NO172231B - POLYAMIDS USED AS ANTISTATIC AGENTS FOR FILAMENTS AND FIBROSICAL MATERIALS AND DETERGENT MIXTURE INCLUDING SUCH - Google Patents

Description

The invention relates to polyamides of trialkylacetic acid(s) and polyamine(s) which are diamides and/or triamides and which are useful as antistatic agents for filamentary and fibrous materials.

Because modern synthetic organic detergents are such excellent cleaners, laundry washed with them often lacks desirable softness. Synthetic polymeric fibers in the fabrics of much such laundry are susceptible to disadvantageous accumulations of static charges that occur during machine drying or when the fabrics are rubbed against other materials. Much research has been carried out to discover materials which, when incorporated into detergent compositions or rinse water, or when otherwise supplied, would reduce any static charges on the laundry or would inhibit the accumulation of such charges. The new alkanamides have been found to be adsorbable from washing and rinsing water of fiber materials, such as e.g. the substances in laundry items, and in particular antistatic polymeric fibers in such, such as e.g. polyesters. They have been found to give such substances particularly good antistatic properties so that the accumulation and development of electrostatic charges on them is prevented. More specifically, the invention relates to the multifunctional amides of trialkylacetic acids and the multifunctional amines where the trialkylacetic acid residues contain 1-10 carbon atoms in each of the alkyl parts, and where the multifunctional amine residues, which are usually aliphatic, contain from 2 to 5 amino groups. Such compounds are referred to as polyamides and polyamines, or polyamides and polyamines. The invention also includes antistatic detergents that contain one or more of the compounds according to the invention.

The polyamines which can be used to produce the antistatic polyamides of the invention are described in a brochure published by Texaco Chemical Company, "JEFFAMINE Poly-oxypropyleneamines", copyright Jefferson Chemical Company,

Inc., 1978. Formulas for such polyamines are given on pages 2 and 3, and typical physical properties are given on pages

3 and 4. Applications of the "Jeffamines" for textile applications and related materials are listed and summarized. Antistatic treatments of textiles were in some cases done using the reaction between polyoxyethylenediamine or a similar polyamine and a suitable acid to produce an antistatic polyamide. Among the interesting literature references referred to are Japanese Patent Nos. 71/07,461, 71/29,914 and 71/32,519, and US Patent No. 3,558,419. However, none of the literature references describe or suggest a polyamide according to the present invention.

Neodecanoic and neopentanoic acids are marketed by Exxon Chemical Americas and are described in a brochure published by Exxon Chemical "Neo Acids Properties, Chemistry and Applications", 1982. Other neoalkanoic acids have also been made, such as neoheptanoic acid, neonanonic acid and mixed neododecanoic, neotridecanoic and neotetradecanoic acids. Amides of neoacids and methods for their preparation are generally discussed on page 10, column 1 of the brochure, and uses of various neodecanamides are mentioned. However, nothing is mentioned about the described polyamides according to the present invention or about their uses as antistatic agents for laundry.

In US patent no. 4,440,666, which is directed to a hydrocarbon liquid containing a minor part of a reaction product between a polyalkylene polyamine and a neoacid with 5-20 carbon atoms where the amide acts as a corrosion inhibitor, the polyamides according to the present invention are not disclosed and it is not suggested that such compounds will have antistatic properties.

Quaternary ammonium salts, such as di-(lower-alkyl)-di(higher-alkyl)-ammonium halides, e.g. dimethyl-distearaylammonium chloride, has been used as fabric softener in detergents, in fabric softening mixtures for addition to the rinse water and in paper, foamed materials and other substrates intended for introduction into clothes dryers where they transfer such cationic materials to the laundry that is thrown around. Certain amines have also been found to be useful in some such applications. As such cationic materials react unfavorably with anionic detergents, their use in anionic detergent mixtures results in undesirable reaction products and loss of washing effect. Such cationic materials also react with optical brighteners and cause a reduction in whitening.

It is an important feature of the present invention that certain neutral amides have been discovered which are water-insoluble and which can be in a desired oily or plastic, flowable or spreadable state at normal operating temperatures, e.g. 10-90°C, preferably 10-60°C. Certain amides which have the desired physical characteristics, are adsorbable or otherwise depositable on clothes from the washing water or rinse water in a washing machine, or can be deposited on drying clothes in the dryer, are polyamides of neoalkanoic acids.

The results obtained are generally better than those obtained by using higher alkyl isostearamides, as described in US Patent No. 4,497,715, and are even better than those obtained by using mononeoalkanamides as antistatics, which are described in our US Patent Application No. .716,871. Although the isostearamides and mononeoalkanamides are very effective antistatics that do not react unfavorably with anionic detergents, at least some of the present polyamides are even more effective in antistatic activity such that percentages in compositions and frequency of application can be significantly reduced, which leads to significant savings and to better products.

The present invention thus provides polyamides of trialkylacetic acid(s) and polyamine(s) which are diamides and/or triamides and which are usable as antistatic agents for filamentary and fibrous materials. The polyamides are characterized by the fact that the trialkylacetic acid residues contain 1-10 carbon atoms in each of the alkyl parts and that the sum of the number of carbon atoms in the alkyl parts in each trialkylacetic acid residue is from 3 to 12, and that the polyamine residue is a diamine or triamine residue with alkylene groups and/or polyoxyalkylenealkylene groups that bind together the amide groups in the polyamide, which polyamides are selected from and

where A is selected from alkyl with 1-20 carbon atoms and hydrogen, T is selected from methyl and hydrogen, R is a neoalkyl with 4-13 carbon atoms, n is a number from 1 to 40 and each of x, y and z are numbers from 1 to 8 and together from 4 to 10.

The invention also provides a detergent mixture, comprising a cleaning part of a synthetic organic detergent and a part of an antistatic agent which provides antistatic properties to clothes during washing and which is applicable for filamentary and fibrous materials. The detergent mixture is characterized by the fact that the polyamides specified above are used as antistatic agents.

Infrared absorption spectra for several representative polyamides according to the invention are shown in the drawings, where: Fig. 1 is such an absorption spectrum for the trineodecanamide of the polyoxypropylene triamine sold as "Jeffamine T-403", Fig. 2 is such a spectrum for the dineodecanamide of the polyoxypropylenediamine sold as "Jeffamine D-230", Fig. 3 is such a spectrum for the dineodecanamide of neodecanoic acid and hexamethylenediamine, and Fig. 4 is such a spectrum for the dineodecanamide of neodecanoic acid and ethylenediamine.

Neodecanoic acid is synthesized by reacting a branched nonene and carbon monoxide under high pressure at an elevated temperature in the presence of an aqueous acid catalyst (Koch reaction). The formula for the free acid is:

where the number of carbon atoms in R<1>+ R2 + R<3> is 8, approx. 31% of neo-

decanoic acid has a structure where R2 and R<3> are both methyl and R<1> is hexyl, 67% have the formula where R2 is methyl, R3 has a carbon atom content that is greater than that of methyl and less than that of R<1>, and R<1> has a carbon atom content that is less than that of hexyl, and greater than that of R<3>, and 2% has a formula where R<2> and R<3> both have a carbon atom content that is greater than that of methyl and less than that of R<1>, and R<1> has a carbon atom content that is less than that of hexyl and greater than that of R2 and R<3>. The dissociation constant (Ka) of neodecanoic acid is 4.20 x IO"<6>. Among other neoalkanoic acids that are available and can be used, those with 5-14 or 5-16 carbon atoms can be mentioned, such as, for example, neopentane, neoheptane -, neononan, neodecano, neododecano, neotridecano and neotetradecanoic acids.

As previously mentioned, the polyamines are preferably diamines or triamines. The triamines are preferably alkylene-polyoxyalkylene triamines, such as e.g. those sold by Texaco Chemical Company under the trademark "Jeffamine". Among such materials, "Jeffamine T-403" having the formula: where A = ethyl, T = methyl and x+y+z=5.3, is preferred. In the diamines, both amino groups are linked together by means of an alkylene polyoxyalkylene residue or by means of a lower alkylene group. Among the commercially available amines containing oxyalkylene groups, the "Jeffamines" are preferred, and the formula for the compounds is:

In this formula, T is methyl and n is in the range 2-10, preferably 2-7. Among such compounds that can be used are: "Jeffamine D-230" where n has an average of 2.6, "Jeffamine D-400" where n is 5.6 and "Jeffamine D-2000" where n is 33.1 . Among these diamines, the most preferred is "Jeffamine D-230". Among the non-alkylated diamines that can be used, one finds alkylenediamines with 2-6 carbon atoms, such as e.g. ethylenediamine and hexamethylenediamine.

Instead of using neoalkanoic acids for the production of the present polyamides, the corresponding acyl halides can be used. Usually acid chlorides are used, such as neodecanoyl chloride, which is available from Pennwalt Corporation and is described in their product brochure entitled "Acids Chlorides", September 1982, which also generally describes reactions between acid chlorides and amines.

The preferred triamides according to the invention have the formula: where A is selected from the group consisting of alkyl with 1-20 carbon atoms and hydrogen, T is selected from the group consisting of methyl and hydrogen, R is a neoalkyl with 4-13 carbon atoms, and x, y and z are each a number from 1 to 8, and together 4 to 10. Preferably, A is an alkyl of 1-4 carbon atoms, T is methyl, R is a neoalkyl of 4-9 carbon atoms, and x, y and z are each a number from 1 to 3, which together amounts to from 4 to 8. It is even more preferred that A is an alkyl with 1-3 carbon atoms, T is methyl, R is neoalkyl with 4 or 9 carbon atoms and x, y and z is each a number from 1 to 3, which on average together amounts to 4.5 to 6, preferably A is ethyl, T is methyl, R is neoalkyl with 9 or approx. 9 carbon atoms and x, y and z are each numbers from 1 to 3, with an average sum of approx. 5.3. The preferred diamides according to the invention have the formula:

where T is selected from the group consisting of methyl and hydrogen,

R is a neoalkyl with 4-13 carbon atoms and n is from 1 to

40. It is preferred that T is methyl, R is neoalkyl with 4 -

9 carbon atoms and n is a number from 2 to 10. Even more preferred is that T is methyl, R is neoalkyl with 4-9 carbon atoms and n is a number from 2 to 7. Preferably T is methyl, R is a neoalkyl with 9 or approx. 9 carbon atoms and n is an average of approx. 5.6. Other useful diamides are the diamides of a neoalkanoic acid of 5-10 carbon atoms and an alkylenediamine of 2-6 carbon atoms. Among these compounds, N,N1-ethylene-bis-neodecanamide and N,N'-hexamethylene-bis-neodecanamide are preferred.

The polyamides according to the invention can be produced by reacting a neoalkanoyl chloride with a suitable polyamine, but a less expensive synthesis takes place directly from the suitable neoalkanoic acid by reacting it with such a polyamine at an elevated temperature. Unfortunately, the product of such reaction is often darker in color than desirable, apparently at least in part because the reaction is run at an elevated temperature. It has been found that the use of ethylene glycol in the reaction mixture as a "catalyst" allows the reaction to be carried out at a lower temperature and thereby improves the product color. Currently, efforts are being made to find other catalysts which will promote the direct condensation reaction and which will give a product with an improved colour. The product color can be improved by using the more expensive reaction with neoalkanoyl chloride.

In the direct condensation process, the trialkylacetic acid (neoalkanoic acid) and the polyamine are often reacted at a suitable elevated temperature, often in the range 180-320°C, e.g. 230-250°C, during a time period of 0.5-8 hours, preferably 1-4 hours and often using a nitrogen or inert gas "blanket" over the reaction mixture, stirring being carried out throughout the reaction, and condensation water is continuously removed during the reaction. However, in certain processes, especially exothermic ones, cooling may be preferred, and the reactions may take place at room temperature or just above it. The melting points of the products will normally be low, so that the products will desirably be liquids, preferably viscous, oil-active liquids. Such a physical state is unusual for primary and secondary amides of similar or lower molecular weight due to strong inter-molecular forces characteristic of the amide functionality. The viscous, oil-active liquid state of the polyamides according to the present invention is considered highly desirable because it makes it easier to achieve antistatic action when the polyamides are incorporated into antistatic detergent mixtures. It is also important that the polyamides according to the invention are only slightly water-soluble, but still easily distributable in an aqueous medium at normal washing temperature, such as e.g. in the range 10-90°C, often 20-60°C. When choosing polyamine and neoalkanoic acid reactants, the selection of such reactants with desired proportions of hydrophilic and hydrophobic groups, such as e.g. ethylene oxide and propylene oxide (or butylene oxide), control of the hydrophilic-lipophilic balance of the antistatic agent to be made, thereby "fine-tuning" its water solubility so that it can become an effective antistatic agent in the intended product or for the intended use.

It has been found that the best antistatic agents for use in detergent compositions or fabric softener compositions, or for use in wash and rinse operations, are those made from a neoalkanoic acid, such as e.g. neodecanoic acid, and a polyoxypropylene triamine, such as e.g. "Jeffamine T-403". Other "Jeffamines", such as The "Jeffamines D-230", "D-400" and "D-2000" can also be used to make the polyamides according to the invention, and among these "Jeffamine D-230" is the best, obviously because the other "Jeffamines" result in products that are less effective as antistatic agents due to the high content of oxypropylene groups, higher molecular weights and lack of hydrophilic characteristics, which help to lower their adsorption on fiber surfaces. When the polyamide is ethylenediamine or hexamethylenediamine, polyamides are obtained which provide antistatic activity during laundry, but it is not as effective as with the polyamides prepared from the described trial-chillacetic acid and "Jeffamine T-403" or "Jeffamine D-230".

From the formulas and descriptions of constituents and sub-st i tuents thereof, it will be seen that the amine radicals of the polyamines (including diamines) are completely converted to amide form. Although such amides are highly preferred, however, polyamines which are incompletely converted into amides and which are at least 2/3 converted into amides can also be used as antistatic agents. They will have some of the undesirable properties of quaternary ammonium salts in that they can be reactive with anionic detergents, but it is expected that such reaction and resulting reduction in washing performance and increase in fabric staining will generally be tolerable as only a portion of the amine radicals will not have been converted to non-reactive amides. Any adverse effects due to the presence of unreacted amine groups can be counteracted by mixing with polyamides according to the invention, which are completely converted to amide.

Mixtures of the diamides and triamides according to the invention can be used in any desired and effective ratio. E.g. thus N,N'-ethylene-bis-neodecanamide can be mixed with N,N'-hexamethylene-bis-neodecanamide, N,N'-hexamethylene-bis-neopentanamide or with the tri-neodecanamide of "Jeffamine T-403", and the latter can be mixed with the di-neodecanamide of "Jeffamine D-230", just to name a few of the possible combinations.

The polyamides according to the present invention can be used to treat various fiber materials, including polyesters, nylons, polyacrylates and acetates, mixtures of some or all of these materials and mixtures of any such materials with natural fibers, such as e.g. cotton, to lower the tendency of such to accumulate unfavorable static charges. They can also be used to treat non-fibrous polymeric materials, such as video tapes, camera film and photographs, film, audio tapes, plastic film and molded (and otherwise shaped) plastic objects, such as e.g. articles made of polyvinyl chloride (or polyvinyl chloride sheets). In such treatments, the polyamides can be applied directly or in slurry or solution, such as liquids, masses, gels, foams or sprays, to the surfaces of the objects to be treated, in relatively small proportions, usually with a ratio of polyamide to treated material lying in the area 0.00005 to 0.1% by weight.

The polyamides according to the invention are particularly advantageous for use in detergent mixtures of the anionic type because, unlike quaternary ammonium halides, they do not react unfavorably with anionic detergents and do not form complexes with optical brighteners. They thus do not form undesirable fat reaction products which can be deposited on and spoil the appearance of washed clothes, and they do not cause a reduction in the cleaning activity of the detergent mixture. In preferred detergent compositions, the synthetic organic detergent will be of the sulphate and/or sulphonate type, usually comprising a higher aliphatic chain, such as a higher alkyl with 8-20 carbon atoms, preferably 10-18, in the lipophilic part thereof. Preferably, such materials will be present in the form of water-soluble salts, e.g. sodium salts. Although the present polyamides can be used in non-ionic detergent mixtures or detergent mixtures of different types, including amphoteric, ampholytic and zwitterionic detergents, the detergent will preferably be an anionic detergent and will usually be one or more of the following: higher alkylbenzene sulfonates, higher fatty alcohol sulfates, olefin sulfonates, paraffin sulfonates, monoglyceride sulfates, fatty alcohol ethoxylate sulfates, higher fatty acid sulfonate esters of isethionic acid, higher fatty acyl sarcosides and acyl and sulfonamides of N-methyltaurine. In such detergents, a higher aliphatic group will normally be present which is preferably straight chain and which will usually contain 8-20 carbon atoms, preferably 12-18. When lower alkoxy chains are present in the detergent, as in the aforementioned ethoxylate sulfate, there will usually be from 3 to 30 ethoxy residues, preferably 3 to 10. Such detergents will normally be used as sodium salts even if other water-soluble salts, such as e.g. potassium, ammonium and triethanolamine salts can also be used, depending on the circumstances.

For applications involving extra heavy laundry, the detergent mixture will usually contain a builder to increase the washing effect of the anionic detergent, particularly in hard water. Among the various builders that can be used, those that are preferred include: the polyphosphates sodium tripolyphosphate and tetrasodium pyrophosphate, carbonates, bicarbonates, sesquicarbonates, silicates, sesquisilicates, citrates, nitrile triacetates and polyacetal carboxylates, all of which are water-soluble salts, and the water-softening zeolites, such as hydrated <®>Zeolite A, which is water insoluble.

The proportion of the invented neoalkanamide in the detergent mixture will be a proportion that gives antistatic properties to washed clothes that adsorb the invented polyamide during washing, and this will normally be in the range of approx. 0.5-20% by weight of the detergent mixture, preferably 1-10% and preferably 2-7%, and most preferably 3-5%, e.g. 4%.

In addition to the polyamide, the detergent and the builder, the invented detergent mixture will also usually contain some water. The proportion of water in such particulate solid products will normally be in the range of 2-20%, e.g. about 8%. It is desirable that the particulate material is in the form of spray-dried (or agglomerated or partially agglomerated) balls of detergent mixture, with particle sizes in the range 0.105-2.0 mm, preferably 0.15-2.0 mm. Other forms of detergent mixture can be made, including liquids, gels, masses, sticks and pieces, and the particulate mixtures and the mixtures in such other forms will also normally contain functional and aesthetic auxiliaries, and may contain fillers. Such auxiliaries and fillers will normally comprise the rest of the detergents. Among the auxiliaries that can be used, one finds: fluorescent or optical brightening agents, such as e.g. stilbene lightening agents, anti-redeposition agents, such as e.g. sodium carboxymethylcellulose, polymers that promote dirt dissolution, such as e.g. "Alkaril QCF", a polyoxyethylene-terephthalate-polyethylene-terephthalate copolymer, fabric softeners, such as bentonite, anti-gelling agents (for use in the mixer), such as e.g. citric acid and magnesium sulphate, colours, such as e.g. ultramarine blue pigment, and dyes, whiteners, such as e.g. titanium dioxide, enzymes, such as mixed proteolytic and amylolytic enzymes, and perfumes. Among the fillers or bulking agents occasionally used, sodium sulfate is the most preferred, although sodium chloride has also been used. Water, lower alcohols, glycols, co-solvents, hydrotropes and antifreeze additives may also be present in liquid detergent mixtures.

The proportions of detergent, builder, invented polyamide antistatic agent and water in the invented particulate antistatic detergent will normally be within the ranges 5 - 35%, 10 - 85%, 0.5 - 20% and 2 - 20% respectively. Preferred shares are respectively 8 - 30%, 25 - 70%, 1 - 10% and 3 - 15%, with more preferred shares being respectively 10 - 25%, 30 - 70%, 2 - 7% and 5 - 12%. The water content includes hydrate water which is removed using the standard water test, heating for 1 hour at 105°C, and water thus removed is not included in the percentages given for the other components.

When the detergent mixture is to be in particulate form, it can be made by spray-drying an aqueous mixture of the various components into free-flowing ball form, using well-known drying equipment such as a standard spray-drying method. However, even greater antistatic activity can be observed when the polyamide antistatic agent is not spray-dried together with the rest of the detergent mixture, but is sprayed, or otherwise applied, to spray-dried particles of the rest of the detergent mixture, the base beads or a detergent mixture made by mixing, and preferably agglomerating, of particulate matter. In a preferred method for producing non-ionic detergent mixtures, the polyamide is dissolved and/or dispersed in a recipe proportion of liquefiable non-ionic detergent at an elevated temperature (40-50°C), and the resulting liquid is sprayed onto and absorbed by porous spray dryers -bored building blocks. The aforementioned improved antistatic results can also be achieved by adding the polyamide antistatic agent to the washing water and adding separately the detergent mixture or its components. For such applications, the antistatic agent can be made in an ordinary powder form, ready for use as an additive to detergents by first mixing with a suitable carrier, e.g. "Microcel" (a synthetic calcium silicate powder), a filler, e.g. particulate sodium sulfate, or a fabric softener, e.g. bentonite, a builder or mixture of builders, or other suitable substance or other suitable substances. Very promising carriers are <®>Fresh Start detergent base beads, which may be porous spray-dried beads of mixed sodium carbonate and sodium bicarbonate (for non-phosphate detergents) or may contain sodium tripolyphosphate in spray-dried form. Such base balls of "Fresh Start" can contain up to 40% polyamide, e.g. 5-35% of the triamide of neodecanoic acid and the amine "Jeffamine T-403", and will still be free-flowing particles. Rinsing compositions may sometimes contain only the inventive polyamide dissolved in a suitable dissolution medium or dispersed in an aqueous liquid medium, often preferably by means of a hydrotropic or other surfactant or solubilizing agent. The proportion of antistatic agent will preferably be kept at approximately the same level as in the antistatic particulate detergent previously discussed, e.g. 0.5-20%, although less could be used because the antistatic agent will usually be more substantial in the absence of the detergent and builder. In liquid preparations for use in the rinsing water, the proportion of solvent or liquid will normally be from 50 to 90%, while any content of surface-active material or hydrotrope will usually be in the range of 0.1-5%. A quaternary ammonium halide is also present and the proportion of this would preferably be in the range of 1 part of the quaternary compound to 1/2-10 parts of polyamide antistatic agent. When a polyurethane or cellulose foam strip or a cloth or paper substrate is impregnated with the antistatic agent according to the invention (usually by weight from 10 to 100% of the weight of the substrate), a fatty substance, such as e.g. monoglyceride or diglyceride of higher fatty acids also be present to assist in the deposition of the polyamide on the surfaces of the fabric fibers. A suitable such material is diglyceride of fatty acids from coconut oil e.

When the polyamide antistatic agent according to the invention is added to the laundry during washing or rinsing by adsorption on the laundry from the washing water or the rinsing water, the concentration of the detergent mixture or the rinsing preparation in the washing water will be sufficient to give antistatic properties to the washed laundry, e.g. cloth items made of polyester or mixed fabrics of polyester and cotton. Such an effective concentration will normally be in the range 0.002-0.05% polyamide and preferably such a range will be 0.004-0.02%. The concentration of the detergent mixture or rinse aid mixture in the washing water will normally be in the range 0.05-0.5%, preferably 0.08-0.2%.

Example 1

146 g of "Jeffamine T-403" polyoxypropylene triamine was reacted with 165 g of Exxon neodecanoic acid (first class fineness)

in a 1-liter, 3-necked glass flask fitted with a magnetic stirrer, a heating mantle, and an ice condenser. The condensation reaction was carried out at a temperature of 250°C and was monitored by observing the water collected from the condenser. After 6 hours, the reaction was essentially complete and the flask was removed from the heating mantle. It was set aside until it had cooled to room temperature and the contents were then transferred to a 1-litre separatory funnel where it was washed with solutions consisting respectively of: water, ethanol and hydrochloric acid; water and ethanol; aqueous sodium hydroxide; and distilled water, until neutrality. After completion of the washing, the excess water was poured off and the washed product was dried in a vacuum rotary evaporator, yielding 260 g of product.

The product was a relatively dark colored oil with a melting point less than 0°C and a refractive index (ND20°C) of 1.4745. The infrared absorption spectrum for

the produced polyamide, which is the triamide of neodecanoic acid and the polyoxypropylene triamine, is reproduced in fig. 1. A nuclear magnetic resonance spectrum was obtained which proved to be consistent with the expected structure.

When 10 by weight of the reactants (approx. 30 g) of ethylene glycol is present in the reaction mixture as a catalyst for the condensation reaction, the temperature of the reaction mixture can be reduced to 23°C and the produced amide is more light-coloured.

An even lighter colored oily liquid product can be obtained by using neodaconoyl chloride instead of neodecanoic acid. In addition, the reaction temperature can be lowered. Consequently, the product obtained is lighter in color. For the neodecanoyl chloride reaction with "Jeffamine T-403", the weight of neodecanoyl chloride used was 190 g and the reaction was carried out at 300°C or less (using an ice bath to keep the temperature low as the reaction is exothermic) for a period of 3 hours, after which turnover is assumed to be complete. In addition to the aforementioned reactants, there is also present in the 1 liter 3-necked flask (which is equipped with a condenser with a Drierite tube, a thermometer, a Chesapeake stirrer and a dropping funnel) 700 ml of diethyl ether as a solvent- medium for the reaction, and 1 gmol (101 g) of triethylamine (which acts as an HCl trap).

After completion of the neodecanoyl chloride addition,

the ice bath was removed from the flask and the reaction mixture was allowed to warm to room temperature, after which it was stirred for an additional 1 to 3 hours. It was then transferred to a 2-liter separatory funnel and washed twice with water,

once with 5% aqueous hydrochloric acid and once with 5% aqueous sodium hydroxide, followed by one or more washes with distilled water until the product was neutral as measured by pH paper. Any remaining ether was removed using a steam bath and the product was finished on a vacuum rotary evaporator. The manufactured product is colorless to light beige in colour, is pure and exhibits the infrared and N.M.R. spectra as previously described for the same product prepared using the condensation method.

Example 2

In a variation of the acid chloride production method for the preparation of polyoxypropylene-tri-neodecanamide, using a 3-liter, 3-necked flask with a Chesapeake stirrer, condenser, thermometer, dropping funnel, and ice bath, 206 g of "Jeffamine T -403" polyoxypropylene triamine, 600 ml methylene chloride and 135 g triethylamine to the flask. Keeping the temperature below 30°C by controlling the rate of addition, 255 g of neodecanoyl chloride (obtained from Pennwalt Corporation) was added to the flask through the dropping funnel. After addition of neodecanoyl chloride, the reaction mixture was kept at approx. room temperature and it was stirred for another 3 hours. It was then washed twice with 500 ml portions of distilled water, twice with equal portions of 10% sodium hydroxide solution (in water) and then with water until it appeared neutral on pH paper. The resulting methylene chloride solution of polyoxypropylene-tri-neodecanamide was then filtered through anhydrous sodium sulfate, the methylene chloride was evaporated and the amide product was recovered.

Example 3

Polyoxypropylene-di-neodecanamide was prepared by the condensation method using a 500 ml 3-necked flask equipped with a magnetic stirrer, a heating element, a condenser with a Dean Stark trap and a thermometer with a heat monitoring control for the heating element. A nitrogen inlet was connected to the flask so that nitrogen gas could be held above the surface of the reaction mixture to cover it. 95 g of "Jeffamine D-230" polyoxypropylenediamine with an approximate molecular weight of 230 (containing an average of 2.6 moles of propylene oxide per mole of diamine) and 172 g of neodecanoic acid were added to the flask. The mixture was covered with nitrogen, heated to a temperature in the range of 270-300°C and held at this temperature for 5 hours. The reaction was then considered complete and the reaction product was then transferred to a separatory funnel and washed three times with 5% aqueous sodium hydroxide solution followed by three washes with distilled water. The excess water was removed and the product was dried in a rotary evaporator.

Example 4

Using similar methods as in

examples 1 to 3, but with the conditions given in table 1 below, other amides according to the invention were made.

The physical characteristics of the products of this example and examples 1-3 were measured and infrared spectra and nuclear magnetic resonance spectra (proton and C-^) were run on some of the products. The melting points of all products are less than 0°C. Refractive indices are 1.4782 for the ethylenediamine-neodecanoic acid condensation product, 1.4742 for the hexamethylenediamine-neodecanoic acid condensation product, 1.4667 for the "Jeffamine D-230" neodecanoic acid condensation product, and 1.4745 for the "Jeffamine T-403" neodecanoyl chloride- the reaction product. Copies of the infrared spectra for TRI-DEC, J-DEC, H-DEC and E-DEC are reproduced in fig. 1-4. These and all the prepared multi-neodecanamides subjected to infrared analysis showed similar infrared absorption bands in terms of: secondary amide (N-H), where the absorption is strong at 3350 cm<-1>; secondary amine carboxyl (C=0) where the absorption is strong at 1633 cm ^; and ether part (C-O) where the absorption is very strong at 1100 cm for the polyoxypropylene amides (made from the "Jeffamines").

Proton and C, -. nuclear magnetic resonance spectra run on TRI-DEC are consistent with the structure of this amide. These spectra were very complex due to the presence of the isomeric mixtures.

Example 5

A spray-dried detergent mixture of the above composition was prepared by spray-drying an aqueous mixture of 60% solids content in a conventional counter-current spray-drying tower to produce spray-dried detergent balls without perfume, after which the balls were perfumed by spraying the surfaces with the proportion according to the recipe of liquid perfume. The product was sieved so that the particle sizes were in the range 0.15-2.0 mm. Next, 5 parts of dialkanoamide or trialkanoamide of the types described in the examples above were sprayed onto 100 parts of detergent mixture balls to prepare antistatic detergent mixtures. Instead of mixing the alkanoamide with the detergent mixture to make an antistatic detergent mixture, it can be added to the wash water and sometimes preferably added to the rinse water. The effects of the presence of the different antistatic materials in the prepared detergent mixtures were evaluated by washing test fabrics in a washing machine and drying in an electric automatic clothes dryer, after which the fabrics were evaluated with respect to static electricity accumulations using a test panel of judges and an apparatus for measurement of electric charges. A ballast load was used in the washing machine together with the test items. The ballast charge (2.3 kg) consisted of one-third terry wash cloths, one-third percale pieces (35.6 x 38.1 cm) and one-third 65% dacron - 35% cotton pieces (35.6 x 38.1 cm without permanent pressing ). The test fabrics used for measuring antistatic effect consisted of: double knit twill, 65% dacron - 35% cotton with permanent press, blue permanent press and nylon. In the test procedures used, the washing machine, after thorough cleaning of the washing and drying parts using denatured alcohol followed by air drying, was set to a 14 minute wash time using 64.3 liters of water at 49°C. The "hot" wash is one where the normal machine cycle is used, including a cold rinse with tap water. The detergent mixture containing the antistatic agent was added to the washing water after the machine had been filled, the machine was allowed to move for approx. 10 seconds and then the ballast fill of terry towels and other cloths (2.3 kg) and various synthetic polymeric test cloths were added separately while agitation was allowed to continue. The various substances were then removed and placed in the electric dryer where they were dried over a period of approx. 2 hours. The test cloths and the two terry towels from the ballast were then dried for a further 10 minutes and the test cloths were then evaluated for static cling by a test panel of experienced judges. Before instrumental static measurements were then carried out, the test garments were hung in a low humidity room (25% relative humidity) overnight. To determine the static charges on the average test material instrumentally,

all the static test cloth pieces were rubbed with wool under controlled conditions at a relative humidity in the range of 25-30%, after which the electrostatic charges on the cloth pieces were measured and a static index number was calculated. It was found that differences of 6 index number units (in kilovolts) are significant and indicate that consumers will notice the difference in static cling of washed materials.

The following table gives index numbers for detergent mixtures according to this example and for some previously known mixtures, when the washing machine is filled with 100 g of detergent mixture plus 5 g of antistatic agent, i.e. 0.155% based on the washing water.

From the data in Table 2, it will be seen that TRI-DEC is the most effective antistatic of the materials tested, both in terms of measured values for static charge and absence of static charge and static cling, as reported by a test panel of experienced judges . The other products according to the present invention that were tested, however, also resulted in improvements with regard to static control of synthetic substances, such as e.g. polyesters, and is thus useful as ingredients in detergent mixtures for that purpose. When such materials were incorporated into the rinse water in comparable concentrations of the active ingredient, such antistatic effects were also achieved on the synthetic substances present, especially polyesters. When antistatic agents are present in drying products, such as papers or polyurethane foam for contact with clothes while they are tossed around in the dryer, or when they are sprayed on clothes in the dryer, desirable antistatic effects are also obtained, especially for polyester-containing fabrics. For use when drying laundry, the proportion of antistatic agent is approx. the same as that used when the detergent mixtures are used when washing clothes, which for TRI-DEC is approx. 0.2%. Proportions of antistatic agents for rinsing and drying applications may, however, be in the ranges used for use in the detergent mixtures, based on the laundry being treated.

Experiments such as those described in this example have determined that in order to achieve complete absence of static charge on average laundry loads containing synthetics, including polyesters, at least 3.5% TRI-DEC should be present in the detergent composition. To achieve comparable activity with other polyamides according to the invention, one should have at least 5% H-DEC, E-DEC or J-DEC (D-230). Of the former leading non-cationic antistatic agents, T-DEC and CISA, at least 7.5 and 9% respectively will normally be used (to achieve the same antistatic activity).

The comparatively small percentage of TRI-DEC required to eliminate any static charges on washed and machine-dried laundry facilitates the preparation of the detergent compositions according to the invention. As it was noticed that spray-drying the antistatic together with the detergent mixture components reduces antistatic activity, it is desirable to subsequently add antistatic to previously spray-dried detergent mixture balls, as described earlier in this example. Post-addition of larger proportions of the normally liquid antistatic agent can result in a manufactured particulate detergent with noticeably poorer trickling characteristics than one containing less antistatic agent. Accordingly, in addition to being more economical, the use of the antistatic agents of the invention in detergent compositions allows the production of an effective product having more desirable physical characteristics, e.g. paddling ability.

The various antistatic agents described above were also tested for actual deposition on washed laundry surfaces using an ESCA (Electronic Surface Composition Analysis) apparatus. By means of such testing, it was determined that the molecular surface layer on dacron fabrics that were washed with the detergent mixture according to the invention consisted of 70% by weight TRI-DEC, while H-DEC, E-DEC and J-DEC by comparison constituted 38% by weight respectively , 25 wt% and 36 wt%, and CISA and T-DEC 28 and 35 wt% respectively. As the adsorptions of the diamides and of the monoamides are approximately the same, while the antistatic activity of the diamides is higher, the antistatic activity of the present compounds also depends on the amide content as well as on adsorption on the washed substances. The triamides, such as TRI-DEC, has a higher amide content and is best adsorbed, leading to excellent antistatic effects.

In the washing tests at normal washing temperature, 49°C, and with 3.5% TRI-DEC content in the detergent mixtures using a ballast load of laundry of 19 kg, the polymeric test fabrics showed slight static charge in the opinion of the panelists, the static value being 19 kilovolts. When the wash water temperature was lowered to 38°C, 27°C, and 15.5°C, the static values dropped to 16, 17, and 12, respectively, and the observed static charge (of the panel) was in each case zero.

At the different washing temperatures mentioned immediately above, the cleaning activity of the detergent mixture is essentially the same, regardless of whether it contains the antistatic agent. Consequently, the antistatic has no detrimental effect on the washing performance, unlike quaternary ammonium halide statics which interfere with the washing activity of anionic detergents by reacting with them.

Example 6

TRI-DEC was sprayed onto the surface of porous spray-dried non-phosphate <®>Fresh Start base spheres comprising approx. 40% sodium carbonate, 40% sodium bicarbonate, 2% sodium silicate, 12% water and 6% various auxiliary substances (including fluorescent lightening agents, dyes and pigments) so that the antistatic content was 30% by weight. When appropriate, the base balls can also contain sodium tripolyphosphate to an extent of 30%, with the carbonate and bicarbonate content being reduced to 25%. The resulting product is shakeable and usable as an additive to detergent mixtures, especially anionic detergent mixtures, to contribute antistatic activity and building activity to these.

Claims (6)

1. Polyamides of trialkylacetic acid(s) and polyamine(s) which are diamides and/or triamides and which are usable as antistatic agents for filamentary and fibrous materials, characterized in that the trialkylacetic acid residues contain 1-10 carbon atoms in each of the alkyl parts and that the sum of the number of carbon atoms in the alkyl parts in each trialkylacetic acid residue is from 3 to 12, and that the polyamine residue is a diamine or triamine residue with alkylene groups and/or polyoxyalkylenealkylene groups that bind together the amide groups in the polyamide, which polyamides are selected from where A is selected from alkyl with 1-20 carbon atoms and hydrogen, T is selected from methyl and hydrogen, R is a neoalkyl with 4-13 carbon atoms, n is a number from 1 to 40 and each of x, y and z are numbers from 1 to 8 and together from 4 to 10. 2. Polyamide according to claim 1, characterized in that it has the formula where A is an alkyl residue of 1-4 carbon atoms, T is methyl, R is a neoalkyl residue of 4-9 carbon atoms and x, y and z are each numbers from 1 to 3, which together are from 4 to 8. 3. Polyamide according to claim 2, characterized in that A is ethyl, R is neoalkyl with 9 carbon atoms and x, y and z are each numbers from 1 to 3, the sum of the numbers being 5.3 on average. 4. Detergent mixture, comprising a cleaning part of a synthetic organic detergent and a part of an antistatic agent which provides antistatic properties to clothes during washing and which is applicable to filamentary and fibrous materials, characterized in that polyamide(s) of trialkylacetic acid(s) and polyamine(s) are used as antistatic agents where the trialkylacetic acid residues contain 1-10 carbon atoms in each of the alkyl parts and that the sum of the number of carbon atoms in the alkyl parts in each trialkylacetic acid residue is from 3 to 12, and that the polyamine residue is a diamine or triamine residue with alkylene groups and/or polyoxyalkylenealkylene groups which bind together the amide groups in the polyamide, which polyamides are selected from where A is selected from alkyl with 1-20 carbon atoms and hydrogen, T is selected from methyl and hydrogen, R is a neoalkyl with 4-13 carbon atoms, n is a number from 1 to 40 and each of x, y and z are numbers from 1 to 8 and together from 4 to 10. 5. Detergent mixture according to claim 4, characterized in that the polyamides are a polyamide according to claim 2 or 3. 6. Detergent mixture according to claim 4 which is available in particulate form, comprising 5-35% by weight synthetic organic detergent of sulphate and/or sulphonate type and 10-85% builder(s) for such synthetic organic detergent, characterized in that the proportion of antistatic polyamide is from 1 to 10%.