r 2,786,869 United States Patent ‘ Patented Mar. 26, 1957

l 2 tically, mixtures of tert-alkylamine such as are available on the market. Typical mixtures are those containing ‘ 2,786,869 C12H25NH2 to C15H31NH2 or C18H3'INH2 to C24H49NH2 N-TRIALKYLCARBINYL-N-(HYDROXYETHYL or C15H31- to C24H49NH2. These may be represented by POLYOXYETHYL) GLYCINES the formula Peter L. de Benneville and Homer J. Sims, Philadelphia, 31 Pa., assignors to Rohrn & Haas Company, Philadelphia, R’-—-C—NH2 Pa., a corporation of Delaware Rs No Drawing. Application June 16, 1954, 10 As catalysts in the ?rst step of the process of this Serial No. 437,273 invention, wherein the hydroxyethyl group is introduced, 9 Claims.‘ (or. 260-534) there may be used any of the strong acids, such as hy drochloric, hydrobromic, sulfuric, arylsulfonic, alkanesul fonic, or phosphoric. The preferred amount of this cat This invention relatesto-compounds of the structure 15 alyst is 10 to 30 mole percent of the amine. With R1 '(CH2CH2O),.H ‘ , amines from 12 carbon atoms upward it is exceedingly di?icult to introduce more than one hydroxyethyl group in a tert-alkylamine molecule. Such amines‘yicld ?nal 3 \CHrCOOH products which have the desired balance of properties. ' wherein R1, R2, and R3 are alkyl groups containing a 20 The ?rst reaction with ethylene oxide is effected by total of 11 to 23 carbon atoms and n is an integer having bringing together ethylene oxide and tert-alkylamine, a value from 5 to about 50 or more, preferably 5 to 25. usually by passing ethylene oxide into amine and catalyst, These compounds may be called N-(trialkylcarbinyl)-N at temperatures from 0° to 180° C. The preferred tem (hydroxyethylpolyoxyethyl)glycines or N-carboxymeth peratures for reaction are between 60?’ and 95° C. yl-N-trialkylcarbinylaminopolyethoxyethanols. ‘ 25 Upon addition of one mole of ethylene oxide per mole As these names suggest, these compounds are poly of a said tert-alkylamine in the presence of an acid cat ether alcohols and glycines. They possess in ‘addition alyst reaction ceases. The acid catalyst is then de to the ether chain which‘ confers marked polarproperties stroyed, as by adding a base. Sodium or potassium hy a zwitter-ion which can react with either acids or bases droxide, sodium or potassium carbonate, or calcium hy to form :salts and thereby change the surface active char droxide may be used for this purpose. A concentrated acteristics of the compounds. In contrast to the usual aqueous alkali solution may be used and the resulting non-ionic surface active agents, these compounds supply aqueous layer is drawn off. If an aqueous solution is not anti-corrosive action. They confer anti-static properties used, the sludge or salt which forms is ?ltered off. The to plastic surfaces, including the surfaces of synthetic reaction mixture is then stripped of any remaining water, ?bers. They are preferentially absorbed on various 35 as by heating under reduced pressure. This step is solids, including pigments, ores, and other minerals and necessary to avoid formation of polyethylene glycols in can thus assist in classi?cation, ?otation, dispersion, and the subsequent reaction. adhesion. They can be used as anti-foam agents, as in In the next stage of reaction the monohydroxyethyl paper manufacture. They have bactericidal and fungici compound is treated with 0.5 to 5 mole percent of an dal properties. They can be used as emulsi?ers and as 40 alkaline catalyst and with ethylene oxide in an amount deemulsi?ers. They are effective wetting agents in many to give the particular kind of product required. Sodium textile and paper applications. Also, the compounds of. hydroxide or potassium hydroxide provide good catalytic this invention can be incorporated into plastisols and action, but alkali metal alcoholates, such as sodium meth organasols to reduce the viscosity thereof. 45 oxide or potassium butoxide may also be used. The re The compounds of this invention can be considered to action may be run under ordinary or elevated pressures. be derived from tert-alkylamines through an interesting A pressure of 10 to 20 p. s. i. provides a rapid‘rate‘of series of reactions which are eifective because of the reaction at temperatures from 100° to 200° C. The pre peculiar nature of the trialkylcarbinyl group in its rela ferred range is 130° to 170° C. \ tionship to the rest of the molecule. The course of re 50 When four or more units of ethylene oxide have been action is also determined by the size of the trialkylcar taken up at this stage per molecule of hydroxyethylated binyl groups used, these being of 12 to 24 carbon atoms. tert alkylamine, ?nal products are obtained which are With this particular kind of group of the de?ned size the water-soluble. As the number of ethoxy groups increases ?rst stages of reaction lead to the introduction of a poly above four, improved solubility and increased polarity > are observed. The products can thus be adjusted to give i ethoxyethanol group replacing only one of the two hydro 55 gens on the nitrogen of the primary amine, RN'I-Iz, al an optimum effect for any speci?c application. I though it would appear that both are of equal value and Details of typical procedures for preparing the l activity. Two steps are required to introduce a poly RNH(CH2CH2O)71.H 1 ethoxyethanol group, the ?rst giving an N-hydroxyethyl compounds are given in the following section. t compound and the second carrying this compound to 60 i the polyethoxyethanol. When the polyethoxyethanol PREPARATION A group has been introduced, giving compounds of the There were mixed in a reaction vessel equipped with formula RNH(CH2CH20)1LH, these compounds are re stirrer, thermometer, and inlet tube 286 parts of a techni acted with formaldehyde and hydrogen cyanide or the cal tert-octadecylamine, which comprised chie?y C18 equivalent thereof, to give monocyanomethylated prod 65 amines with some higher tert-alkyl primary amines, and ucts, RN(CH2CH) (CH2CH2O)nH. These are now sub 28.6 parts of aqueous 35% hydrochloric acid. The mix jected to hydrolysis with an aqueous alkali metal hydrox ture was stirred and heated to about 90° C., whereupon ide solution and the resulting salt separated or converted ethylene oxide was introduced through the inlet tube. to the acid form, RN(CHZCOOH)(CH2CH20)1LH The temperature was held at 90°-94° C. and the pres As, trialkylcarbinylamines there may be used any of 70 sure at one to ?ve pounds gauge until 44 parts of ethylene the primary N-tertiary alkylamines having 12 to 24 car oxide had been added. The water was then taken off bon atoms. Single entities may be used or, more prac under reduced pressure and about 200 parts of aqueous 2,786,869

5%‘v sodium hydroxide'isolution added. The water layer No. 371,194, ?led by Gerard C. Riley on July 29, 1953, was taken off and a second 200 part portion'of 5%- so the‘ assignment'of' which is‘ in-the‘hands'of'a- common dium hydroxide added and then separated. The washed assignee. Suf?cient of the disclosure has been here in oil was stripped under low pressure and ?ltered to give troduced to give a clear and complete exposition of the 3'30‘~parts of‘aiclear‘redv oil. This‘ had a neutral equiva preparation of the tert-alkylaminopolyethoxyethanols lentiof132‘6', thus ‘corresponding essentially to'N-hydroxy which are required for the preparation of the glycines of ethyl-tert-octadecylamine, the theoretical'netural equiva~ this invention. lent being 330. After a tert-alkylaminopolyethoxyethanol has" been A portion of 99 parts of this oil was treatedlwith 0.3 formed, it is reacted with formaldehydeand hydrogen part of potassium hydroxide: There was added thereto 10 cyanide, thus over a period of four hours 132~parts of ethylene oxide RNH(GH2GH2O),.H-+;HOHO + HCN~‘-—-+ with the temperature held at 160°—170° C. at one to ?ve pounds pressure (gauge). The reaction mixture was treated. with;1;3 parts of; 20% sulfuric, acid, stripped, andi?ltered. ' 15 The order in which these reactants are mixed or com The ?nal product wasaiclear red oil which was soluble bined is not critical. Excess formaldehyde and hydrogen in water to. giVeFsUrfa‘ce active solutions and which cor cyanide are permissible and may be supplied to the re responded;inicompositio'nlto‘ action mixture as separate reactants. Again, the tert alkylaminopolyethoxyethanol may be- ?rst‘ treated‘ with tei'f-CiaH1'zNH'( CH2‘CH20) roCHzCI-IQOH - 20 formaldehyde, asfrom the aqueous solutions of com PREPARATION B merce and hydrogen cyanide then added as liquid or gas A technical mixture of"trialkylcarb'inylamines' from at temperatures from 0° to 50° C. or more. It is more C18 to Czt‘having'a‘neutral equivalent of 360 was re convenient, however, to react formaldehyde and cyanide acted'as in Preparation‘ A with‘ a molarproportion of in a separate step to-form glycolonitrile and this ethylene oxide. There‘ was thereby, formed an N-hy 25 with the tert-alkylaminopolyethoxyethanol. This reac-~ droxyethyl-tert-carbinylamine having a neutral equivalent tion may be carried out in water or an alcohol-water of ‘405, a density at 50° C. of 0.865, and a congealing mixture at temperatures of about 20° to 100° C. The temperature of —15° C. glycolonitrile may be formedby-reacting-formaldehyde Portions of this product were taken and reacted as and hydrogen cyanide or an alkali'metal cyanide'and. above with various‘ proportions of ethylene oxide to give acid; asiis known. tert-carbinylaminopolyethoxyethanols.> Reaction in the Thev N - cyanomethylated tert - alkylaminopolyethoxy proportion of one mole, of N-hydroxyethyl-tert-carbinyl ethanol is? now hydrolyzed. This is done by- heating it amine to‘?ve moles ofv ethylene oxide gave a product with anl‘aqueous solution‘ of an alkali‘ metal hydroxide. having an average of‘?ve ethoxy groups, having a density Temperatures from’ 90° to 120° C. are suitable. Am of 0.938’ at 50° C. and a congealing temperature of 0° 35 monia isevolved andithe sodium or potassium or equiva C., andbeing' scarcely soluble‘ in water, but soluble in lent‘ salt-10f the carboxymethyl derivative is formed; such organic solvents as benzene. The solutions in or This salt maybe used as such or it may be’ converted ganic solvents‘ took up ‘water. to the‘ acid form. This‘ is' readily accomplished by? treat- The product formed from a proportion of one mole of ing the salt with a strong. inorganic acid, such as aqueous‘ hydroxyethylamine' to‘ten moles of ethylene oxide had a 40 sulfuric ‘or hydrochloric acid to bringthe solution below composition CnH2n+1NH(CH2CH2O)ioCHzCHiOH, had pH 7. The inorganic salt formed is conveniently re a density'ofi0.9r70 at 50° C. and a congealing point of moved by taking upthe reaction product in a solvent in 6° C., and‘was spontaneously emulsi?able in water. which'the saltais insoluble and ?ltering o? the salt. There The'product formed from a proportion of hydroxy are, of course, applications for'which removal‘ of inor ethylamine'to oxide of 1:15 corresponded in composition ganic salt. is unnecessary and then this lastv step is not to CnH2h+1NH(CH2CH20)15CH2CH2OH, had a density required. of 1.005 at'50°' and a congealing point of 8° C., and was Typical'preparations of the compounds of this inven soluble'in water up to 62°‘ C. . v tion are presented in the following illustrative examples, The product formed from a proportion- of hydroxy wherein parts are 'by Weight. ethylamine to oxide from. 1:20 corresponded in composi 50 Example.‘ 1 tion to‘ CnH2n+1NH(CH2CH2O)20CH2CH2OH, had a density of.1‘.020 to 50° C. and'a congealing point of 12° As the starting material-in this synthesis'rthereiis se C., and was‘ soluble in water up to 94° C. lected a commercial tert-alkylaminewhich has an average molecular weight of.320'andtwhich‘consists of a mixture PREPARATION ’ C ' 55 of'amines' of the formula RNI-I2,.where R represents alkyl Ethylene-oxide was passed at 80° C. intoa mixture of groups of'15 to 24' carbon atoms joinedIto‘ the nitrogen 200‘ parts'of trialkylcarbinylamine‘containing‘ chie?yr a at a tertiary carbon atomthereof. This amine is reacted tert-'dodecyl group together with some higher alkyl groups withz'ethylene. oxide, as described above‘,.in two- stages up to tert-pentadecyl,“20'parts of aqueous 35% hydro to give. an.N-polyethoxyethanol product with an average chloric acid, and 15 ‘parts of water. After three hours 32 60 —C2H4— group content of 15. parts of ethylene oxide" hadibeenireacted. The reaction There are‘mixed 99 parts of this tert-alkylarninopoly mixture was. washed with aqueous 15% sodium hyr ethoxyethanol ‘and 8 parts ofan aqueous 71.4% glycoloni droxide solution and with 250 parts of water. The re trile' solution, which‘ has been made by bringing for action mixture was then'distilledl After unreacted amines maldehyde and'hydrogen cyanide together in an aqueous had been taken-off, a main fractionof 139 parts of N 65 solution at 20 f‘-25° C. in the presence of a small amount hydroxyethyltrialkylcarbinylamine was obtained at 157 °— of pyridine as catalyst and then acidifying the solution. 1169" C./ 15 mm. The residue amounted to 14 parts. The mixture is stirred and heated at 50° C. for 4.5 hours. The, main fraction, havinga neutral equivalent of 235, The reaction mixture is then heated under .reduced pres was treated as‘ abovelwithi three mole percent of. sodium sure to remove. water. Thisleaves' a residueyof 102 parts, hydroxide and with ethylene oxide in amole ratio .of. 70 which. is identi?ed as . a, composition’ of the. formula: 10i1, oxide to" amine. The product gave clear. solutions. RN(CH2CN) (CH2CH2O)15H. This material contains by in water which-are highly surface active, giving. rapid analysis 2.76% of nitrogen; The theoreticalv nitrogen wettingout, and'havingeffective emulsifyingaction. content is. 2.72%. The preparation of‘. tert-aminoalkylaminopolyethox‘ - There are mixed-90 parts. of: the. above composition,. ethanols is described». and claimed inapplication. Serial. 75 50. partsv of. water, and. 12 partsof aqueous :50%.- sodium. 2,786,869 6 hydroxide solution. The mixture is heated under re?ux two hours. At this point the desired aminonitrile has for 15.5 hours. Ammonia is evolved and is collected to been formed, but it need not be isolated. Instead, this indicate the progress of hydrolysis. When ammonia is reaction mixture is treated with 54 parts of water and no longer given off, the reaction mixture is cooled and 12 parts of aqueous 50% sodium hydroxide solution and adjusted to a pH between 5 and 6, as shown by Bogen’s heated under re?ux with evolution of ammonia. The indicator, by adding 11 parts of aqueous 50% sulfuric solution is brought to a pH of 6 by addition of about acid solution. Addition is made of 100 parts of isopropyl 11 parts of aqueous 50% sulfuric acid solution. Iso< alcohol. A salt separates and is ?ltered oif. The ?l propyl alcohol is added to give precipitation of sodium trate is heated to distill oil the alcohol. The product sulfate, about 200 parts being required. The solution is is treated with 200 parts of toluene which is distilled oil 10 evaporated. The residue is treated with 200 parts of tolu to remove moisture present. The last traces of toluene ene, which is distilled oif. A residue of 169 parts re are removed under reduced pressure. The residual prod— mains. Analysis shows 1.2% ash and titration with uct amounts to 67 parts. It contains no inorganic mat standard 0.1 N sodium hydroxide solution shows that at ter as shown by a failure to give ash and corresponds this point 70% of the theoretical carboxyl groups are in ‘composition fairly closely to that of the compound present. RN(CH2COOH) (CH2CH2O)15H. Part of this product is treated again with caustic soda The addition of 1% of this material to a plastisol (made solution to complete hydrolysis. The product is also from equal weights of a dispersion grade of polyvinyl tested in a plastisol, addition of 1% giving a 48% vde chloride and di-2-ethylhexyl phthalate) reduces the vis crease in viscosity. cosity thereof about 45% . 20 Example 4 This material acts as a potent corrosion inhibitor in 10% hydrochloric acid. The tert-alkylaminopolyethoxyethanol of Preparation A is taken as the starting material. This compound cor Example 2 responds closely to the formula The starting amine used in this preparation is the same 25 ‘as that used in Example 1. It is reacted with ethylene oxide as above to introduce ?ve ethoxy groups. To 154 There are mixed 75 parts of this compound and 8 parts parts of this tert-alkylaminotetraethoxyethanol there is of aqueous 72% glycolonitrile solution. The mixture is added 20.4 parts of aqueous 70% glycolonitrile solution. stirred and heated to about 55° C. for four hours and This mixture is stirred and heated at 50° C. for two 30 then heated under reduced pressure to remove Water. hours. The residue corresponds closely in composition to that To this reaction mixture are added 50 parts of water of C18H37N(CH2CN) (CH2CH20)11H, containing 3.58% and 32 parts of aqueous 50% sodium hydroxide solution. of nitrogen (theory 3.57% ). This mixture is heated under re?ux until evolution of There are mixed 75 parts of this intermediate, 40 parts > ammonia is complete. The resulting solution is acidi?ed 35 of Water, and 10 parts of aqueous 50% sodium hydroxide with dilute sulfuric acid to a pH of 6. Isopropyl alcohol solution. This mixture is heated under re?ux for 16 is added to precipitate sodium sulfate, 300 parts being hours. Ammonia is evolved in about the theoretical thus required. The precipitated salt is ?ltered off. The amount. Sulfuric acid is added until the pH of the mix ?ltrate is stripped of isopropyl alcohol. The resulting ture is about 5. Isopropyl alcohol is added until precipi residue is treated with 200 parts of toluene which is dis 40 tation of sodium sulfate is complete. It is ?ltered off. tilled o? to give a residue which is heated under reduced The ?ltrate is evaporated under reduced pressure. The pressure to give 150 parts of an amber-colored product. residue is treated with toluene and the toluene is distilled By analysis this material contains 2.7% of nitrogen and off. The residue is stripped under reduced pressure. gave 0.2% of ash. This material corresponds in com The product is essentially free of ash and corresponds in composition to C1sH37N(CHzCOOH) (CH2CH2O)11H. position to RN(CH2COOH)(CH2CH2O)5H, for which 45 the theoretical nitrogen content is 2.7%. Example 5 When a plastisol from 50% polyvinyl chloride and 50% dioctyl phthalate is treated with 1% of its weight The tert-alkylaminopolyethoxyethanol of Preparation of the above product, there occurs a 41% reduction in C (74 parts) is mixed with nine parts of glycolonitrile 72% solution. This mixture is heated at 50° to 60° C. viscosity. This reduction is well, although not com 50 pletely, retained on storage. for ?ve hours and heated under reduced pressure with The product possesses corrosion inhibiting action, as evolution of water. The residue is the cyanomethylated can be shown by a standard test wherein steel panels are derivative, being chie?y subjected to 10% hydrochloric acid for six hours at 175° C12H25N (CHzCN) (CHzCHzO) 11H C. 55 This product has been examined for anti-bacterial ac with small amounts of higher alkyl derivatives. The tion. Against Salmonella typhosa it has a phenol coe?i nitrogen is 4.14%. The theory for the C12 compound is cient of 4.2. Against Microcaccus pyogenes var. aureus 4.19%. it shows a phenol coef?cient of 17. There are mixed 75 parts of this product, 45 parts of An 0.1% solution in water gives a surface tension of 60 water, and 12 parts of aqueous 50% sodium hydroxide 25.5 dynes per cm. The solutions have good wetting ac solution. This mixture is heated under re?ux overnight tion. Wetting out time by the ?oating patch test is 7 with evolution of ammonia. The reaction mixture is seconds at 1%, 17 seconds at 0.5% and 31 seconds at cooled, treated with 50% sulfuric acid as above to a pH 0.25%. of 5 to 6. Isopropyl alcohol is added until precipitation Example 3 65 of sodium sulfate is ‘complete. This salt is ?ltered 0E In this preparation the above tert-alkylamine is used, and the ?ltrate is concentrated under reduced pressure. but reaction with ethylene oxide is carried on until 25 Water is stripped off with toluene as before to give a prod ethoxy groups have been added. There are mixed 170 uct chie?y of the composition parts of the resulting secondary amine, C12H25N(CH2COOH) (CHzCHzO) 11H RNH ( CHzCHzO ) 25H 70 which may be identi?ed as a N-carboxymethyl-N-tert 8.1 parts of 37% aqueous formaldehyde, and then 2.7 dodecylaminopolyethoxyethanol. parts of cold hydrogen cyanide. The mixture is stirred The same procedure can be applied to produce com at room temperature for several hours, left standing for pounds with 12 to 24 carbon atoms in the tert~alkyl group 16 hours, and heated with stirring at at about 50° C. for 75 and from 5 to 25 to 50 or more ethoxy groups. For 2,786,869; somepurp‘oses» of :wetting, and, emulsifying compounds - heating/it with ,aqueousralkali-met-al hydroxide solution. with 40,_ to‘ 60 ethoxy-~ groups,» are .very ‘desirable. 7. Ahprocess forv preparing N~carboxymethyl-N-tert Weclaim: ' alkylaminopolyethoxyethanols which comprises reacting 1. Compounds, of: the )structure' an N-hydroxyethylpolyoxyethyl - N - tert-alkylamine in whichthe said'alkyl group contains 12. to, 24 carbon Rl' (GHzCHzO);.H“ atoms with glycolonitrile, whereby an N-cyanomethyl-N RITOfN ‘ hydroxyethylpolyoxyethyl-N-tert-alkylamine is- formed, 113' omooorr. and hydrolyzing said amine by heating it with aqueous alkali metal: hydroxide solution, bringing- the resulting where‘gR'l,v R2,',and‘R3 are alkyl, groups totaling11‘to'23 10 solution‘toa pH below 7, and separating an:N-carboxy carb'onatoms and'nis aninteger from 5 to about 50. methyl-N-tert-alkylaminopolyethoxyethanol. 2. carboxymethyllN-tertadodecylaminopolyethoxy 8.- Therprocess of claim7in which the tert-alkylamine eth’anols‘having four. to forty-nine ethoxy groups. is . tert-dodecylarnine. 3." N - carboxymethyl-Nitert-dodecylarninopolyethoxy; 9. The process of claim 7 in which the tert-alkylamine ethanol with ten ethoxy groups. 15 is tert-octadecylamine. 4. N-carboxymethyl-N-tert-octadecylaminopolyethoxy ethanol,‘ having four. to forty-nine eth'oxy groups. References Cited in the ?le of this patent 5; N