Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
  • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
  • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
  • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
  • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

• novel compounds are surface active and substantive to fibrous materials such as cotton, wool and synthetics. They are useful as detergents or as components of detergent compositions. Preferred compounds function very effectively as softening agents, either alone or in conjunction with other detergent composition materials. Additionally, they may be used as starting materials for the manufacture of corresponding N-oxldes, which also may be employed as detergents and textile softeners.
• the present invented compounds are useful surface active agents. They possess detergent activity in both hard and soft waters and at both elevated and lower temperatures. In addition, preferred compounds are excellent in textile softening activity, even when used in the washing, rather than the rinsing step of a laundering operation. Such an activity evidences a high degree of substantivity, which is unexpected in a surface active material which itself functions to release adsorbed and absorbed substances from materials being washed.
• the compounds are also generally capable of making washed textiles and other articles anti-static. Additionally they are usually desirably low-foaming in wash water.
• R is an aliphatic hydrocarbon radical of 4 to 20 carbon atoms
• R and R are divalent, aliphatic or aromatic hydrocarbon radicals of l to 9 carbon atoms
• X and Y are hydrogen or a salt-forming element or radical.
• R and R may be the same or different and X and Y may be the same or different. If either X or Y is an element, it is preferred that it should be an alkali metal, an alkaline earth metal or other suitable salbforming metal, capable of making the compounds water soluble.
• X or Y is a radical, it is preferred that such be ammonium, alkylamine or alkanolamine, either mono-, di-, or tri-alkylamine or mono-, dior tri-alkanolamine, in which the alkyl and alkanol groups of the salt-forming amines are of l to 4 carbon atoms, preferably 2 to 3 carbon atoms.
• the compounds are those wherein R is an aliphatic hydrocarbon radical of 12 to 20 carbon atoms, R and R are aliphatic alkylene radicals of l to 2 carbon atoms, and X and Y are monovalent salt-forming ions, including alkali metal, ammonium, mono-, diand tri-alkylamine and mono-, diand tri-alkanolamine.
• R and R are the same and that X and Y are the same.
• X and Y stand for a monovalent portion of any salt-forming ion.
• a divalent ion such as magnesium
• it could be joined to both the carboxylic groups of the present compounds or could be joined to only one of them, with another valence bond either otherwise tied up, as with a different anion, or with it joined to the carboxylic groups of different iminodicarboxylic acids.
• mixed salts may be formed,'as may be acid-salt compounds.
• the preferred compounds mentioned above are found to be excellent as textile softeners, especiallyfor cotton articles, which may be washed with them, even in the presence of builders, other deters'ive compounds and additives. They may be used in normal washing, including rinsing operations.
• the most preferred compounds are the salts of N-(2-hydroxy-higher alkyl) iminodi-lower carboxylic acids, wherein the higher alkyl is of 14 to 22 carbon atoms and is of straight chain structure.
• the most preferred is acetic acid, so that the most preferred of these compounds are the N-(2- other compounds within the scope of the present invention are also useful surface active agents, wetting agents, emulsifiers and detergents, but might not produce to the same extent the extremely desirable softening activity shown by the most preferred compounds of this invention. In fact, in some instances such compounds might be essentially ineffective as practical softeners, although they will often have the unexpected advantage of being highly useful for their detergency or other surface active properties, often in both hard and soft waters, and at elevated or comparatively low washing temperatures.
• the hydrocarbyl groups of R include both saturated and relatively slightly unsaturated groups. Thus, one or two double bonds per R are acceptable and are within the present invention, although it is preferred to em ploy alkyl groups as R.
• alkyl groups straight chain alkyls, terminally joined to the carbon to which the hydroxyl group is attached are highly preferred and are those described herein, unless indicated differently, although those alkyl groups which are not terminally joined also possess utility, as do various alkyl groups of non-linear structure.
• medially joined keryl (alkyl derived from kerosene) groups may be employed for R and there may also be used various polymeric materials, such as propylene tetramer and pentamer, a preferred form of which is such a mixture thereof as to average 13 carbon atoms per group.
• R and R are preferably short chain alkylene, usually of l to 2 carbon atoms, but longer chain alkylenes and divalent hydrocarbyl radicals containing aromatic moieties are also useful to make detergent and softener products.
• the alkylenes will be present with a carbon content of the alkylene groups, R and R of four or less but in some instances as many as 9 carbon atoms may be found in such group to be good for making novel and useful surface active materials.
• aromatic materials it is preferred that they be derivatives of benzene, usually with no more than two substituents on the benzene ring, in addition to joinder of the benzene ring to the rest of the present molecule.
• X and Y while they may be hydrogen, are preferably salt-forming ions.
• the salts made are usually more stable and freer flowing than the acids and because the product is most frequently employed in alkaline solutions, it is therefore preferably in the salt form.
• the salt-forming ions those which are monovalent are generally preferred, usually because of their greater water solubility, which is an important feature in the use of the present compounds in aqueous systems. However, even if water solubility is low, salts of low solubility can be employed as washing agents in other polar media and may be useful in an aqueous medium, especially if solvents or solubilizers are present.
• novel compounds of the present invention can be prepared by reacting a hydrocarbon-1,2-epoxide with an iminodicarboxylic acid. Such reactions are in accordance with the equation:
• the reaction normally goes in aqueous solution wherein iminodicarboxylic acid, as the salt dissolved in the aqueous medium, is mixed well with an approximately stoichiometric proportion of the hydrocarbonl,2-epoxide.'Often, an additional solvent, such as alcohol, is employed, together with heat.
• the product is generally separated by conventional techniques, which may include treatments with a ketone to produce an oily precipitate, deoiling of such precipitate and conversion of the residue to a crystalline solid, which may be recrystallized from an alcohol to a desired purified product.
• the iminodiacids and their salts are known compounds, as are the hydrocarbon epoxides. Methods for making such compounds from readily available starting materials are also known to those of skill in the art. Accordingly, they need not be described herein. Similarly, methods for making hydrocarbon-1,2-epoxides are known, and details thereof need not be given here.
• reaction in the reaction of although stoichiometric proportions are preferred, it is within the present invention to employ an excess of either reagent, depending upon the circumstances, with the usual excess not exceeding 50 percent and rarely exceeding 20 percent.
• the reaction may be effected at various temperatures, it is normally preferred to initiate it at approximately room temperature, e.g., 30C.
• the iminodiacid reactant is dissolved in an aqueous medium and it is preferred to utilize deionized water for such medium.
• the proportion of water employed may be relatively small, and usually it is preferred to use from 25 to 200 percent of the total weight of the reactants.
• the epoxide usually as a liquid
• the epoxide is admixed with the dissolved reagent.
• Such admixing may take from 10 seconds to 1 hour and during mixing the temperature of the reaction mixture is held within the mentioned room temperature range.
• the temperature is usually raised to from 50 C. to 110 C., depending upon the materials being reacted.
• the temperature most conveniently employed is the reflux temperature of the reaction mix.
• the reaction mixture is held at such temperature for a period of from about 1 hour to about 42 hours, after which it is considered that the reaction is complete.
• a one-phase system is found, from which the product may be obtained by precipitating with a suitable lower ketone, e.g., acetone, methyl ethyl ketone, diisopropyl ketone or other ketone having one to four carbon atoms in the alkyl groups thereof.
• a suitable lower ketone e.g., acetone, methyl ethyl ketone, diisopropyl ketone or other ketone having one to four carbon atoms in the alkyl groups thereof.
• Conversion to a solid crystal form may often be effected by treatment with a lower alcohol, such isopropanol or ethanol, after which purification may be effected by recrystallization from such solvent.
• the products obtained are usually white or lightcolored solids, which in some cases may have a yellowish tinge.
• the solids may be somewhat hygroscopic but usually are sufficiently free-flowing to be employed, either by themselves or with other materials, as surface active agents or softeners for textiles.
• novel compounds produced are normally utilized in aqueous solution, either alone or with additives to produce improved detersive solutions or emulsions and to act as wetting agents. They are also used in such compositions to soften fabrics, especially cotton textiles, although they also soften other fabrics, such as wool and synthetics.
• the invented compounds usefully wash and soften textiles in a single operation. Such activity, wherein the softening agents are effective despite being added tothe wash water, rather than the rinse water, and wherein they themselves actto remove other substances from the fibers or laundry being washed, is considered to be unusual. Such softening effect appears to depend in significant part upon the substantivity of the invented compounds to the fibers.
• many of the present compounds are highly useful in combination detergent-softeners. The advantages of such compounds, as opposed to separate detersive and softening materials, have been recited previously.
• the salt of iminodiacetic acid employed is the dipotassium salt, the di-ammonium salt, the di-triethanolamine salt or the mixed sodium-potassium salt, and the same general method for manufacture described aboveis employed, the corresponding N-(2-hydroxy-dodecyl)- iminodiacetates are obtained.
• the stoichiometrically equivalent amounts of such iminodiacetates will be employed in such reactions. Similar results are obtained when the acid form is employed.
• Example 1 The procedure of Example 1 is also followed, utilizing different iminodicarboxylates, such as iminodipropionic acid, disodium salt; iminodibutyric acid, dipotassium salt; iminoacetic-propionic acid,
• the times of reaction are extended or the temperatures are increased to promote reaction, whereas in other instances, a shorter time is needed and lower temperatures are employed, as will be evident to those of skill in the art.
• the recovery methods utilized may be varied in specific situations to allow the production of the greatest proportion of the purest compounds.
• Example 2 The procedure of Example 1 is followed except that 480 parts of n-hexadecane-l,2-epoxide are employed instead of the 368 parts of n-dodecane-1,2-epoxide, and the refluxing is continued for 24 hours. At the end of that time, the reaction mixture has become water soluble and a single phase is produced.
• the desired product, N-(2-hydroxy-n-hexadecyl)-iminodiacetic acid, disodium salt, is recovered by the method described in Example 1.
• the product is a white powder of similar characteristics to that produced by the method of Example 1.
• the cycloalkyl epoxides and the highly branched alkyl epoxides may also be employed, as may be the slightly unsaturated hydrocarbyl epoxides, such as the olefinic or dienic epoxides.
• the products resulting are useful surface active agents and in many cases possess exceptionally good textile-softening properties.
• EXAMPLE 3 Although the products described in Example 1 and 2 possess general utilities as surface active agents, surface tension reducing agents, emulsifiers, detergents or softening agents for textiles, especially useful softening and detersive actions are noted for those compounds wherein R is of 12 to carbon atoms.
• An especially useful compound of this type is N-(Z-hydroxyhexadecyl)-iminodiacetic acid, disodium salt, which is representative of the best such compounds.
• N-(2- hydroxyhexadecyl)-iminodiacetic acid, disodium salt When tested for efficacy as a fabric softener, N-(2- hydroxyhexadecyl)-iminodiacetic acid, disodium salt, obtains a rating of 10+, indicating an excellent softening effect on cotton materials.
• the test is run using onehalf of a terrycloth towel in 3 gallons of 100 p.p.m. hardness water, at 120F. containing a detergent composition comprising 6.6 grams of sodium tripolyphosphate and two grams of N-(Z-hydroxyhexadecyl-iminodiacetic acid, disodium salt. After washing in a mini-basket of a General Electric Company automatic washing machine, the towel is rinsed in the usual way and is essentially freed of water.
• the Spangler soil detergency tests are run using 15 percent of each of the mentioned compounds, 35 percent sodium tripolyphosphate and 50 percent sodium sulfate, to make a textile-softening and detergent composition.
• concentration of such washing preparation employed is 0.15 percent in water, which corresponds to the recommended usage of such materials in a home automatic washing machine.
• Three cotton percale swatches, each 3 inches by 6 inches, are first soiled with Spangler soil, which is a mixture of airborne and sebum soils. They are then washed in a Tergotometer evaluating washing machine, using waters of two different hardnesses, at two different temperatures, as indicated.
• the swatches are rinsed and are tested for whiteness, using a color difference meter.
• the comparison of readings, using the Rd scale, between the materials before and after washing, is made and the delta Rd is calculated.
• Linear tridecyl benzene sulfonate, as the sodium salt, is usuallyemployed as a standard of comparison for detergency in this test.
• R is alkyl of 12 to 20 carbon atoms, or alkenyl of 4 to 20 carbon atoms containing one or two ethylenic double bonds
• R and R are alkylene radicals of l to 9 carbon atoms
• X and Y which may be the same or different, are selected from the group consisting of hydrogen, alkali metal, ammonium, monoalkylamine, dialkylamine, trialkylamine, mono-alkanolamine, dialkanolamine, and trialkanolamine, in
• alkyl and alkanol groups are of l to 4 carbon atoms.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 0
  • BE BE759533D patent/BE759533A/xx unknown
• 1969
  • 1969-11-28 US US00880992A patent/US3725473A/en not_active Expired - Lifetime
  • 1969-11-28 US US00880915A patent/US3726797A/en not_active Expired - Lifetime
  • 1969-11-28 US US00880991A patent/US3755435A/en not_active Expired - Lifetime
  • 1969-11-28 US US880977A patent/US3700607A/en not_active Expired - Lifetime
  • 1969-11-28 US US00880909A patent/US3728385A/en not_active Expired - Lifetime
• 1970
  • 1970-11-03 CA CA097,293A patent/CA942458A/en not_active Expired
  • 1970-11-06 CA CA097,622A patent/CA941557A/en not_active Expired
  • 1970-11-06 CA CA097,621A patent/CA941556A/en not_active Expired
  • 1970-11-11 GB GB5368970A patent/GB1319130A/en not_active Expired
  • 1970-11-21 DE DE19702057355 patent/DE2057355A1/de active Pending
  • 1970-11-24 FR FR7042106A patent/FR2099030A5/fr not_active Expired
  • 1970-11-25 CH CH1264774A patent/CH569695A5/xx not_active IP Right Cessation
  • 1970-11-25 CH CH1742970A patent/CH558332A/xx not_active IP Right Cessation
  • 1970-11-30 NL NL7017496A patent/NL7017496A/xx unknown
• 1973
  • 1973-01-17 US US324314A patent/US3864389A/en not_active Expired - Lifetime

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