Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/402—Amides imides, sulfamic acids
  • D06M13/405—Acylated polyalkylene polyamines

Definitions

• the invention relates to quaternary amidoammonium salts, processes for their preparation and their use.
• the most commonly used fabric softener in this class of compounds is distearyldimethylammonium chloride (see S. Billenstein et al, J. Am. Oil Chem. Society 61 (1984), pages 353-357).
• Textile plasticizers of this type have excellent softening properties, but also have some disadvantages.
• the fabrics treated with it have a reduced absorbency compared to the untreated fabrics, which the consumer e.g. for clothing that is worn in contact with the skin and for terry towels is perceived as unpleasant.
• Such textile softeners can often not be completely removed from the fabric during washing, so that - even with the correct dosage - the softening active substances sometimes accumulate, which likewise reduces the suction effect of the textiles.
• Another serious disadvantage of these fabric softeners is the corrosive effect caused by the chloride anion on metal surfaces, for example on parts of the washing machine.
• Quaternary ammonium compounds are described in Dutch patent application 68/08958 and US Pat. No. 3,591,405, the hydrophobic radicals of which represent hydroxyalkyl groups or alkyl groups linked to the nitrogen via ethoxy groups.
• the quaternary ammonium compounds described in the cited publications were not able to assert themselves in the long term as textile softeners, since either such modified quaternary ammonium compounds are difficult to obtain from a preparative point of view, and therefore cannot be produced on an industrial scale and are therefore out of the question for practical use, or because the softening effect is too low.
• the present invention was therefore based on the object of providing new quaternary ammonium compounds which can be obtained in a simple manner from readily accessible starting materials and, moreover, enable access to a large number of analogously structured products by means of a method which is variable by the choice of the starting materials.
• the new compounds should maintain the absorbency of the textiles treated with them with a good softening effect and should be able to be removed without residue when the textiles are washed. Furthermore, a corrosive effect of the plasticizers against metal parts should be avoided.
• the invention also relates to the use of quaternary amidoammonium salts of the general formula (I) in which R ', R 2 , R 3 , R 4 , R 5 , m, n, p, q, r and X have the above meanings, for the finishing of textiles.
• the quaternary amidoammonium salts of the general formula (1) are new compounds.
• the individual radicals denoted by R 'on the nitrogen atoms can have the same or different meanings. The same applies to the radicals R 2 and R 3 and for the indices m.
• the respective nitrogen atoms of the compounds of the general formula (I) can also carry a group of the general formula (II) at the position denoted by R 1 .
• R 1 the position denoted by R 1 .
• Quaternary amidoammonium salts of the general formula (I) which are preferred according to the invention because they impart good softening activity carry groups of the general formula (II) in one or more of the positions denoted by R 1 in the general formula (I), in which R 4 is hydrogen or Methyl and p represent an integer in the range from 2 to 8.
• radicals R 2 on the nitrogen atoms "terminal" in the chain can also have the same or different meanings. They represent hydrogen, an alkyl group with 1 to 22 C atoms, an alkenyl group with 8 to 22 C atoms or a group of the above general formula (11).
• the straight-chain radicals are methyl, ethyl, propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Uneicosyl and Docosyl.
• R 2 on the two terminal N atoms can also represent their branched chain isomers. It is also possible here for the two R 2 radicals on the terminal N atoms of the compounds of the general formula (I) to have the same or different meanings.
• the radicals R 2 can, however, also stand for alkenyl groups with 8 to 22 carbon atoms.
• the alkenyl radicals are therefore the radicals octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyi, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, uneicosenyl or docosenyl.
• the double bonds can be anywhere on the alkenyl group.
• alkenyl radicals with one double bond in the chain there can also be those radicals with two or more double bonds in the chain. Their positions within the chain are also not subject to any restrictions.
• alkyl groups it is also possible with the alkenyl groups to provide branched-chain radicals.
• alkyl and alkenyl radicals with 8 to 22 carbon atoms which are suitable as radicals R 2 can also be substituted at any point in the hydrocarbon chain with hydroxyl groups.
• Preferred compounds of the general formula (I) are those in which the groups R 2 are derived from those compounds which are obtainable from natural fats or oils by appropriate oleochemical syntheses.
• the spectrum of the compounds of the general formula (I) advantageously includes those compounds in which the radicals R 2 are alkyl groups or alkenyl groups having 12 to 18 carbon atoms.
• R 2 in the compounds of the general formula (I) according to the invention can also stand for groups of the general formula (11), in which R 4 is hydrogen, methyl or ethyl and p is an integer from 1 to 10.
• R 4 is hydrogen, methyl or ethyl
• p is an integer from 1 to 10.
• Such groups have already been defined above in connection with the radicals R 1 in the general formula (I).
• the definition also applies to the radicals which can be at the positions of the general formula (I) denoted by R 2 .
• Quaternary amidoammonium salts of the general formula (I) in which R 1 and R 2 represent such a group of the general formula (11) are particularly preferred.
• R 4 is hydrogen or methyl and p is an integer from 2 to 8.
• Compounds of this general formula are particularly easy to assemble and impart to the laundry which has been treated with aqueous solutions of such compounds , a soft, fluffy handle.
• R 3 represents a group of the above-mentioned general formula (11), the definition of which can be completely adopted at this point, or a group of the general formula (111), in which R 5 denotes an alkylene radical, alkenylene radical or alkadienylene radical with 7 to 21 C atoms.
• the groups R 3 are acyl residues of saturated, monounsaturated or diunsaturated fatty acids with 8 to 22 carbon atoms.
• acyl radicals (III) mentioned thus come from the group caproyl, pelargonoyl, caprinoyl, undecanoyl, lauroyl, tridecanoyl, myristoyl, pentadecanoyl, palmitoyl, margarinoyl, steaoryl, nonadecanoyl, arachinoyl, uneicosoyl and behenoyl.
• Preferred compounds of the general formula (I) are those in which R 3 is acyl radicals of the general formula (III) in which R S is an alkylene radical, alkenylene radical or alkadienylene radical having 11 to 17 carbon atoms.
• acyl residues originate from those fatty acids which are inexpensively obtainable from natural fats and oils in large quantities and usually do not occur in pure form, but rather in the form of mixtures of several homologs with different numbers of carbon atoms in the acyl residue.
• the spectrum of connections that Containing acyl residues with 12 to 18 carbon atoms ranges from coconut oil to palm kernel oil, palm oil, cottonseed oil, sesame oil, sunflower oil, soybean oil, peanut oil, olive oil and rapeseed oil to animal fats such as tallow.
• index m in the above general formula (I) stands for 2 or for 3. This means that either ethylene or propylene radicals connect the individual nitrogen atoms of the quaternary amidoammonium salts to one another.
• p stands for an integer in the range from 1 to 10.
• the respective groups are ethoxy, propoxy or butoxy chains in which 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 ethoxy, propoxy or butoxy radicals are bonded to one another.
• alkoxy radicals are “closed” at the end with an H atom.
• the quaternary amidoammonium salts of the general formula (I) are composed of a cation having q positive charges and an anion X having r negative charges.
• the number of positive charges q corresponds to an integer in the range from 1 to n + 1, i.e. ultimately the number of quaternary N atoms in the cation.
• These positive charges result from the fact that, on at least one nitrogen atom within the cation, the radical R 1 for an organic radical from the group defined in more detail above and the radical R 3 for a radical of the above general formula (III), that is to say an acyl radical which is closer above defined group.
• the number r is an integer greater than or equal to 1, which corresponds to the charge of the acid anion X.
• r cationic residues with q positive charges have to be opposed to anionic residues with r negative charges.
• X in the general formula (I) stands for the anion of a non-oxidizing and non-corrosive inorganic acid or an organic monocarboxylic acid or polycarboxylic acid.
• Preferred inorganic radicals X come from the group phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid and sulfurous acid.
• Preferred acid residues X of organic monocarboxylic acids or polycarboxylic acids come from the group formic, acetic, propionic, glycolic, lactic, maleic, adipic, citric, methylsulfonic, p-toluenesulfonic, benzene and salicylic acid.
• anionic radicals X those from the group of the organic radicals of monocarboxylic acids or polycarboxylic acids are preferred. These give quaternary amidoammonium salts of the general formula (I), which have particularly good finishing properties. Of these, the residues of lactic acid (lactate), glycolic acid (glycolate) or acetic acid (acetate) are particularly preferred.
• Quaternary amidoammonium salts of the general formula (I) which are particularly preferred according to the invention are characterized in that in the general formula (I) the radical R 1 is a group of the general formula (11) in which R 4 is methyl and p is 5; 2 also for a radical of the general formula (11) in which R 4 is hydrogen and p is 1, R 3 for a radical of the general formula (111) in which R 5 is an alkylene radical having 15 to 17 carbon atoms , n for 0, m for 2, X for a lactic acid residue (lactate) and q and r for 1.
• Preferred compounds of this type which are derived from aminoethylethanolamine (AEEA) and are formed by acylation with stearic acid or one of its derivatives and subsequent reaction with propylene oxide, have an excellent softening effect and give the laundry a soft and fluffy feel.
• AEEA aminoethylethanolamine
• the compounds of the general formula (I) can be present in a mixture with fully acylated amines.
• diamines or higher amines of the general formula (IV) whose individual groups are defined in more detail below, acylated with carboxylic acids or their esters of the general formula (V) in which R 5 is an alkylene radical, alkenylene radical or alkadienylene radical having 7 to 21 carbon atoms and R 7 is hydrogen, a methyl radical, ethyl radical or glyceryl radical.
• R 5 is an alkylene radical, alkenylene radical or alkadienylene radical having 7 to 21 carbon atoms
• R 7 is hydrogen, a methyl radical, ethyl radical or glyceryl radical.
• the radicals R 1 which may be the same or different from one another within the amine (IV), represent a lone pair of electrons, an alkyl group having 1 to 4 carbon atoms or a group of the general formula (11) in which R 4 is hydrogen, methyl or ethyl and p is 1.
• R 4 is hydrogen, methyl or ethyl and p is 1.
• the radicals R 2 which may be the same or different from one another in the molecule (IV), represent hydrogen, an alkyl group having 1 to 22 C atoms, an alkenyl group having 8 to 22 C atoms or a group of the above general formula (11) in which R 4 is hydrogen, methyl or ethyl and p is 1.
• R 4 is hydrogen, methyl or ethyl and p is 1.
• R 6 represents a lone pair of electrons or hydrogen. Limiting the meaning of the radical R 6 in the general formula (IV) is that R 6 is a free electron pair if R 1 is an organic radical from the group defined in more detail above, or that R 6 is hydrogen if R 1 stands for a free pair of electrons. In addition, in the amines of the general formula (IV) at least one of the radicals R 2 and R 6 must be hydrogen.
• the reaction of the acylation of the amines of the general formula (IV) with carboxylic acids or their esters of the general formula (V) is carried out in a preferred embodiment of the process according to the invention at elevated temperature.
• the acylation advantageously takes place at temperatures in the range from 85 to 200.degree. This ensures that a sufficient proportion of free amino functions in the compounds of the general formula (IV) is converted into amido functions of the corresponding carboxylic acid.
• a certain molar ratio of the amine (IV) to the carboxylic acid or its esters (V) must be set before the acylation reaction begins. This is preferably in the range from 1: 0.5 to 1: 3.
• a molar ratio (IV): (V) of 1: 0.6 to 1: 2.5 is advantageously set and the mixture of the two components is then used Brought reaction. The corresponding amidoamines acylated on one or more nitrogen atoms are obtained in a satisfactory to very good yield.
• the acylation reaction is carried out in a polar organic solvent in which the components dissolve in a sufficient amount. It is particularly preferred to work in a lower alcohol. Of the lower alcohols containing 1 to 6 carbon atoms, isopropanol has proven particularly useful.
• diamines of the general formula (IV) are used in which R 1 is for a lone pair of electrons or a group of the general formula (11) in which R 4 is hydrogen and p 1 is R 2 is Hydrogen or a group of the general formula (11), in which R 4 is hydrogen and p is 1, and n is 0 and m is 2.
• AEEA aminoethylethanolamine
• carboxylic acids or their esters of the general formula (V) for the acylation, in which R 5 represents alkylene radicals having 15 to 17 C atoms.
• the resulting amines acylated with srearoyl residues show particularly good results when used in the finishing of textiles.
• the acids of the general formula (VI) are thus inorganic acids from the group phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid and sulfurous acid and organic acids (carboxylic acids) from the group formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, maleic acid, adipic acid, Citric acid, methylsulfonic acid, p-toluenesulfonic acid, benzoic acid and salicylic acid in question.
• organic monocarboxylic acids from the group of acetic acid, glycolic acid and lactic acid are preferred for the formation of the acid addition salts, since the salts formed have a particularly good effect when used as softening agents for textiles.
• the amount of the acid of the formula (VI) is preferably such that an amino function of the acylation product is reacted with an acid function.
• the reaction of the formation of the acid addition salts is also carried out according to methods known per se from the prior art. It has proven useful to work in water or a mixture of water and an organic solvent.
• a lower alcohol is preferably used as the organic solvent. From the group of such alcohols with 1 to 6 carbon atoms, isopropanol is preferably used as the organic solvent, since it is particularly easy to remove from the product mixture due to its volatility.
• aliphatic diols, such as glycol or 1,2-propanediol, or their oligomers can also be used as organic solvents.
• the acid addition salts formed are alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide in the presence of 10 to 80% by weight of water, based on the total batch.
• one or more ethoxy, propoxy and / or butoxy groups are inserted into all of the amine N-H bonds still available within the molecule of the acid addition salts formed in the previous step.
• the length of the alkoxy chains depends on the molar ratio of acid addition salt: alkoxylation reagent. In preferred embodiments of the process according to the invention, this molar ratio is in the range from 1: 1 to 1:10.
• alkoxylation reagent either only one of the alkylene oxides mentioned or any mixtures of the alkylene oxides mentioned.
• chains of ethoxy, propoxy and or or butoxy groups with statistical chain length distribution and optionally distribution of the ethoxy, propoxy and butoxy radicals are also formed.
• Ethylene oxide and / or propylene oxide is preferably used as the alkoxylation reagent.
• the molar ratio is more preferably in the range from 1: 3 to 1: 5.
• the alkoxylation reaction is carried out under pressure.
• the pressure is usually in the range from 1.1 to 4 bar, preferably from 2 to 3.5 bar.
• the insertion reaction of the alkylene oxides into the remaining amine N-H bonds at 70 to 100 ° C., preferably at 80 to 90 ° C. takes place completely within 1 to 5 hours, but usually already in 1 to 2 hours.
• reaction products from the reaction mixture in a manner known per se. This is done, for example, by completely removing any solvents used in the process from the reaction mixture at a slightly reduced pressure and / or slightly elevated temperature.
• masses of the quaternary amidoammonium salts of the general formula (I) which are melted at elevated temperature but are solid at room temperature are advantageously obtained.
• conversions in the range from 80 to 99%, based on the amine functions present after the acylation reaction are achieved.
• the quaternary amidoammonium salts of the general formula (I) obtained in the course of the process are cationic surfactants which can be used to finish textiles.
• the compounds (I) have a surprisingly good softening effect on cotton fabrics, which surpasses that of compounds known from the prior art.
• the compounds of the general formula (I) have the advantage over conventional finishing agents that the absorbency present in the untreated tissue is less impaired by the finishing treatment with the compounds according to the invention.
• the compounds according to the present invention are conveniently used in aqueous solutions, emulsions or dispersions which contain 10 to 30% by weight of the compounds of the general formula (I).
• the cationic surfactants are drawn onto the fabric and, after drying, give it a soft feel and good fluffiness. As stated, the absorbency is impaired less than with known agents.
• the connections can be completely removed from the textiles in subsequent washing processes and consequently do not accumulate on the fibers.
• the product had an acid number (SZ) - determined analogously to DGF method C-V2 - of 2.2, which, based on the lactic acid used, corresponds to a degree of conversion of 92%.
• the lactic acid had not reacted with ethylene oxide, as was found by lowering the pH to 2.5 using hydrochloric acid and subsequent potentiometric titration with sodium hydroxide solution.
• the lactic acid missing in the acid number determination could be recovered almost quantitatively.
• 850 g (1.0 mol) of hardened beef tallow were determined according to known methods at 95 to 100 ° C. with 69.7 g (0.67 mol) of hydroxyethylethylenediamine (AEEA) up to an amine nitrogen content of the product of 1.25% by titration with perchloric acid in acetic acid medium.
• AEEA hydroxyethylethylenediamine
• reaction product obtained 250.6 g (0.22 equivalents) of the reaction product obtained were mixed together with 22.0 g (0.22 mol) of 90% lactic acid, 20.0 g of isopropanol and 57.8 g of water in an autoclave and with stirring 80 to 85 ° C and a pressure of 3.5 bar within 4 h with 49.2 g (1.12 mol) of ethylene oxide to react. A mass which was solid at room temperature and had an acid number of 1.7 was obtained. This corresponds to a lactic acid conversion of 95%.
• a product which had a low viscosity at 70 ° C. was obtained and solidified to a lard-like mass at room temperature.
• the acid number was 2.0. This corresponds to a degree of conversion of 94% based on lactic acid.
• the reaction mixture was reacted in an autoclave at from 80 to 85 C and a maximum pressure of 3 bar within 4 h with 109.3 g (2.48 mol) of ethylene oxide.
• the substance solidifying at room temperature to a lard-like mass had an acid number of 3.4. This corresponds to a degree of conversion, based on acetic acid, of 95.1%.
• the product was then mixed with 33.9 g (0.34 mol) of 90% lactic acid, 23.7 g of isopropanol and 46.4 g of water and in an autoclave at 80 to 85 ° C and a maximum pressure of 3 bar within 4 h reacted with 74.5 g (1.69 mol) of ethylene oxide.
• the substance which was liquid at elevated temperature and solidified at room temperature, had an acid number of 1.0. This results in a degree of conversion based on lactic acid of 97.9%.
• Example 2 60 g of the reaction product of hardened beef tallow and hydroxyethylethylenediamine described in Example 2 were mixed at 80 ° C. to give a 20% dispersion after the addition of 4 g of acetic acid and 256 g of water. A product which flowed well after cooling to room temperature was obtained.
• the melt of the products obtained according to Examples 1 to 6 was mixed at 80 to 85 ° C. with sufficient water to result in aqueous dilute dispersions which contained 10, 15 and 20% of the quaternary amidoammonium salt according to the invention. After cooling to room temperature, the flow behavior of the dispersions was assessed visually.
• a low viscosity is advantageous for later dilution to finishing liquors for treating textiles, since this enables a homogeneous distribution of the active ingredients used as finishing agents to be achieved more quickly. In addition, this has a favorable influence on the induction behavior in washing machines.
• Approx. 30 g of a cotton terry cloth hardened by repeated washing were immersed in 600 ml of an aqueous washing liquor, each containing 0.15 g (based on 100% active ingredient) of the quaternary amidoammonium salts according to the invention, for 3 minutes and agitated.
• the terry fabrics were then spun and air dried.
• test subjects rated the textiles treated with the agent of Comparative Example 1 even worse than those textiles that had been treated with a finishing agent of the prior art (distearyldimethylammonium chloride).
• the test subjects were able to find significantly better results with textiles which had been treated with quaternary amidoammonium salts according to the invention. Without exception, these were rated as "soft” or "very soft”.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=6340540

Family Applications (1)

Country Status (5)

Families Citing this family (1)

Citations (3)

• 1987
  • 1987-11-14 DE DE19873738780 patent/DE3738780A1/de not_active Withdrawn
• 1988
  • 1988-11-07 EP EP19880118505 patent/EP0316701A3/fr not_active Withdrawn
  • 1988-11-11 ZA ZA888463A patent/ZA888463B/xx unknown
  • 1988-11-11 BR BR888805924A patent/BR8805924A/pt unknown
  • 1988-11-14 JP JP63288702A patent/JPH01153666A/ja active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events