibit corrosion. compounds may be described by the formulae: THE HYDROXY ALIPEHATIC CYCLIC AMIDNE (1) The expression "cyclic amidines' is employed in its usual sense to indicate ring compounds in which there 50 are present either 5 or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional (2) carbon atoms completing the ring. All the carbon atoms may be substituted. In the present instance the nitrogen 55 atom of the ring involving two monovalent linkages (the 1-position) is substituted with an hydroxy aliphatic group, i.e., -(RO)H groups where R is alkylene and n is a whole number, for example, 1-5 or higher. (3) These cyclic amidines are further characterized as 60 being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid, such as a low molal fatty acid, a 2,987,515 3 4 high molal fatty acid, or comparable acids, polycarboxy Examples of dienoic acids comprise the pentadienoic acids, and the like. acids, the hexadienoic acids, for example, sorbic acid, the For details of the preparation of imidazolines sub octadienoic acids, for example, linoleic, and the like. stituted in the 2-position from amines, see the following Examples of the trienoic acids comprise the octadec U.S. Patents, U.S. No. 1,999,989 dated April 30, 1935, atrienoic acids, for example, linolenic acid, eleostearic Max Bockmuhl et al.; U.S. No. 2,155,877 dated April 25, acid, pseudo-eleostearic acid, and the like. 1939, Edmund Waldmann et al., and U.S. No. 2,155,878 Carboxylic acids containing functional groups such as dated April 25, 1939, Edmund Waldmann et al. Also hydroxy groups can be employed. Hydroxy acids, par see Chem. Rev. 32, 47 (43), and Chem. Rev. 54,593 (54). ticularly the alpha hydroxy acids comprise glycolic acid, Equally suitable for use in preparing compounds use lactic acid, the hydroxyvaleric acids, the hydroxy caproic ful in our invention and for the preparation of tetra acids, the hydroxyheptanoic acids, the hydroxy caprylic hydropyrimidines substituted in the 2-position are the acids, the hydroxynonanoic acids, the hydroxycapric acids, corresponding polyamines containing at least one pri the hydroxydecanoic acids, the hydroxy lauric acids, the mary amino group and one secondary amino group, or hydroxy tridecanoic acids, the hydroxymyristic acids, the another primary amino group separated from the first 5 hydroxypentadecanoic acids, the hydroxypalmitic acids, primary amino group by three carbon atoms instead of the hydroxyhexadecanoic acids, the hydroxyheptadecanoic being separated by only 2 carbons as with imidazolines. acids, the hydroxy stearic acids, the hydroxyoctadecenoic This reaction as in the case of the imidazoline is generally acids, for example, ricinoleic acid, ricinelaidic acid, hy carried out by heating the reactants to a temperature at droxyoctadecynoic acids, for example, ricinstearolic acid, which 2 moles of water are evolved and ring closure is 20 the hydroxyeicosanoic acids, for example, hydroxyara effected. For details of the preparation of tetrahydro chidic acid, the hydroxydocosanoic acids, for example, hy pyrimidines, see German Patent No. 700,371 dated De droxybehenic acid, and the like. cember 18, 1940 to Edmund Waldmann and August Examples of acetylated hydroxyacids comprise ricin Chwala; German Patent No. 701,322 dated January 14, oleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricin 1941, to Karl Kiescher, Ernst Urech and Willi Klarer 25 oleic acid, and the like. and U.S. Patent No. 2,194,419 dated March 19, 1940 Examples of the cyclic aliphatic carboxylic acids com to August Chwala. prise those found in petroleum called naphthenic acids, Substituted imidazolines and tetrahydropyrimidine are hydnocarbic and chaumoogric acids, cyclopentane car obtained from a variety of acids beginning with the one boxylic acids, cyclohexanecarboxylic acid, campholic carbon acid (formic) through and including higher fatty 30 acid, fencholic acids, and the like. acids or the equivalent having as many as 30 carbon Examples of aromatic monocarboxylic acids comprise atoms, for example from 8-22 carbons. Modified fatty benzoic acid, substituted benzoic acids, for example, the acids also can be employed as, for example, phenyl stearic toluic acids, the xyleneoic acids, alkoxy benzoic acid, acid or the like. Cyclic acids may be employed, includ phenyl benzoic acid, naphthalene carboxylic acid, and ing naphthenic acids. A variety of other acids including 35 the like. benzoic acid, substituted benzoic acid, salicyclic acid, Mixed higher fatty acids derived from animal or vege and the like, have been employed to furnish the residue table sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn R oil, cottonseed oil, sardine oil, tallow, soya-bean oil, pea 40 nut oil, castor oil, seals oils, whale oil, shark oil, and from the acid RCOOH in which the C of the residue other fish oils, teaseed oil, partially or completely hydro Ré genated animal and vegetable oils are advantageously em ployed. Fatty and similar acids include those derived is part of the ring. The fatty acids employed, for exam from various waxes, such as beeswax, spermaceti, mon ple, may be saturated or unsaturated. They may be hy tan wax, Japan wax, coccerin and carnauba wax. Such droxylated or nonhydroxylated. Branched long chain acids include carnaubic acid, cerotic acid, lacceric acid, fatty acids may be employed. See J. Am. Chem. Soc. montanic acid, psyllastearic acid, etc. One may also em 74,2523 (1952). This applies also to the lower molecu ploy higher molecular weight carboxylic acids derived by lar weight acids as well. oxidation and other methods, such as from paraffin wax, Among sources of such acids may be mentioned straight petroleum and similar hydrocarbons; resinic and hydro chain and branched chain, saturated and unsaturated, ali 50 phatic, cycloaliphatic, aromatic, hydro-aromatic, aralkyl aromatic acids, such as hexahydrobenzoic acid, hydro acids, etc. genated naphthoic, hydrogenated carboxy diphenyl, naph Examples of Saturated aliphatic monocarboxylic acids thenic, and abietic acid; aralkyl and aromatic acids, such comprise: acetic, proprionic, butyric, valeric, caproic, as Twitchell fatty acids, naphthoic acid, carboxydiphenyl heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, 55 pyridine carboxylic acid, blown oils, blown oil fatty acids tridecanoic, myriatic, pentadecanoic, palmitic, hepta and the like. - decanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, Other suitable acids include phenylstearic acid, benzoyl docosanoic, triconsanoic, tetracosanoic, pentacosanoic, nonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, cerotic, heptacosanoic, montanic, nonacosanoic, melisaic chlorstearic acid, etc. and the like. 60 Examples of the polycarboxylic acids comprise those Examples of ethylenic unsaturated aliphatic acids com of the aliphatic series, for example, oxalic, malonic, suc prise: acrylic, methacrylic, crotonic, anglic, teglic, the cinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, pentenoic acids, the hexenoic acids, for example, hydro nonanedicarboxylic acid, decanedicarboxylic acids, undec Sorbic acid, the heptenoic acids, the octenoic acids, the anedicarboxylic acids, and the like. nonenoic acids, the decenoic acids, for example, obtusilic 65 Examples of unsaturated aliphatic polycarboxylic acids acid, the undecenoic acids, the dodencenoic acids, for comprise fumaric, maleic, mesoconic, citraconic, glutonic, example, lauroleic, linderic, etc., the tridecenoic acids, the itaconic, muconic, acenitic acids, and the like. tetradeconoic acids, for example, myristoleic acid, the Examples of aromatic polycarboxylic acids comprise pentadecenoic acids, the hexadecenoic acids, for example, phthalic, isophthalic acids, terephthalic acids, substituted palmitoleic acid, the heptadecenoic acids, the octadec 70 derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. deriva enoic acids, for example, petrosilenic acid, oleic acid, tives), biphenyldicarboxylic acid, diphenylether dicar olaidic acid, the nonadecenoic acids, for example, the boxylic acids, diphenylsulfone dicarboxylic acids and the eicosenoic acids, the docosenoic acids, for example, erucic like. acid, brassidic acid, cetoleic acid, the tetracosenic acids, Higher aromatic polycarboxylic acids containing more and the like. 75 than two carboxylic groups comprise homimellitic, tri

2,987,515 5 6 mellitic, trimesic, mellophanic, prehnitic, pyromellitic for example, 1-10, but preferably 1-5, and CB2 is, for acids, mellitic, acid, and the like. Other polycarboxylic acids comprise the dimeric, tri example, a divalent radical of the formula: meric and poly acids, for example, Emery Industries polymeric acids (such as those described in U.S. Patent -CEs-CE- -CH-CH-CH- -CH-CE 2,763,612), and the like. Other polycarboxylic acids H comprise those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be ad -CE-C- -C-C-CH vantageously employed. &H, &H, ÖH, In addition, acid precursors such as esters, acid chlo 10 rides, glycerides, etc. can be employed in place of the etc. free acid. In general, the hydroxyalkyl cyclic amidines are pre Where the acid contains functional groups such as pared by reacting a polyamine containing a terminal hydroxy groups, this should be taken into consideration alkanol group with a carboxylic acid at temperatures of in subsequent reaction with the isocyanate in calculating 5 from 150-175 C. employing an azeotroping agent such the stoichiometry of the reaction. as Xylene to remove water. A reaction time of 3-4 Hydroxy substituted imidazolines and tetrahydro hours is employed. Completion of reaction is judged by pyrimidines can be obtained in the manner described the separation of 2 moles of H2O for each carboxylic above from a wide variety of polyamines containing hy acid group. The products are in general dark viscous droxy groups. Thus, where one starts with a polyamine, 20 oils. for example, a diamine of the following formula Since the preparation of cyclic amidines is so well known (see above cited patents) it is not believed that any examples are necessary to illustrate such a well H H known procedure. However, for purposes of illustra NHR-N-R-O or NE-R-N-(OR.) OB 25 tion the following are included. where R has 2 or 3 carbon chains in the main chain, one Example 10a obtains the hydroxyalkylene compounds useful in this invention. In addition, one can start with ethylene di A solution of 1 mole of hydroxyethyl ethylene diamine, amine or with 1,2-propylene diamine, 1,3-propylene 30 diamine or other polyamines and then react the cyclic HO CELCINCHCH-NH amidine so obtained with alkylene oxides so as to pro duce a terminal hydroxy group since the nitrogen bonded hydrogen on the 1-position on the ring reacts with and 1 mole of oleic acid in 300 grams of xylene are alkylene oxides. In addition the hydroxyalkylene group 35 charged to a flask and brought to reflux, the mixture can be oxyalkylated. being heated under a Dean-Stark water trap, condenser Alkylene oxides comprise those of the general for in order to distill off the water-Xylene azeotrope mixture, mula, to separate the water and to continuously return xylene to the reaction mixture. Reflux is continued at a tem R-CH-CH 40 perature of 160-170° C. for about 3% hours until about Yo/ 2 moles of water is removed. The product is wnere R is hydrogen or an alkyl group. Among the CH-CH alkylene oxides that may be employed are ethylene, propylene, butylene, octylene, etc. oxides, etc. Other 45 N N-CECHOH oxyalkylation agents such as glycide, epichlorohydrine, N c^ etc. can also be employed. & Ha Thus hydroxy compounds within the scope of this in wention which react with isocyanates comprise com Example 9b pounds of the formulae: The above example is repeated except that hydroxy ethyl propylene diamine 1-3, N R-C 2 3CB). H N 55 iO CHCHN-CH2CH2CHNH D is employed in place of hydroxyethylethylene diamine and stearic acid is employed in place of oleic acid. The -'sn 2 N product produced is (CB), C-R-C CB)n N/ 60 N b D (H, (H, N N-CH2CH2OH where 65 s/ Re Example 4c is the residue derived from the carboxylic acid, where R Example 1.0a is repeated with the same amine is a hydrocarbon radical having, for example, up to about 70 30 carbon atoms, hydrocarbons in which the carbon atom chain is interrupted by oxygen, etc., n is 2 or 3; and B is a O CHCH-NCHCH-NH, hydrogen or a hydrocarbon radical, for example, an alkyl E. radical; and D is a hydroxy aliphatic radical, for example (2 moles), except that a polycarboxylic acid, sebacic -ROH or -(RO),OH, wherein x is a whole number, 75 acid (1 mole) is employed. Instead of two moles of 2,987,515 8 water being removed, as in the prior example, about 4 Example 28a moles of water, are removed. The product is Example 11a is repeated except that 2 moles of ethyl C-C CH-CH ene oxide are employed. The product is | HO-C-C-N N N N-CHCHO 5 C-C, N N-(CaCO) S/ C Example 20d & He Example 4c is repeated except that a different amine, 10 Since the above examples are typical methods of prep aration, it would be repetitious to repeat the details of HO CHCHCHCHCH-NH. each preparation. Therefore, the reactants employed by H us in preparing other hydroxycyclic amidines of these types are listed in the following tables: (2 moles) and a different polycarboxylic acid, tereph- 15 thalic acid (1 mole), are employed. As in the prior TABLE I example, 4 moles of water are removed. The product is

NS -R c es C (H, (H, (H, (H, 20 R EO CH-C-N N N N-CECHO 2 S. Ex. RCOOSource R Ye1 (D-Scy No. of RC 25 ld.----- Lauric------CHCHO In general, to form the polyoxyalkylated hydroxy cyclic exanoic CH2CH2OE amidines, the hydroxyalkylcyclic amidine is first prepared Sowalerie CHCH2OH Stearic CCEO in the manner shown above and then reacted with alkylene Melissic------CECOE oxides by the conventional manner of oxyalkylation to Phenyl Stearic. CECEO Benzoic------CECHOE the desired degree of oxyalkylation using a jacketed CreSotiric - CHCFO stainless steel autoclave in the manner described in U.S. Naphtheni CECBOE Patent 2,792,369. The following examples are illustra Oleic- CICEO tive: Oleic- CHCOCECHO (H, gii, Example Ila 35 12a---- Oleic------CHCHOCH2CH2OH. One mole of 13a.-- Lauric------CH2CH2OCECHO i4a-...-- Palitic- CICOCCEO 15a---- Cerotic------CECHOCHCFO 16al p-tert-Butylbenzoic. CH2CH2OCH2CEOE 17a---- Benzoic------CECOCCOE. N N-CECEO 18a.---- Toluic--- - CHCHOCH2CH2O 9a--- Naphthenic CCEOCH2CH2OH. s/ 40 20a. --Benzoic.-- CCH3OCH2CH2O 21a----22 Methyloctadecanoic.Formic------CECHOCH2CHOCECEOCHCHodCHOCHCHOH 28a---- Capric------CH3COCEICOCECHO 24a.---- Stearic----- CH2CH2OCECHOCECHO 250---- Phenylstearic. CCOCECHOCCOE (50% solution in xylene) is reacted with 1 mole of eth 26a.... CreSotinic.-- - CHCOCECEOCHCIOE ylene oxide at a temperature of 125-130° C. and a pres Linoleic CECHOCH2COCHCHOH sure of 10-15 p.s. i. The time regulator is set to add Oleic----- CECIOCCEOCEICO ethylene oxide over /2 hour followed by additional stir 3-methoxy CHCHOCECHOCH2CH2O ring for another /2 hour to insure complete reaction. 30d.---- Naphtheric CECEOCH3COCECEOH Ethylene oxide is readily taken up by the reactants. The product is TABLE II 50 (H-H, N N-CEICO CH-CHOH S S/ - OC C R & Ha 55 Ex. No. RCOOSource of RC R

Example 12a Ib------Formio.------CHCH2OH. 2b.-- Acetic.- CECHO 3b.-- CECH2OH The above example is repeated using a propylene oxide 60 Alb- CECH2OH. 5b. Sowaleric------(CH) CHCHOH and 6b. TrimethylAcetic CECHO 7b. Pelargonic------CECHO 8b- Lauric-...- CH CEO CHCHOH 9t.-- Stearic--- CECHOH GH, 10b. Arachidic------CECHOE 116--- Eicosane-carboxylic- (CE) CHCHOH N g -c-CH-OH 65 12b--- Cerotic------CECEO 13b----- Melissic------CHCOE C17H33 14th-- Phenyl Stearic. CCOE 5b. Benzoic------CHCHO CHCHO 16b b-methylbenz CH2CH2OH. 7. Cresotinic.... CH2CH2OH. under similar conditions. The product is 18b- p-methybenzo CHCHOF 19b. P-tert-Butyl-benzoic- CH2CH2OH. 70 20--- 3-methoxybenzoic.-- CH2CH2OH. 21b------Oleic------CH2CH2OH. (H-H, (H. C3 Undecylenic- - CECO N N-CECHO (HoH Linoleic------CH2CH2OH Butyric.------CHCHOH s/ 25b------Methyloctadecanoic------CHCHO

C17H33 5

2,987,515 O A preferred subgenus of this invention is that wherein the above partial structural formulae represents the poly isocyanate and more specifically the diisocyanates, which of course contain two distinct and separate isocyanate N2 N / 5 groups. Representative compounds of this subgenus are C-R-C the polymethylene diisocyanates such as ethylene diso cyanate, trimethylene diisocyanate, tetramethylene diso Ex. IOOC-R-COOE R cyanate, pentamethylene diisocyanate, etc.; the alkylene No. Source of -CRC diisocyanates such as propylene-1,2-diisocyanate, butyl ic----- Malonic------CECHO O ene-1,2-diisocyanate, butylene 1,3-diisocyanate, butylene 2c----- Adipic--- CCHO 2,3-diisocyanate; the alkylidine diisocyanates such as eth 3c----- Suberie- CHCHOI 4c----- Sebacic------CCEOH ylidenediisocyanate, butylidene diisocyanate, and heptyli 5c----- Nonodecane dicar- CHCH2OH boxylic. dene diisocyanate. The cycloalkylene diisocyanates such Biglycolic------CHCHOH as cyclopentylene-1,3- diisocyanate, cyclohexylene-1,2- Eise Bis(gly- CECHOH 5 diisocyanate, cyclohexalene-1,4-diisocyanate; the aromat O Methylene dibenzoic. CHCHOE ic diisocyanates such as m-phenylenediisocyanates, p-phen Steary Malonic CHCHO Phthalic CCHOH ylene diisocyanate, 1-methylphenylene-2, 4-diisocyanate, Succini CH2CHOCH2CEO 1-methylphenylene-2, 6-diisocyanate, 3,3'-bitolylene-4,4'- Glutari CH2CH2O CH2CO diisocyanate, naphthylene-1, 4-diisocyanate, naphthylene Piraetic CHCHO CHCEO 20 Azelaic--- CHCHOCHCFOH 1,5-diisocyanate; aliphatic-aromatic diisocyanates, such as Eicosanedicarboxylic CECHO CH2CH2O Dilinoleic------CH2CH2O CHCHO Xylene-1, 4-diisocyanate, xylene-1, 3-diisocyanate, 4,4'- ISOphthalic.------CECHO CHICEOH diphenylenemethane diisocyanate, 4,4'-diphenylenemeth Diglycolic------CH2CH2O CH2CH2O Lauryl Malonic------CEI CEO CH2CHOR ane diisocyanate, 4.4'-diphenylenepropane diisocyanate, Methylene dibenzoic. CH2CH2O CH2CO etc. Malonic------CHCHO CHCHO CHCHOH 25 Succinic.------CH2CH2O CH2CHO CH2CO The diisocyanates of the types listed in the above para Suberic------CECHO C2H2CH2O CHCHO graph are the ones which are most preferred for purposes Pimelic------CH2CH2OCH2CH2O CECHOH Ngesane dicar- CB2ClHO CH2CH2O CECHOH of this invention. Examples of compounds containing Oxylic, more than two reactive groups of formula-CNZ and of Diglycolic------CE2CEO CHCHO CHCHO Methylene dibenzoic. CEI CEO C2E2CH2O CHCHO the preferred subgenus -N=C=O which can be used, Stearylmalonic- - CH2CH2O C2E2CH2O CHCHO 30 there may be mentioned 1,2,4-benzene triisocyanate and Steary succinie CHCHOCH2CHO CHCHOH. butane-1,2,2-triisocyanate. Terephthalic------CaCH2O C2H2CH2O CHCEO Of course, it should be remembered that the polyiso thiocyanates may be used instead of the polyisocyanates and representative examples would be those given above TABLE W 35 With the single change that the oxygen atom is substituted by sulfur. Corresponding monoisocyanate derivatives of the above diisocyanates were also reacted, but, in general, they ex R-N 2 O.NS hibit far less activity in corrosion than the corresponding C-ru-R-C 40 diisocyanates, for example, alkylisocyanate (e.g. methyl, Ex, No. HOOC-R-COO R €thyl, propyl, butyl, octadecyl, etc.); cycloalkyl (e.g. cy Source of -CRC clopentylisocyanates, cyclohexylisocyanates) aryllisocya nates (e.g. phenyl, naphthyl, etc.) alkaryl isocyanates id------Malonie------CCHO (e.g. tolyl isocyanates, xylyl isocyanates), and the like. CHCH2OH. 45 CHCHO The reactions involving isocyanates with urethane pre CH2CH2O (CH3)CHCHOE Cursors are conducted in the same manner isocyanates CEICEO have been reacted with other suitable reactants (see, for CHCHOCH2CHOH CHCHOH example, Chem. Rev. 43, 203-218 (1948), 57, 47.76 Nonodecane dicarboxylic--- CH2CH2OH. (1957). Eicosane dicarboxylic.------CH2CH2OH. 50 Diglycolic------CHCHOH THEHE URETHANE PRODUCTS Ethylene bisglycolic------. (CE) CECHO Methylene carboxylic acid (C) CHCHOH Dillinoleic----- CHCH-OH The products of this invention are urethanes, for ex Stearyl Imaonic CHCHOH ample, Laurylsuccinic- CHCHOF Isotetradecyl succini CHCHOH Phthalic------CHCHOCHCHOH 55 Sophthalic. CECHOH N -\ N-X-C-N-R Terephthalic. CHCHOH N/ 2id------Glutaconic------CHCO sR THE SOCYANATE REACTANT 60 The isocyanate employed to react with the urethane where a comprises precursor can vary widely. In general, they may be expressed as R-(CNZ), where z is oxygen or sulfur. This R'O (RO), etc. includes isocyanates and isothiosyanates and mixed iso 65 cyanates and isothiocyanates. For convenience this in wherein the hydroxy precursor and a monoisocyanate as vention will be discussed largely in terms of isocyanates. reacted and In the above formula R is an aliphatic radical, a cyclo aliphatic radical, an aromatic radical and the like, and ^ H x is a whole number equal to 1 or greater, for example 70 N N-X-C-N as 1 to 3. N/ However, we prefer to employ the diisocyanates in pre paring derivatives used as anti-corrosion agents since R 2 they exhibit much greater activity than the monoiso cyanates. 5 in the case of the diisocyanate, 2,987,515 11 12 Where the bicyclic amidines are used as hydroxy pre hour at 60-75 C. The addition is controlled so as to cursors, the following compounds are formed: maintain this temperature. The resulting product is then diluted with xylene so that it has 50% by weight of the A. H product. The following examples are illustrative. The N^ Y-X---R 5 products formed are generally dark viscous liquids. N/ C Example 10ab R To two moles of w t g H N1 N-x-E--R O NA^ with the mono-isocyanates, and polymers are probably N N-CHCHOEI formed with diisocyanates, as may be expressed by the following formula 15 Ha in a well-stirred reaction vessel is added one mole of a NYA. Y-xSo-ri---x-o H H 50% solution of toluene-2,4-diisocyanate in xylene over s/ a period of 30 minutes. The temperature during addition k 20 was 60-70° C. The product formed is

O O 2 N H H || N1 Y N N-CHC-O-CN -N-C-O CHCH-N N N / S / N2 A. 25 C C CH Where the isocyanate is a isothiocyanate, the product C17H3s CH33 would be the analogous thiourethane, thus, Example 10alD NYA. Y-X---RE. N/ 30 The process of the prior example is repeated except that p,p' diphenylmethane diisocyanate is employed. The prod R uct is O H. O. - N -CECH-O-C-N CH N-C-O-CHCH-N N N c^ Yé C17H33 C17Has Example 10aC would be The process of the prior example is repeated except ^ H. that dianisidine diisocyanate, N^ Y-x-E-R-R CHO N/ 45 O CH3 C R oc-K) ( > No. is employed. The product O CH O CH3 O. H H. O N N-CHCHO-C-N --CO CHCH-N. N. S/g Na CHas - CH and Example 10aA A. g E The process of the prior example is repeated except NY Y-x-E-i a-R" that hexamethylene diisocyanate was employed. The N / C 60 product is k 2 O E EO would be N N-CHCH-O-C-N-(CH2)6-N-C-O-CHCH-N N A. i S/ Né N^ Y-X---R" 65 Ca C17H33 N / Example 10aG R 2 The process of the prior example is repeated except and the others correspondingly changed to where the 7 that one mole of O O - -- group is replaced with -C- N - N-CH2CH2OH. In general, the urethane is prepared by adding the iso S/ cyanate (a 50% solution, by weight, in Xylene) to the hydroxy-cyclic amidine over a period of /2 hour to 1 75 Ca3

2,987,515 3. 4. and one mole of octadecyl isocyanate is employed to yield and 1 mole of m-toluene diisocyanate are employed to yield O H. NN/ N-CHCO-C-N-C1s 5 ? O H. H O|| ? C N N-CHCHO-C-N -N-C-O CHCH-N N Htd33 S/C . - NaC d CE 1735 17H35 Example 10aH O The above process is repeated except that 2 moles of Example 9b.A. The process of the prior example is repeated except that hexamethylene diisocyanate is employed to yield 5 N-CCH2OH. and 1 mole of 15 naphthalene diisocyanate are employed 20 s/ N1 to yield 1785 C1E35 O Example 3cA. N-C-O CHCH-N N 25 N2 The process of the prior example is repeated except &H1733 that one mole of

30 N ?S-CHCH-0--N O E. Hochsch-N C-(CH2)6-C3. N -CHCH-OH C133 0. and one mole of m-toluene diisocyanate are employed to Example 10aF 35 yield a polymeric material, of the probable structure: The process of the prior example is repeated except O O that 2-naphthylisocyanate is employed. The product H H II formed is N N-CHCHO-C-N -N-C-O CECH 40 N2 N/ C-(CH2)6-C O H CE N N-CHCHO-C-N n & His 45 Example 3cB The process of the prior example is repeated except Example 9bB that one mole of The process of the prior example is repeated except that 50

?y HO CHCH-N 2N NN N-CHCHOH N N-CCHOF C-(CH2)6-C y 55 and 2 moles of octadecyl isocyanate are employed to yield C17H35 d e employed to yield H O O E. and ethyl isocyanate ar ploy y1 Cat-3-ochsch, N N -ch.ch,0-8-cin, O H. 60 cfcc.H.Sc N-CCHO-C-N-CHs N/ Example 28aB bits The process of the prior example is repeated except 65 that 2 moles of Example 9bC The process of the prior example is repeated except les of that 2 moles O. N-(CH2CH2O)3H

N N-CECHOF nc^ and 1 mole of p,p' diphenylmethane diisocyanate are CH35 75 employed to yield 2,987,515 15 6 O O | H. H || N N-(CHCHO)-C- CE N S/ &Ha Example 20aB 9bE Diphenylmethane, 4,4-diisocyanate 23b A. Hexamethylene diisocyanate The process of the prior example is repeated except 23bB 2,4-toluene diisocyanate that 2 moles of 10 23bC Diphenylmethane 4,4-diisocyanate 3CA 2,4-toluene diisocyanate 3cB Octadecyl isocyanate N N-(CH2CH2O).H. 3cC Dianisidine diisocyanate S/ 3cD Diphenylmethane 4,4-diisocyanate 5 4dA 2,4-toluene diisocyanate 4dB Dianisidine diisocyanate USE AS CORROSION INHIBITOR More specifically, this phase of the invention relates and one mole of 15 naphthalene diisocyanate are em 20 to the inhibition of corrosion in the petroleum industry ployed to yield with specific reference to producing wells, pipe lines, re fineries, tank storage, etc. The use of a corrosion inhibiting agent in the oil H. O. 25 industry and other industries, and particularly for the N-C-(OCH2CH)-N N protection of ferrous metals, is well known. For ex ample, see U.S. Patents Nos. 2,736,658 dated February (H N1 28, 1954, to Pfohl et al., and 2,756,211 dated July 24, N -(CH, CH,0)-C-N > 1956, to Jones, and 2,727,003 dated December 13, 1955, C to Hughes. 30 More specifically then, and particularly from the stand point of oil production, this aspect of the invention relates to inhibiting corrosion caused by hydrogen sulfide, car bon dioxide, inorganic acids, organic acids, combinations 35 of each with oxygen, and with each other and oxygen. A large number of urethanes have been prepared. More particularly, it relates to treating wells to mitigate Since the method of preparing these compounds is quite metal corrosion and associated difficulties. simple, these results are presented in the following table It should also be pointed out that the corrosiveness of to save repetition of preparative detail. Each urethane oil well brines will vary from well to well, and the pro will have the basic number shown in the prior tables, 40 portion of corrosion inhibiting agent added to the well for example, 1a, 10a, etc. indicative of the hydroxy cyclic fluids should also be varied from well to well. Thus, in amidine employed. In addition, it will bear capital letter some wells it may be possible to effectively control cor A, B, C, D, etc. which indicates that it has been reacted rosion by the addition of as little as 5 p.p.m. of our with an isocyanate. In each example one mole of iso new compositions to the well fluids, whereas in other cyanate group was employed per mol of hydroxy group wells, it may be necessary to add 200 p.p.m. or more. In using our improved compositions for protecting on the cyclic amidine. oil well tubing, casing and other equipment which comes ABLE W in contact with the corrosive oil-brine production, we find Preparation of urethanes that excellent results are obtained by injecting an appro 50 priate quantity of selected composition into a producing 1a A Hexamethylene diisocyanate well so that it mingles with the oil-brine mixture and 1aB Mixed isomers of toluene diisocyanate come into contact with the casing, tubing, pumps and 1aC Dianisidine diisocyanate other producing equipment. We, for example, introduce 1aD 1,5-naphthalene diisocyanate the inhibiting composition into the top of the casing, thus 1aE Diphenylmethane, 4,4'-diisocyanate 5 5 causing it to flow down into the well and thence back 10aA Hexamethylene diisocyanate through the tubing, etc. In general, we have found that 10aB 2,4-toluene diisocyanate this procedure suffices to inhibit corrosion throughout 10aC Dianisidine diisocyanate the entire system of production, and collection, even in 10a) Diphenylmethane, 4,4'-diisocyanate cluding field tankage. 10aB Ethyl isocyanate 60 In case serious emulsion or gel problems are encoun 10af d-naphthylisocyanate tered, demulsifiers are advantageously added. This is 10aG octadecyl isocyanate important not only to avoid the troublesome emulsions 10ah 15 naphthalene diisocyanate and gels themselves, but also to improve corrosion in 10al Mixed isomers of 2,4-toluene diisocyanate hibition. The explanation of less effective corrosion in 14a A Hexamethylene diisocyanate 65 hibition in the presence of emulsions apparently is that 14aB 2,4-toluene diisocyanate the inhibitor is somewhat surface-active. That is, it 20aA 1,5-naphthalene diisocyanate is concentrated at interfacial surfaces. Since this surface 28aA, Hexamethylene diisocyanate is great in an emulsion, most of the inhibitor will be con 28aB b,b'-diphenylmethane diisocyanate centrated in these interfaces and little will remain in the 28a0 2,4-toluene diisocyanate 70 body of the oil for deposition on the metal Surfaces. 28ad Dianisidine diisocyanate In many wells, oil-in-water type emulsions often occur 9bA Hexamethylene diisocyanate naturally. In such wells the inhibitors herein described 9bB Ethyl isocyanate tending to form water-in-oil type emulsions, often de 9bC 2,4-toluene diisocyanate crease the emulsion problems naturally present. Thus, 9bD Dianisidine diisocyanate 75 in addition to being effective corrosion inhibitors, the

2,987,515 17 18 herein described products tend to eliminate emulsion with other well-known corrosion inhibitors, for example, problems which sometimes appear when some of the the cyclic amidine structures, the amido cyclic amidine present day inhibitors are used in oil wells or refinery structures, and the amino cyclic amidine structures, as processing. disclosed in the Blair and Gross Reissue Patent No. The method of carrying out our process is relatively 23,227. When the herein described products are mixed simple in principle. The corrosion preventive reagent with corrosion inhibitors of the conventional type in the is dissolved in the liquid corrosive medium in small ratio of one-to-three, one-to-one, three-to-one, or the like, amounts and is thus kept in contact with the metal sur in numerous instances the effectiveness of the corrosion face to be protected. Alternatively, the corrosion in inhibitor thus obtained is often significantly greater than hibitor may be applied first to the metal surface, either O the use of either one alone. as is, or as a solution in some carrier liquid or paste. Since these products are basic they can be combined Continuous application, as in the corrosive solution, is with various acids to produce salts in which oil solu the preferred method, however. bility is increased or decreased. Likewise, water solu The present process finds particular utility in the pro bility is increased or decreased. For instance, the prod tection of metal equipment of oil and gas wells, especially 5 ucts are mixed with one or more moles of an acid, such those containing or producing an acidic constituent such as higher fatty acids, dimerized fatty acids, naphthenic as H2S, CO2, inorganic, organic acids, Oa and the like. acids, acids obtained by the oxidation of hydrocarbons, as For the protection of such wells, the reagent, either well as sulfonic acids such as dodecylbenzene sulfonic undiluted or dissolved in a suitable solvent, is fed down acid, petroleum mahogany acids, petroleum green acids, the annulus of the well between the casing and producing 20 etc. tubing where it becomes commingled with the fluid in What has been said in regard to the acids which in the well and is pumped or flowed from the well with crease oil solubility and decrease water solubility applies these fluids, thus contacting the inner wall of the casing, with equal force and effect to acids of the type, such as the outer and inner wall of tubing, and the inner sur acetic acid, hydroxyacetic acid, gluconic acid, etc., all of face of all well-head fittings, connections and flow lines 25 which obviously introduce hydrophile character when they handling the corrosive fluid. form salts or complexes, if complexes are formed. For . Where the inhibitor composition is a liquid, it is con example, any of the acids described above is preparing ventionally fed into the well annulus by means of a motor the cyclic amidines are useful in preparing these salts. driven chemical injector pump, or it may be dumped As pointed out previously, the addition of corrosion periodically (e.g., once every day or two) into the 30 inhibitors, particularly in the form of a solution by means annulus by means of a so-called "boll weevil' device or of a metering pump or the like, is common practice. similar arrangement. Where the inhibitor is a solid, it is The particular corrosion inhibitors herein described are dropped into the well as a solid lump or stick, blown in as applied in the same manner as other corrosion inhibitors a powder with gas, or it may be washed in with a small intended for use for the same purpose. For sake of stream of the well fluids or other liquid. Where there 35 brevity, as to the use of the corrosion inhibitor and its is gas pressure on the casing, it is necessary, of course, solution in a suitable solvent such as mineral oil, methyl to employ any of these treating methods through a pres ethyl ketone, Xylene, kerosene, high boiling aromatic sol sure equalizing chamber equipped to allow introduction vent, or even water. of reagent into the chamber, equalization of pressure The following examples are presented to illustrate the : between chamber and casing, and travel of reagent from 40 superiority of the instant compounds as corrosion in chamber to well casing. hibitors. Occasionally, oil and gas wells are completed in such Static weight loss tests a manner that there is no opening between the annulus and the bottom of the tubing or pump. This results, for These tests have been run on both synthetic and natur example, when the tubing is surrounded at some point ally occuring fluids. The test procedure involved the by a packing held by the casing or earth formation below measurement of the corrosive action of the fluids in the casing. In such wells the reagent may be introduced hibited by the compositions herein described upon sand into the tubing through a pressure equalizing vessel, after blasted S.A.E. 1020 steel coupons measuring 78 x 34 stopping the flow of fluids. After being so treated the inches under conditions approximating those found in well should be left closed in for a period of time suffi 50 an actual producing well, and the comparison thereof cient to permit the reagent to drop to the bottom of the with results obtained by subjecting identical test cou well. pons to the corrosive action of identical fluids containing For injection into the well annulus, the corrosion in no inhibitor. hibitor is usually employed as a solution in a suitable Clean pint bottles were charged with 200 ml. of 10% solvent, such as mineral oil, methylethyl ketone, xylene, 55 Sodium chloride solution saturated with hydrogen sul kerosene, or even water. The selection of solvent will fate and 200 ml. of mineral spirits and a predetermined depend much upon the exact reagent being used and its amount of inhibitor was then added. In all cases the solubility characteristics. It is also generally desirable to inhibitor concentration was based on the total volume employ a solvent which will yield a solution of low of fluid. Weighed coupons were then added, the bottles freezing point, so as to obviate the necessity of heating tightly sealed and allowed to remain at room tempera the solution and injection equipment during winter use. 60 ture for 3 days. The coupons were then removed, cleaned For treating wells with packed-off tubing, the use of by immersion in inhibited 10% hydrochloric acid, dried solid “sticks' or plugs of inhibitor is especially convenient. and weighed. These are prepared by blending the inhibitor with a min The changes in the weight of the coupons during the eral wax, asphalt or resin in a proportion sufficient to corrosion test were taken as a measurement of the effec give a moderately hard and high-melting solid which can 65 tiveness of the inhibitor compositions. Protection per be handled and fed into the well conveniently. centage was calculated for each test coupon taken from The amount of corrosion preventive agent required in the inhibited fluids in accordance with the following our process varies with the corrosiveness of the system, formula: but where a continuous or semi-continuous treating pro 70 cedure is carried out as described above, the addition X 100 = Percent protection of reagent in the proportion of from 5 parts per million to 1000 parts per million or more parts of corrosive fluid in which Li is the loss in weight of the coupons taken will generally provide protection. from uninhibited fluids and La is the loss in weight of The corrosion inhibitors can be used in combination 75 coupons which were subjected to the inhibited fluids, 2,987,515 19 20 Static weight loss tests TABLE VI At 100 p.p.m. based on total fluids) -CH, CH, of

Ex. aam--arm-a- Percent Remarks Protection R Diisocyanate

10alD------CrHaBlank. ---...--4:4::phenyl------80.9 The fluids in all 100A.------C17H83 hexamethylene.----lethale. ERE. 10aB------C17H33 2,4-tolune---- ated with HS 100C.------CH33 dianisidine.------pH 6.65. The 10d.------C17Ha8 Me Ers of fiuids were 0% 100B------. C17Has Mixed,4-toluene. isomers , of sodiulin chloride 2,4-toluene and mineral C17H33 None ------spirits. 1 Free alcohol. Stirring tests cent protection can be-- - determined- . . . by the followinga sa . . . . . 25 formula: 4. These tests are run on synthetic fluids. The procedure A- . . .v involvesa . . . the. . . comparison. . . . of the amount of ironw . in. . .solu- .: accx1,4x100-Percent = Percent protectionprotectio tion after a predetermined interval of time of contact of a. standardized iron surface with a twophase corrosive me- 30 wheresample Ai and is Athe is present the same light value absorbed for an by inhibited an uninhibited. sample. dium with similar determinations in systems containing TABLE VII inhibitors. Stirring tests at room temperature Six hundred ml. beakers equipped with stirrers and All inhibitors were used at 40 p.p.m. based on total fluid) heaters are charged with 400 ml. of 10% sodium chloride containing 500 p.p.m. acetic acid and 100 ml. of mineral 88 RSE St Percent spirits. The liquids are brought to temperature and a Inhibitor Ek sale 'E' 1.x. 1 inch sand blasted coupon is suspended by means (A1) (A of a glass hook approximately midway into the liquid --- phase of the beaker. The stirrer is adjusted to agitate 40 SE:::::::::::::::::::::::::::: : : 8:3 the liquids at such a rate as to provide good mixing of SH: III. 3. s: the two layers. SSR. ...I. 5 39 After 30 minutes samples of the aqueous phase are laB------28 4. 85.6 bytaken measuring and the theiron color content formed of each by the sample addition is determined of hydro 8:a::::::::::::::::: 3. i 3.2 chloric acid and potassium thiocyanate in a photoelectric colorimeter. N -ch.choir 28 22 21, 2 The protection afforded by an inhibitor is measured C by comparison of the amount of light absorbed by in- 50 & Ha hibited and uninhibited samples run simultaneously. Per TABLE VIII Stirring tests at 140°F. 40 p.p.m. based on total fluids

N N-CHCHOH

Inhibitor Percent Percent Ex, Absorption Absorption - Percent Blank Sample Protection R Diisocyanate (A1) (A

10GB------C17H3s 2,4-toluene.--- 6 S9.6 10a A.-- C17H3 hexamethylene 58 8 86.3 10a- CH33 15-naphthalene. 58 9 84.5 100I.------C17Has Mixed somers 2,4-toluene.--- 58 7 88.0 0ad------C1Eas diphenylmethane-...------58 81.0 100C------C17H33 dianisidine-...------60 7 89.5 10B------Chas Mixed isomer of 2,4-toluene. 60 7 89.5 Commercial A. Inhibitor-...------60 27 55.0 Commercial B Inhibitor- 21 65.0

20 66.2 Commercial Dinhibitor 19 67.9 Chas None ------a--- 53 0, 2 It has been noted that some compounds have a definite actuation energy so these tests are y E.t r00n temperatures as Well as at elevated temperatures. 88 COO.

2,987,515 2 - - 22 Tanker: tests (cycle test) In pumping wells it has been found that when penetra This test was described by Malcomson et al. (Annual tions are lowered to a value of 1 MPY or less, generally Meeting of the Society of Naval Architects and Marine acceptable protection can be expected. Tolerable rates Engineers, New York, Nov. 1952). It involves the may range up to 4 MPY. Obviously the lower values measurement by weight loss ofcoupons which have been 5 are more acceptable. subjected to the corrosive action of sea water and a Experience has shown good correlation between pene hydrocarbonweek with sea for water a weekand air, followed and the bycomparison contact forthere one to historytration rates as shown by coupons and the well. corrosion. . . the weight loss of coupons subjected to a similar test - - - in which a small amount of inhibitor has been added to 10 The effectiveness of the described compositions in in the hydrocarbon phase hibiting corrosion occurring in oil wells can be better and TABLE IX more fully understood by reference to the results obtained. Cycle test in the aforementioned well tests. In these tests a six (All inhibitors were used at 100 p.p.m.) week control period was first set aside during which time p.).nl. three sets of coupons were used in each well with the ex Inhibitor Wigs, PGE posure time of each set being approximately two weeks, -- --- (Mg.) Protection after which interval the MPY values were determined as 20.1 ------previously described. During this control period a well 28 S8 20 known commercial corrosion inhibitor previously deter 55.8 3. mined to be the best for the well was used in the wells 33 6 at a rate of approximately two gallons per week per well Commercial Inhibitor A.------14.0 8 with treatment being semi-weekly at approximately one 25 gallon per treatment per well. At the end of this control N-CHCHOH 200. 6 4.5 period the new composition 10aB was injected using the S/ same treating procedure and rate as during the previous dahs control period. The results of these tests are described in the following table:

Control Periodi With 10ab Well Name and Number 1M/8-M122 M122-M/15 MI5-M119 Ave. M73-MI16 MI16-M130 M/1-M/15 Ave. Koogler #86.-- 9,30 10,07 14.33 10.90 10,07 0.44 1,72 4.08 Hull-bigginsKoogler #92------6.84 1, 52 5,90 4.79 1.15 03 1,33 1.17 #16------3.69 1,05 1.21 1.98 0.87 0.48 57 0.97 Bender Dia----- 8.42 6.65 4.25 6.44 2,71 5.53 3.05 3.76 1 Mindicates amonth without specific designation.

In using the improved compositions for the protec The unexpected superiority of the instant compounds tion of oil well casing, tubing, and other equipment over the untreated hydroxyaliphatic amidines and other which comes in contact with the corrosive oil and brine, of the best commercially available inhibitors has clearly excellent results have been obtained by injecting an been demonstrated. appropriate quantity of the selected composition into a producing well so that it mingles with the oil brine mix 50 OTHER USES ture and comes in contact with the casing, tubing, pumps These products are effective not only as corrosion in and other producing equipment. For example, the in hibitors but can be used for a number of other purposes. hibiting composition may be introduced into the top of For instance, they can be used as asphalt additives to the casing, thus causing it to flow down into the well and increase the adhesiveness of the asphalt to the mineral back through the tubing. This system suffices to inhibit 55 aggregates. In the form of water soluble salts, they are corrosion in the entire system. useful as bactericides in the secondary recovery of oil. Using this system compound 10aB was used in four The hydroxyaliphatic amidines may be subjected to ex producing wells in Kansas. To evaluate the protection tensive oxyalkylation by means of ethylene oxide, propy afforded by this chemical, small, mild steel plates which lene oxide, butylene oxide, or the like prior to reaction had been sand-blasted and weighed were exposed to the 60 with the isocyanate. These are oxyalkylated and still well fluids by insertion into the flow line near the well have oil solubility as, for example, by the addition of head for periods of two weeks. The specimens were propylene oxide or butylene oxide, or are oxyalkylated retained on a plug by means of a plastic which afforded to produce water solubility as, for example, by means of insulation for the plates so as to prevent interference ethylene oxide or glycide. They are also oxyalkylated by galvanic currents. After exposure the coupons were 65. by combinations of propylene oxide and ethylene oxide cleaned by a brief contact with inhibited hydrochloric so that both water solubility and oil solubility remain. acid, dried and weighed. Thereupon they are reacted with isocyanates. Such The results were expressed in mils penetration per year products are useful for a variety of purposes and partic which expresses the depth of surface, in thousandths of ularly for those where nonionic surfactants or sequestered an inch, removed in a year assuming the corrosion had 70 cationic surfactants are indicated. occurred uniformly over the entire surface. This value In addition, the compounds of this invention have the was readily calculated by the simple formula following application: Agriculture: Additive for kerosene, phenothiazine, MIPY Weight of Metal Removed pyrethrum sprays, fungicides, herbicidal oils. Density of MetalX Areax Years 1000 Anti-static treatment: for hotel rugs, hospital floors, 2,987,515. 23 24 automobile upholstery, plastic and wax polishes, wool 4. A compound of the formula oils, lubricants for synthetic fibers...... N. - Building materials: water repellent treatment for plas M. S. ... a N. ter, concrete, cement, roofing materials, air entrainment, (céo-R-cC sch), floor sealers, linoleum. Yn Cosmetics: formulation of anti-perspirants, deodorants, (h)-1 r(H):- sun screens, hair preparations. De-emulsifying: in antibiotic extraction, breaking ("-ly"). crude oil and water-gas for emulsions. Detergents; metal cleaning emulsions, lens cleaners, 10. floor oils, dry cleaning detergents, radiator flushes, cess R ly pool acid, boiler scale solvents, germicidal corrosion inhibited acid detergents for dairies, enamel equipment, where R is hydrocarbon having 1-36 carbon atoms and R' toilet bowls. is hydrocarbon moiety of hydrocarbon isocyanate having Leather: flat liquoring oils, pickling, acid degreasing, 5 1-30 carbon atoms, R' being in both instances always dye fixative. the same. Metals: rust preventive oils, cutting oils, water dis 5. A compound of the formula N N placing compounds, pickling inhibitor, solvent degreasing. N 2 Paints: for improved adhesion of primers, preventing (CH) water spotting in lacquers, anti-skinning, pigment flushing, 20 Y1. c-R-cC N 3CH), grinding and dispersing, anti-feathering in inks...... , Petroleum: germicide in flood water treatment, de emulsifying fuel oil additives, anti-strip agent in asphalt girlO 1-3 g tor fans emulsions and cutbacks. - Textiles: in rubberizing, textile oils, dyeing assistants, 25 softening agents. Miscellaneous: bentonite-amine complexes, metal amine complexes, preparation of pentachlorphenates, where R is hydrocarbon having 1-36 carbon atoms and R' quaternaries, plastisols, and rodent repellents. w - is hydrocarbon moiety of hydrocarbon isocyanate having Having thus described our invention, what we claim 30 1-30 carbon atoms, R' being in both instances always as new and desire to obtain by Letters Patent, is the same. 1. A compound of the formula 6. A compound of the formula

(CB)-3C-R-C1.s 2N.CB) 2-3 N1 Y rA-1 r. where R is hydrocarbon having 1-36 carbon atoms and 40 R’ is hydrocarbon moiety of hydrocarbon isocyanate hav b=o (-o ing 1-30 carbon atoms. N-H i-H 7. A compound of the formula k k CH) O H. where B is selected from the group consisting of hydro 45 s’ Sonio - r gen and lower alkyl, A is lower alkylene having at least s/ two carbon atoms, R is hydrocarbon having 1-36 carbon k wn2 atoms, and R is hydrocarbon moiety of hydrocarbon isocyanate having 1-30 carbon atoms, R' being in both where R is hydrocarbon having 1-36 carbon atoms, and instances always the same. 50 R’ is hydrocarbon moiety of hydrocarbon isocyanate hav 2. A compound of the formula ing 1-30 carbon atoms. Scip- | 8. A compound of the formula N N-(AO)--C-N N / -R 55 g cha-i-b-och, CH,- N N N-CHCHO-C-N-CH R 2 N2 N / C-(CH2)6C - where B is selected from the group consisting of hydro 9. A urethane formed by reacting one mole of gen and lower alkyl, A is lower alkylene having at least 60 two carbon atoms, R is hydrocarbon having 1-36 carbon Ns -N- atoms, and R is hydrocarbon moiety of hydrocarbon isocyanate having 1-30 carbon atoms. N/3-(cE)-( N 3. A compound of the formula ÖH, . bH, bH, bH bH S/ C with one mole of m-toluene diisocyanate. 10. A compound of the formula R 70 where B is selected from the group consisting of hydro gen and lower alkyl, A is lower alkylene having at least San 3-CHCH-O-5-N-(CH)- --O-CHCH-N. 2 two carbon atoms, R is hydrocarbon having 1-36 carbon C y atoms, and R is hydrocarbon moiety of hydrocarbon k isocyanate having 1-30 carbon atoms. - - - 75 ?ihis diHis

8,987,516 25 26 11. A compound of the formula

NSnc^ -OHCH-O--i-KX-chi-g X---0-CHCH- Nc1N bha dih, 12. A compound of the formula 16. A compound of the formula O N-CBC-O-C-N -N-C-O CHCH-N N n/ Ya O H. C C CH S/ -CHCH,0-- C1s Cas C 13. A compound of the formula 5 duha OCI OC O 8 O -CBCO-C-N N-C-O CECH-N N s/ -enon-->{s-looner N1 tha Iss 14. A compound of the formula 17. A compound of the formula O O. E. N-C-OCLC-- N 25 N N-CCHO-C-N-CH N 1 Sn/ C dutie bah, 30 References Cited in the file of this patent -CHCH.-- UNITED STATES PATENTS So O B 2,468,163 Blair et al. ------Apr. 26, 1949 & He 2,516,626 Haury ------July 25, 1950 15. A compound of the formula 35 2,640,029 Blair et al. ------May 26, 1953 2,662,080 Smith ------Dec. 8, 1953 2,794,810 Cusic ------June 4, 1957 Sn/N-CECH-0---Chs -omeno OTHER REFERENCES Chem. Abstracts, Index to vol. 51, p. 1245S, December CH 40 1951.