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Publication numberUS2267965 A
Publication typeGrant
Publication dateDec 30, 1941
Filing dateJul 18, 1939
Priority dateJul 18, 1939
Publication numberUS 2267965 A, US 2267965A, US-A-2267965, US2267965 A, US2267965A
InventorsAlexander L Wilson
Original AssigneeCarbide & Carbon Chem Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydroxyalkyl glyoxalidines
US 2267965 A
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Description  (OCR text may contain errors)

Patented Dec. 30, 1941 2,267,965 nrpnoxraurrr. GLYOXALIDINES Alexander L. Wilson, Sharpsburg, Carbide and Carbon Chemicals corporation of New York No Drawing. Application Pa., assignor to Corporation, a

July 18, 1939,"

Serial No. 285,081

9 Claims.

This application is a continuation-in-part of my-copending application Serial No. 191,191, flied February 18, 1938.

This invention relates to the production of certain glyoxalidines, or dihydroimidazoles (imidazolines), to wit, those containing alkyl side chains and including at least one hydroxyalkyl side chain. More specifically, the invention comprises the condensation of fatty acid compounds having from 10 to carbon atoms in the molecule, or mixtures of these, with hydroxyalkyl alkylene polyamines to produce substituted glyoxalidines- While it is possible by this process to obtain the tetrasubstituted glyoxalidines, this invention is particularly concerned with the production of the 1,2-disubstituted and the 1,2,4 or

1,2,5-trisubstituted glyoxalidines in which at least one substituent group is a hydroxyalkyl radical.

The new compounds are characterized as being either high-boiling viscous liquids, or lowmelting, waxy solids and by being highly polar andstrongly basic. They are colloidally dispersible in cold water, giving rise to viscous solutions, and they are completely soluble in acids, such as dilute hydrochloric acid. The glyoxalidine compounds of this invention may be used for various purposes, and it has been found that they are especially valuable as emulsifying agents, detergents, wetting, softening and scouring agents, and for other uses where their properties of surface activity can be employed. The new substances, and their salts and soaps, when used as emulsifying agents, are particularly emicacious'for producing stable dispersions of mineral oils, or other oleaginous substances and water. The new substances are also valuable as softening and finishing agents for textiles, according to processes set forth in application Serial No. 276,122, filed May 27, 1939, by B. G. Wilkes and A. L. Wilson, and as assistants in dyeing textiles to improve the fastness and other qualities of the dyeing operation.

The production of the substituted glyoxalidines of this invention may be accomplished by dehydrating fatty acid amides of various hydroxyalkyl alkylene polyamines and their substitution products, or, more generally stated, by heating, at temperatures between about 120C. and about 300 0., these amines with free fatty acids, fatty acid esters or amides under such conditions as to effect the splitting out of water in excess of 1.5 mols for each mol of free fatty acid and in excess of 0.5 mol for each mol of combined fatty acid involved. Examples of amines that may be employed in the practice of this invention are hydroxyethyl ethylene diamine, hydroxyisopropyl propylene diamine, hydroxyethyl diethylene triamine hydroxyethyl triethylene tetramine, as well as similar hydroxyalkyl alkylene polyamines. The hydroxyalkyl alkylene polyamines of this invention are of the 1,2 series, that is, at least one amino group and one imino group are attached to adjacent carbon atoms. The term alkylene polyamine" is also defined as including products containing more than one alkylene group. Fatty acid compounds that may be used in the production of the glyoxalidines may include the fatty acids themselves, such as lauric, oieic, linoleic, ricinoleic, stearic and palmitic acids, as well as their salts and esters. Other fatty acids and their salts and esters naturally occurring in such vegetable oils as olive, cocoanut, linseed and cottonseed oils, which have 10 to 20 carbon atoms in their molecule, may also be employed.

The substituted glyoxalidines of this invention may be regarded as dehydration products of substituted ethylene diamines and fatty acids, or their salts and esters. The formation of the glyoxalidine or imidazoline ring from these substances may be considered as a two-step reaction involving, first, the formation of an amide and a molecule of water, and, second, the dehydration of this amide to yield a substituted glyoxalidine and a second molecule of water. Thus, when a fatty acid, such as oleic acid, is employed, two molecules of water ,will be formed per molecule of the starting acid. This reaction is illustrated by the following scheme:

from

wherein It represents an aliphatic radical con i compounds, are represented by the following gentaining from to 20 carbon'ratoms and being theresidue of a higher fatty acid; R1 represents hydrogen or a lower alkyl group; andRz represents an alkylene group, a lower alkyl substituted alkylene group, or ,a radical of the structure CHR1.CHR1 (NH.CHR1'.CHRI1) 12- where R1 remains hydrogen or a lower alkyl group and a: is an integer.

In comparison with the amino alkyl substituted glyoxalidines, disclosed in my copending application Serial No, 191,191, the hydroxyalkyl substituted glyoxalidines of this application are obtained somewhat more readily and with considerably less tendency towards the formation of polyamides or other high-boiling condensation products. Another point of distinction is that,

in preparing the former compounds, it is desirable to use a fairly high molar ratio of alkylene polyamine to fatty acidto insure a high yield of glyoxalidine whereas, in making the latter substances, a satisfactory yield of pure glyoxalidine results when operating with equal molecular quantities of hydroxyalkyl alkylene polyamine and fatty acid. 7

It is true, nevertheless, that the employment ofhigher molar ratios of hydroxyalkyl alkylene polyamine to fatty acid will promote a .higher yield of the desired hydroxyalkyl substituted glyoxalidine but such practice is not required for the success of the reaction. Other factors which act to increase the yield of the hydroxyalkyl substituted glyoxalidines are higher rates of heating attendant with the use of temperatures in the upper portion of the range indicated to be suitable and an increased rate of removal of the water liberated in the condensation. Such an increase may be effected by distilling the water from the reaction vessel as a constant boiling mixture with a volatile water-immiscible diluent. Examples of such liquids are benzene, xylene, toluene, diisopropyl ether, ethyl acetate. ethylene dichloride, and carbon tetrachloride. If a diluent is used in carrying out the reaction, lower temperatures and lower molar ratios of hydroxyalkyl alkylene polyamine may be used and high yields of the desired glyoxalidine obtained nevertheless. This characteristic is illustrated in Example V.

Since the substituted glyoxalidines contain a reactive hydroxy group, it is possible to form esters of these compounds by the reaction of organic acids with the free alcoholic group. Be cause the glyoxalidine compounds are basic, it is possible to form salts or soaps of these compounds by their addition with various acidic substances. including both mineral and organic acids, such as hydrochloric, sulfuric, acetic, ethyl hexoic, and lauric acids. such salts or soaps the solubility of these compounds is enhanced. Quaternary ammonium compounds may also be formed by warming the substituted glyoxalidines with the appropriate reagents, such..as diethyl sulfate, dimethyl sulfate, benzyl chloride and the like. These compounds are usually viscous liquids to wax-like bodies, characterized by their nearly neutral reaction and by their ready solubility in water. These quaternary compounds are perhaps less useful as emulsifying agents and as textile fin- By the formation of,

ishing agents than the substituted glyoxalidines themselves but they possess exceptional qualities as wetting and flotation agents.

The salts, as well as the quaternary ammonium eral structure:

in which R, R1, and R2 are as indicated in the above formula; Y represents an organic or inorganic radical, and R3 is hydrogen, or an alkyl or aralkyl group. The distinction between the salts and the quaternary ammonium compounds is that, in the former, R: is usually hydrogen whereas, in the latter, R3 is usually an alkyl or aralkyl group and Y is generally an inorganic radical.

The following examples will serve to illustrate the invention:

Example I One mol of beta-hydroxyethyl ethylene diamine was mixed with 0.5 mol of commercial oleic acid and heated under reflux for 5 hours until a final temperature of about 270 C. was reached. About 2 mols of water per mol of oleic acid were distilled off during this period. Excess hydroxyethyl ethylene diamine was then removed, and the product, 1-hydroxyethyl-2-heptadecenyl glyoxalidine, was purified by vacuum distillation. This substance was found to be a straw-colored, heavy, viscous liquid, with a specific gravity of 0.935 at 20/20 C. and a boiling point from about 230 to 240 C. at an absolute pressure of 1 mm. of mercury. It was miscible with water at 10 C. to yield viscous solutions and it was completely soluble in dilute hydrochloric and acetic acids. This glyoxalidine is particularly useful for dispersing mineral oils in water and in producing water scourable mineral oils for use as textile lubricants.

Example II One and one-half mols of hydroxyethyl ethylene diamine were mixed with one mol of stearic acid and heated, in the presence of xylene, under reflux for 8 hours at a temperature of from C. to C. About 1.5 mols of water per mol of stearic acid were distilled oil! as a constant boiling mixture with the xylene during this period. Excess amine and xylene were then removed, and the product, 1-hydroxyethyl-2-heptadecyl glyoxalidine, was purified by vacuum distillation. This substance was a light-colored solid, insoluble in water, melting at 45 to 55 C.,

and boiling at 240 to 250 C. atan absolute pressure of 1 mm. of mercury. This product is es- I pecially valuable as a softening and finishing agent for regenerated cellulose fabrics, cotton, and similar fibrous materials and as an assistant in dyeing textiles to improve the fastness and substantivity. It is also useful where surface.

a water-soluble wax-like solid and is valuable as 75 an emulsifying agent and as a textile finishing.

lameness v 3 agent. It is also very useful as adetergent being 1 molar quantities of the reactants used in each unaffected in its action by hard water, or by dilute salt water or even by acid solutio Example III Two mols of hydroxyethyl ethylene cliamine were mixed with one mol of cocoanut fatty acids and heated for 3 hours at a temperature of from 170 C. to 270 C. During this period 1.8 mols of water were distilled off. Excess amine was removed and the product, l-hydroxyethyl-2-undecyl glyoxalidine, was purified by vacuum distillation. This substance was a straw-colored semi-crystalline solid with a melting point of 35 to 40 C., a specific gravity of 0.950 at 20/20 Example IV One mol of oleic acid was heated with two mols of N-beta-hydroxypropyl propylene diamine, believed to consist of the structure H2N.CH. CH:.N.CH2. $11. OH

H: H CH:

and its isomers, for 5 hours at a temperature of from 170 to 273 C. During-this period nearly 2 mols of water were removed by distillation. The excess amine was then removed and the product, l-hyclroxyisopropyl 2 heptadecenyll-methyl glyoxalidine, was purified by vacuum distillation. The pure substance was a light-colored liquid having a specific gravity of 0.920 at 20/20 C. and a boiling point of 225 to 235 C. at an absolute pressure of 1 mm. of mercury. The glyoxalidine was slightly soluble in water and completely soluble in dilute acid solutions. These solutions showed typical surface active properties, such as foaming and emulsifying action.

This compound may be prepared by reacting propylene diamine, having the structure H:C.CH.CH:.NH:

NHg, with propylene oxide, H;CHCCH2 Four isomers are possible dep ending on the amino group hydroxyalkylated and on w ether the propylene oxide adds in its alpha or beta position to the amino group.

Example V No. l norylene No. 2 xylene present present Hy ethyl ethylene dinmine My pm" 104 104 Oleio acid -.do--.. 282 282 xylene do.-.. None 91 Time oi reactio 5 Final temperature. ...C 310 205 Water removed .parts. 27' 7 Appearance of final product Dark sludge Lighthclslar Solubility in water Not miscible M igdllaat -Peroent glyoxalidine by distillation at220 M280 C.and2mm per cent 41 81 From this example, it is apparent that carrying out the reaction in the presence of a waterimmiscible liquid diluent is more than a convenient expedient for removal of the water of dehydration. Decidedly superior results have been obtained by this procedure.

I claim:

1. As surface active agents, substituted glyoxalidines of the formula B-C CHI-R1 HoR,1 I -tH.R. in which R is an aliphatic radical containing from 10 to 20 carbon atoms; R1 is of the group consisting of hydrogen and lower alkyl; and R:

til

is of the group consisting of an alkylene hydrocarbon group, a lower alkyl substituted alkylene hydrocarbon group, and a radical of the structure CHR1.CH R1 (NH.CHR1.CHR1) 1- where a: is an integer.

2. As surface active agents, substituted glyoxalidines of the formula in which R is an aliphatic radical containing from 10 to 20 carbon atoms; R1 is of the group consisting of hydrogen and methyl; and R2 is an alkylene hydrocarbon group, a lower alkyl substituted alkylene hydrocarbon group, or a radical of the structure CHR1.CHR1 (NH.CHR1.CHR1) z:-

where a: is an integer.

3. As surface active agents, salts of the glyoxalidines defined in claim 1.

4. As surface active agents, quaternary ammonium compounds of the glyoxalidines defined in claim 1.

5. As a surface active agent, l-hydroxyethyl-Z- heptadecenyl glyoxaldine, being characterized as a viscous liquid, completely soluble in dilute hydrochloric acid, and boiling from about 230 to 8. Process for making substituted glyoxalidines which comprises heating a mixture containing a free hydroxyalkyl alkylene poiyamine of the 1, 2 series and at least one of group consisting of free fatty acids containing from 10 to 20 carbon atoms, amides of said acids, and esters of said acids, at temperatures between about*120 and about 300 C., and removing water continuously from said mixture during said heating, the temperature and the duration of said heating being so correlated as to cause the splitting out of. water in excess of 1.5 mols for each mol of free fatty acid and in excess of 0.5 moi for each moi of combined fatty acid involved.

with said diluent during said heating, the temperature and the duration of said heating being so correlated as to cause the splitting out of water in excess of 1.5 mole for each moi of fatty acid involved.

ALEXANDER L. WILSON.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2416552 *May 29, 1940Feb 25, 1947Richards Chemical Works IncConversion of alkylolamides into oxazolines
US2418077 *Aug 13, 1943Mar 25, 1947Monsanto Chemicals1, 2-disubstituted-4, 5-dihydroimidazoles
US2450534 *Aug 4, 1945Oct 5, 1948Huber Corp J MEmulsion printing inks
US2496640 *May 18, 1944Feb 7, 1950Nopco Chem CoFat liquoring and alum tanning
US2496641 *Nov 12, 1946Feb 7, 1950Nopco Chem CoFat liquoring and alum tanning
US2508415 *Feb 13, 1946May 23, 1950Monsanto ChemicalsMethod of making 4, 5-dihydroimidazoles
US2509260 *Apr 19, 1946May 30, 1950Us Vanadium CorpMethod of filtration
US2528378 *Sep 20, 1947Oct 31, 1950John J Mccabe JrMetal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2659731 *Sep 26, 1950Nov 17, 1953 Cakbocyclic monocarboxyijc acid
US2662857 *Mar 26, 1948Dec 15, 1953Pennsylvania Salt Mfg CoPickling bath agent
US2669546 *Dec 23, 1949Feb 16, 1954Alrose Chemical CompanyDetergents containing imidazoline lactates
US2781357 *Dec 3, 1954Feb 12, 1957John J Mccabe JrImidazoline derivatives and process
US2874074 *May 8, 1956Feb 17, 1959Nat Aluminate Corp1, 2-substituted imidazolinium salt and treatment of cellulosic fibrous materials therewith
US2875210 *May 17, 1956Feb 24, 1959Nat Aluminate CorpChemical compositions
US2901430 *Nov 6, 1953Aug 25, 1959Gen Aniline & Film CorpCorrosion inhibition
US2953535 *Sep 11, 1957Sep 20, 1960Borden CoResin binder compositions
US2987514 *Mar 3, 1958Jun 6, 1961Petrolite CorpPolyesters
US2987521 *Mar 3, 1958Jun 6, 1961Petrolite CorpPolymeric partial esters of hydrocarbon-diimidazolinylalkanols and dicarboxylic acids
US3047425 *Jul 16, 1959Jul 31, 1962Monsanto ChemicalsMethod for producing flame and soil resistant acrylic polymer fibers containing carpet fabric
US3138610 *Mar 10, 1961Jun 23, 1964Gen Aniline & Film CorpSubstituted imidazolines
US3216957 *Aug 14, 1962Nov 9, 1965Union Carbide CorpAntistatic thermoplastic vinyl resin compositions comprising oxyalkylated imidazolines
US3231494 *Aug 22, 1961Jan 25, 1966Exxon Research Engineering CoRust preventive prepared from sodium nitrite and the reaction product of fatty acid and imidazoline
US3251853 *Feb 2, 1962May 17, 1966Lubrizol CorpOil-soluble acylated amine
US3313825 *Jul 7, 1965Apr 11, 1967Geigy Chem CorpCertain imidazoline salts
US3317556 *Sep 8, 1965May 2, 1967Nopco Chem CoAmphoteric alpha-sulfo-imidazolines
US3468904 *Oct 24, 1965Sep 23, 1969Hodag Chem CorpProduction of light-colored fattyderived amino-containing compounds
US4095941 *Sep 30, 1975Jun 20, 1978Hoechst AktiengesellschaftFiber preparation agents to produce a marked separating capability
US4117231 *May 19, 1977Sep 26, 1978The Miranol Chemical Company, Inc.Nitrogenous condensation products
US4189593 *May 1, 1978Feb 19, 1980Baker Thomas GProcess for making imidazolines
US4212983 *Dec 20, 1978Jul 15, 1980Albright & Wilson LimitedManufacture of imidazoline compounds
US4233451 *Oct 20, 1978Nov 11, 1980The Procter & Gamble CompanyProcess for making imidazolinium salts
US4954635 *Sep 6, 1989Sep 4, 1990The Procter & Gamble CompanyProcess for preparing quaternized imidazoline fabric conditioning compounds
US4968443 *Jul 22, 1988Nov 6, 1990Colgate-Palmolive CompanyAlkyl or alkylbenzene hydroxyethyl imidazoline
US5024677 *Jun 11, 1990Jun 18, 1991Nalco Chemical CompanyMixtures of substituted imidazolines and olefin-substituted cyclic succinimides
US5334329 *Oct 7, 1988Aug 2, 1994The Lubrizol CorporationLubricant and functional fluid compositions exhibiting improved demulsibility
US5334639 *Feb 8, 1993Aug 2, 1994Ppg Industries, Inc.Starch oil sizing composition and glass fibers treated therewith
US5393335 *Apr 23, 1993Feb 28, 1995Ppg Industries, Inc.Consists of low viscosity starch, nonionic and cationic lubricants, water, humectant, silane coupling agent, emulsifier, biocide and defoamer
US5393379 *Apr 22, 1993Feb 28, 1995Ppg Industries, Inc.Wet laid fiberous thermoplastic material and aqueous dispersion for producing same
US5466528 *Oct 17, 1994Nov 14, 1995Ppg Industries, Inc.Chemically treated glass type substrates with vinyl polymer compatibility
US5747431 *Jan 12, 1995May 5, 1998Diversey Lever Inc.Imidazoline derivative, amino amide
US6372918 *Jun 30, 2000Apr 16, 2002Clariant GmbhCorrosion inhibition on apparatuses for conveying and transporting hydrocarbons in oil production and processing which contact salt water systems
EP0002943A1 *Dec 21, 1978Jul 11, 1979Albright & Wilson LimitedProcess for the manufacture of imidazolines
EP1130012A2 *Feb 27, 2001Sep 5, 2001Fratelli Ricci - Fabbrica Prodotti Chimici S.r.l.A process for the preparation of amphoglycinates from vegetable oils and butters and the use thereof
WO2001025214A1 *Sep 28, 2000Apr 12, 2001Hercules IncMethod of producing low-odor imidazolines, imidazolines produced thereby and paper and paper products containing the same
WO2007039488A1 *Sep 22, 2006Apr 12, 2007Basf AgHydroxyalkyl-substituted aminoalkylamides of fatty acids as friction modifying agents
Classifications
U.S. Classification548/350.1, 548/349.1, 564/503, 508/283
International ClassificationC07D233/16
Cooperative ClassificationC07D233/16
European ClassificationC07D233/16